Enhanced catalytic materials with partially embedded catalytic nanoparticles

文档序号：1357775 发布日期：2020-07-24 浏览：22次中文

阅读说明：本技术 具有部分包埋的催化纳米颗粒的强化催化材料 (Enhanced catalytic materials with partially embedded catalytic nanoparticles ) 是由 E·舍尔曼 T·舍尔曼 J·艾森贝格 M·艾森贝格于 2018-10-01 设计创作，主要内容包括：本申请的各个方面提供了可以以多种功能性和/或催化物质为特征的强化催化材料及其形成方法。所述材料可以包括在载体基体内部分包埋的催化纳米颗粒(NP)。所述材料的处理如热、光、微波、等离子和/或化学处理可以导致在NP-基体、NP-孔和基体-孔界面处形成功能相关的如催化或助催化的化学和结构/形态的物质或特征。处理后的材料具有强化特性,如更高的机械稳定性。(Various aspects of the present application provide enhanced catalytic materials that may be characterized by a variety of functional and/or catalytic species and methods of forming the same. The material may include catalytic Nanoparticles (NPs) partially embedded within a carrier matrix. Treatment of the material, such as thermal, optical, microwave, plasma and/or chemical treatment, can result in the formation of functionally related chemical and structural/morphological species or features, such as catalysis or promotion, at the NP-matrix, NP-pore and matrix-pore interfaces. The treated material has enhanced properties, such as higher mechanical stability.)

1. A catalytic material, comprising:

determining an interconnect matrix material of the interconnect channel network; and

a plurality of catalytic nanoparticles having proximal and distal portions, wherein the nanoparticles are partially embedded in a matrix material such that the proximal portions of the nanoparticles are embedded in the matrix material and the distal portions of the nanoparticles are exposed to the interconnecting channels.

2. The catalytic material of claim 1, wherein the proximal portion of the nanoparticles is at least partially physically bonded to the matrix material.

3. The catalytic material of claim 2, wherein the proximal portion is at least partially rougher than the distal portion.

4. The catalytic material of claim 1, wherein the proximal portion is chemically bonded to the matrix material at least in part at an interface of the matrix material and the catalytic nanoparticle.

5. The catalytic material of claim 4, wherein the proximal portion is chemically bound at the interface at least in part by covalent interaction, ionic bonding, by forming: oxides, mixed oxides, oxometalates, aluminates, mixed aluminates, silicates, mixed silicates, aluminosilicates, titanates, mixed titanates, stannates, mixed stannates, stannous salts, mixed stannous salts, ceria oxides, mixed ceria oxides, vanadia oxides, mixed vanadia oxides, boron oxides, zirconia oxides, mixed zirconia oxides, hafnia oxides, mixed hafnia oxides, yttria oxides, mixed yttria oxides, niobium oxide, mixed niobium oxide, iron oxides, mixed iron oxides, tin oxides, mixed tin oxides, cobalt oxides, mixed cobalt oxides, indium oxides, mixed indium oxides, scandium oxides, mixed scandium oxides, rare earth oxides, uranium oxides, thorium oxides, one or more of formula I, formula II, formula III, or a combination thereof, II. Mixed oxides of group III, IV, V, VI elements, heteropolyacids, zeolites, carbides, metal alloys, intermetallic compounds, organometallic compounds, coordination compounds, organic compounds, synthetic or natural polymers, inorganic compounds or combinations thereof.

6. The catalytic material of claim 4, wherein the chemical binding to the support produces a different catalytic species than the unmodified catalytic nanoparticle.

7. The catalytic material of claim 1, wherein the distal portion is chemically modified at the interface between the interconnected channels and the catalytic nanoparticle.

8. The catalytic material of claim 1, wherein the distal portion is physically modified to produce a roughened distal portion or a faceted distal portion.

9. The catalytic material of claim 1, wherein the perimeter of the catalytic nanoparticle is chemically modified at the interface between the matrix material, the catalytic nanoparticle, and the interconnecting channel.

10. The catalytic material of claim 1, wherein the interface between the matrix material and the interconnecting channels is chemically modified.

11. The catalytic material of claim 10, wherein the chemical modification at the interface between the matrix material and the interconnecting channels comprises an interface material deposited on the surface of the matrix material.

12. The catalytic material of claim 11, wherein the interface material is a catalytic material.

13. The catalytic material of claim 10, wherein the chemical modification at the interface between the substrate material and the interconnecting channels comprises an interface material deposited on the surface of the template material prior to assembly and substrate soaking.

14. The catalytic material of claim 13, wherein the interface material is a catalytic material.

15. Catalytic material according to claims 11-14, wherein the interface material is deposited as one or more layers, one or more islands or as a plurality of particles.

16. The catalytic material of claims 11-15, wherein the interface material is further deposited at an interface between the catalytic nanoparticle and the interconnecting channel.

17. The catalytic material of claim 5, wherein the compound comprises a localized oxidation and/or reduction of the interconnected matrix material and/or catalytic nanoparticles proximate to the proximal portion between the matrix material and the catalytic nanoparticles.

18. The catalytic material of claim 1, wherein the proximal portion and the distal portion have different chemical compositions.

19. The catalytic material of claim 1, wherein the proximal and distal portions have at least one of the following differences: different crystallinity, different crystal structure, or different density.

20. The catalytic material of claim 1, wherein the proximal portion of the catalytic nanoparticle and the portion of the matrix material at the interface thereof with the catalytic nanoparticle comprise oppositely charged species.

21. The catalytic material of claim 1, wherein the catalytic nanoparticles comprise a metal.

22. The catalytic material of claim 1, wherein the catalytic nanoparticles comprise two or more metals.

23. The catalytic material of claim 22, wherein the nanoparticles are bimetallic or polymetallic.

24. The catalytic material of claim 22, wherein the nanoparticles of two or more metals comprise nanoparticles of at least some of the first metal and nanoparticles of at least some of the second metal.

25. The catalytic material of claim 22, wherein the proximal portion comprises a first atomic distribution or chemical composition of two or more metals and the distal portion comprises a second atomic distribution or chemical composition of two or more metals, and the first atomic distribution or chemical composition is different from the second atomic distribution or chemical composition.

26. The catalytic material of claim 22, wherein one of the proximal portions is partially oxidized relative to the distal portion or the distal portion is partially oxidized relative to the proximal portion.

27. The catalytic material of claim 22, wherein the distal portion further comprises an outer shell or shell of a metal or metal alloy different from the NP body.

28. The catalytic material of claim 1, wherein the matrix material further comprises a second network of channels smaller than the network of interconnected channels.

29. The catalytic material of claim 1, wherein the matrix material is chemically strengthened.

30. The catalytic material of claim 1, wherein the matrix material is roughened.

31. The catalytic material of claim 1, wherein the matrix material further comprises functional moieties on its surface.

32. The catalytic material of claim 31, wherein the functional moiety alters the surface energy of the base material or serves as a recognition unit for attracting a target moiety.

33. The catalytic material of claim 1, wherein the matrix material further comprises ions from an ion exchange process.

34. The catalytic material of claim 1, wherein the matrix material further comprises a modified oxidation state from a redox process.

35. The catalytic material of claim 1, wherein the matrix material further comprises a wettability gradient on a surface thereof.

36. The catalytic material of claim 1, wherein the proximal portion comprises a first configuration and the distal portion comprises a second configuration having a different number of facets than the first configuration.

37. The catalytic material of claim 36, wherein the second morphology has a greater number of facets than the first morphology.

38. The catalytic material of claims 1-37, wherein the interconnect matrix material comprises silica, alumina, titania, ceria, boron oxide, zirconia, hafnia, yttria, vanadia, niobia, tantalum oxide, iron oxide, cobalt oxide, tin oxide, indium oxide, scandium oxide, rare earth oxide, uranium oxide, thorium oxide, mixed oxides of one or more group I, II, III, IV, V, VI elements, mixtures of oxides of one or more group I, II, III, IV, V, VI elements, aluminates, mixed aluminates, silicates, mixed silicates, aluminosilicates, titanates, mixed titanates, stannates, mixed stannates, stannous salts, mixed stannous salts, metal oxides, heteropolyacids, zeolites, synthetic or natural polymers, metal oxides, heteropolyacids, zeolites, metal oxides, and mixtures thereof, Alloys and mixtures and combinations thereof.

39. The catalytic material of claims 1-38, wherein the catalytic nanoparticles comprise a metal, a metal oxide, a mixed metal oxide, a metal sulfide, a metal pnictide, a bimetallic salt, a composite metal salt, an organic acid metal salt, an inorganic acid metal salt, a composite metal salt, a base, an acid, a metal alloy, a multimetallic substance, an intermetallic compound, an organometallic compound, a coordination compound, one or more platinum group metals, one or more platinum group metal oxides, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, iron oxides, cobalt oxides, nickel oxides, ruthenium oxides, rhodium oxides, palladium oxides, osmium oxides, iridium oxides, platinum oxides, copper oxides, silver oxides, gold oxides, vanadium oxides, niobium oxides, tantalum oxides, chromium oxides, molybdenum oxides, niobium oxides, chromium oxides, molybdenum oxides, platinum, Tungsten oxide, scandium oxide, yttrium oxide, lanthanum oxide, rare earth metal oxide, any of the foregoing in the form of a single crystal, any of the foregoing that provides a specific crystal plane for the channel, and combinations thereof.

40. A catalytic material according to claim 1, wherein the ignition temperature of a chemical reaction catalysed by the catalytic material is at least 3-5 ° lower than the ignition temperature of the same reaction catalysed by a conventional catalytic material of the same composition.

41. The catalytic material of claim 1, wherein the catalytic nanoparticles are mechanically stable in the matrix material when subjected to a temperature of 150 ℃ for a period of more than six months.

42. The catalytic material of claim 1, wherein the nanoparticles grow no more than 1-10% of their original size when subjected to reaction conditions of 150 ℃, no more than 1-20% of their original size when subjected to 500 ℃, and no more than 1-40% of their original size when subjected to 800 ℃.

43. The catalytic material of claim 1, comprising a reduced amount of catalytic NP as compared to a conventional catalytic material, but exhibiting at least equivalent catalytic activity to the conventional catalytic material under the same conditions.

44. A coating comprising the catalytic material of any of claims 1-43.

45. An apparatus comprising the catalytic material of any of claims 1-43 on at least a portion of its surface, wherein the apparatus comprises one of: indoor air heaters, air conditioners, vents, HVAC ducting, fans, blowers, air purifiers, humidifiers, dehumidifiers, indoor electrical equipment, indoor lighting, walls, roofs, and furniture.

46. A method of making a catalytic material, the method comprising:

attaching a plurality of catalytic nanoparticles to a surface of a template component to obtain an NP-decorated template component, the plurality of catalytic nanoparticles having proximal and distal portions;

arranging the modified templating component into an interconnected templating component, wherein the interstices of the interconnected templating component are filled with a filler material;

at least partially removing said template component, whereby said filler material forms an interconnecting matrix material defining a network of interconnecting channels;

wherein the catalytic nanoparticles are partially embedded in a matrix material such that a proximal portion of the catalytic nanoparticles are embedded in the matrix material and a distal portion of the catalytic nanoparticles are exposed to the interconnecting channels.

47. The method of claim 46, wherein at least partially removing the template component further comprises treating the template material, catalytic nanoparticles, and interconnecting template component under annealing or calcination conditions by one of selective dissolution, etching, and sublimation.

48. The method of claim 46, further comprising locally oxidizing the matrix material and/or the catalytic nanoparticles near an interface between the matrix material and the catalytic nanoparticles.

49. The method of claim 46, further comprising locally reducing the matrix material and/or the catalytic nanoparticles near an interface between the matrix material and the catalytic nanoparticles.

50. The method of claim 46, wherein the matrix material further comprises a second material on a surface thereof.

51. The method of claim 46, wherein the second material is a catalytic material different from the material of the catalytic nanoparticle.

52. The method of claim 46, wherein the surface of the interconnecting channel comprises a deposit of a templating component and/or a deposit of residual material formed by partially removing the templating component.

53. The method of claim 52, wherein the deposit of template components or residual material is in the form of non-continuous, or partitioned nanoparticles.

54. The method of claim 46 or 52, wherein the interface between the interconnecting channels and the catalytic nanoparticles comprises a deposit of a templating component or a deposit of residual material formed by partial removal of the templating component.

55. The method of claims 52-54, wherein the deposit or residue is a catalytic material.

56. The method of claims 52-55, wherein the deposit or residue is formed by incomplete combustion or chemical removal of the template material.

57. The method of claims 52-56, wherein the deposit is one of activated carbon, a condensed carbon rich material, a metal, or a metal oxide.

58. The method of claims 52-54, wherein the template material is a composite template material.

59. The method of claim 52-54 or 58, wherein the deposit is a non-catalytic species.

60. The method of claim 46, further comprising subjecting the base material and catalytic nanoparticles to a heat treatment to modify the catalytic nanoparticles, wherein a proximal portion of the modified catalytic nanoparticles has a first chemical composition and a distal portion has a second chemical composition, and the first chemical composition is different than the second chemical composition.

61. The method of claim 60, wherein the first portion and the second portion have different crystallinities or densities.

62. The method of claim 46, wherein the nanoparticles comprise a material prepared from a single metal.

63. The method of claim 46, wherein the catalytic nanoparticle is a multi-metallic nanoparticle comprising two or more metals.

64. The method of claim 63, further comprising heating the base material and the multi-metallic nanoparticles to modify the multi-metallic nanoparticles, wherein the proximal portion comprises a first atomic distribution of the two or more metals and the distal portion comprises a second atomic distribution of the two or more metals, and the first atomic distribution is different from the second atomic distribution.

65. The method of claim 64, wherein the distal portion is partially oxidized relative to the proximal portion or the proximal portion is partially oxidized relative to the distal portion.

66. The method of claim 46, wherein the distal portion comprises a housing.

67. The method of claim 66, further comprising forming the shell by one of solution deposition, etching, and doping by exposure to a salt.

68. The method of claim 67, further comprising forming the shell by reducing or oxidizing conditions.

69. The method of claim 66, further comprising forming the housing by: exposing the catalytic material to a solution containing a metal shell generating precursor, and selectively growing the metal shell on a distal portion of the catalytic nanoparticle.

70. The method of claim 69, wherein the proximal portion and the distal portion have different chemical compositions.

71. The method of claim 46, further comprising subjecting the matrix material and the catalytic nanoparticles to calcination to modify the catalytic nanoparticles, wherein the proximal portion comprises a metal ion and the distal portion comprises an oxide of the metal ion.

72. The method of claim 46, further comprising subjecting the matrix material, the catalytic nanoparticle, and the interconnecting template component to thermal treatment or etching conditions to modify the catalytic nanoparticle, wherein the proximal portion comprises a first morphology and the distal portion comprises a second morphology, and the second morphology has a greater roughness than the first morphology.

73. The method of claim 46, further comprising subjecting the matrix material, the catalytic nanoparticle, and the interconnecting template component to heat treatment or etching conditions to modify the catalytic nanoparticle, wherein the proximal portion comprises a first morphology and the distal portion comprises a second morphology, and the second morphology has a greater number of facets than the first morphology.

74. The method of claim 46, further comprising subjecting the matrix material, the catalytic nanoparticle, and the interconnecting template component to thermal treatment or etching conditions to modify the catalytic nanoparticle, wherein the proximal portion comprises a first crystallinity and the distal portion comprises a second crystallinity, and the second crystallinity is different from the first crystallinity.

75. The method of claim 46, further comprising subjecting the base material, the catalytic nanoparticles, and the interconnecting template component to a heat treatment to change a crystallinity of a portion of the base material at an interface between the catalytic nanoparticles and the base material, wherein the base material has a first crystallinity and the portion of the base material at the interface between the catalytic nanoparticles and the base material has a second crystallinity, and the second crystallinity is different from the first crystallinity.

76. The method of claim 46, further comprising subjecting the matrix material, the catalytic nanoparticles, and the interconnecting template component to a thermal treatment to change a crystal structure of a portion of the matrix material at an interface between the catalytic nanoparticles and the matrix material, wherein the matrix material network has a first crystal structure and the portion of the matrix material at the interface between the catalytic nanoparticles and the matrix material has a second crystal structure, and the second crystal structure is different from the first crystal structure.

77. The method of claim 46, further comprising subjecting the matrix material network, the catalytic nanoparticles, and the interconnecting template component to a thermal treatment to change a roughness of a portion of the matrix material at an interface between the catalytic nanoparticles and the matrix material, wherein the matrix material network has a first roughness and the portion of the matrix material at the interface between the catalytic nanoparticles and the matrix material has a second roughness, and the second roughness is different than the first roughness.

78. The method of claim 46, wherein the matrix material has a first phase, a portion of the matrix material at the interface between the catalytic nanoparticle and the matrix material has a second phase, and the second phase is different from the first phase.

79. The method of claim 78, wherein the first phase or the second phase is amorphous, crystalline, or quasi-crystalline.

80. The method of claim 46, further comprising coating an exterior of the modified template material with a material prior to disposing the modified template material.

81. The method of claim 80, wherein the material is a catalytic material.

82. The method of claim 46, further comprising modifying the embedded nanoparticles.

83. The method of claim 82, wherein modifying the embedded catalytic nanoparticle comprises growing or depositing an outer shell on a surface of a distal portion of the catalytic nanoparticle.

84. The method of claim 82, wherein modifying the embedded catalytic nanoparticles comprises electroplating displacement.

85. The method of claim 82, wherein modifying the embedded catalytic nanoparticle comprises inducing a phase change by heating the catalytic nanoparticle.

86. The method of claim 46, further comprising modifying the substrate material after removing the template material.

87. The method of claim 86, wherein modifying the substrate material comprises heating the substrate material to induce a phase change in the substrate material or to roughen a surface of the substrate material.

88. The method of claim 86, wherein modifying the matrix material comprises selectively etching the matrix material to create a second network of channels.

89. The method of claim 86, wherein modifying the matrix material comprises chemically transforming the matrix material to maintain a shape of the matrix material.

90. The method of claim 86, wherein modifying the base material comprises depositing the functional moiety onto a surface of the base material.

91. The method of claim 87, wherein the functional moiety alters the surface energy of the base material or serves as a recognition element for attracting the target moiety.

92. The method of claim 86, wherein modifying the matrix material further comprises chemically converting the matrix material.

93. The method of claim 92, wherein chemically converting comprises ion exchanging the matrix material.

94. The method of claim 92, wherein chemically converting comprises performing a redox process on the matrix material.

95. The method of claim 86, wherein modifying the matrix material further comprises forming a wettability gradient on a surface of the matrix material.

96. The method of any one of claims 60-71, wherein the catalytic nanoparticle is selected from one of: gold, silver, platinum, palladium, ruthenium, rhodium, cobalt, iron, nickel, osmium, iridium, rhenium, copper, chromium, and combinations thereof.

97. The method of any one of claims 46, 52-61, and 72-77, wherein the catalytic nanoparticle is selected from one of: metals, metal alloys, semiconductors, metal oxides, mixed metal oxides, metal sulfides, and combinations thereof.

98. The method of claim 60, wherein the two or more metals of the catalytic nanoparticles are selected from the group consisting of gold, silver, platinum, palladium, ruthenium, rhodium, cobalt, iron, nickel, osmium, iridium, rhenium, copper, and chromium.

99. The method of any one of claims 46-77, wherein the matrix material is selected from one of: silica, titania, inorganic sol-gel derived oxides, polymers, and combinations thereof.

100. The method of any one of claims 46-77, wherein the template component is selected from one of: polymers, random copolymers, biopolymers, organometallic compounds, supramolecular polymers, and combinations thereof.

101. A catalytic coating comprising the catalytic material prepared by the method of claims 46-100.

102. An apparatus having the catalytic coating of claim 101 on at least a portion of its surface, wherein the apparatus comprises one of: indoor air heaters, air conditioners, vents, HVAC ducting, fans, blowers, air purifiers, humidifiers, dehumidifiers, indoor electrical equipment, indoor lighting, walls, roofs, and furniture.

103. A method of making a catalytic material, the method comprising:

providing a template material, a metal ion, and a matrix precursor, the template material having a ligand with an affinity for the metal ion;

mixing the template material, metal ions, and a matrix precursor, whereby the metal ions form a plurality of catalytic nanoparticles on the template material, the plurality of catalytic nanoparticles having proximal portions and distal portions;

arranging the template material into interconnected template components such that the matrix precursor fills interstices of the interconnected template components;

at least partially removing said template component, whereby the filler material forms an interconnecting matrix material defining a network of interconnecting channels;

104. The method of claim 103, wherein the metal ion is one of: ca. Mg, Ni, Cu, Fe, or a combination thereof.

105. The method of claim 103, wherein the ligand is polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP).

106. A method of making a catalytic material, the method comprising:

providing a template component having nanoparticle precursors therein;

arranging the template components into interconnected template components such that the matrix precursor fills interstices of the interconnected template components;

arranging the stencil component into an interconnected stencil component, wherein gaps of the interconnected stencil component are filled with a filler material;

at least partially removing the template component such that the filler material forms an interconnected matrix material defining a network of interconnected channels, thereby forming a plurality of catalytic nanoparticles having proximal portions and distal portions, wherein the catalytic nanoparticles formed are partially embedded in the matrix material such that the proximal portions of the catalytic nanoparticles are embedded in the matrix material and the distal portions of the catalytic nanoparticles are exposed to the interconnected channels.

107. A method of making a hierarchical porous material, the method comprising:

providing a porous, macro-monolithic substrate having a first porosity and a first average pore size;

applying a co-assembly mixture comprising a template sacrificial material and a matrix precursor material into the pores of the monolithic substrate; and

removing the templating sacrificial material to form a Templated Porous Coating (TPC) within the porous monolithic substrate, wherein the TPC has a second porosity and a second average pore size, and wherein the second average pore size is less than the first average pore size.

108. The method of claim 107, wherein the porous monolithic substrate is a ceramic, cordierite, mullite, zeolite, natural or synthetic clay.

109. The method of claim 107, wherein the porous monolithic substrate comprises an electrically conductive material.

110. The method of claim 107, wherein the porous monolithic substrate comprises a metal, a metal alloy, stainless steel, ferritic steel, austenitic steel, copper, nickel, brass, gold, silver, titanium, tungsten, aluminum, palladium, platinum, graphite, an electrically conductive carbon material, an electrically conductive inorganic material, an electrically conductive organic material, or a combination thereof.

111. A monolithic porous substrate having disposed thereon the catalytic material of claims 1-45.

112. The monolithic porous substrate of claim 111, wherein the monolithic porous substrate is used in a catalytic converter.

113. The monolithic porous substrate of claim 111, wherein the monolithic porous substrate is used in a fuel cell.

114. The monolithic porous substrate of claim 111, wherein the monolithic porous substrate is used in an electrolyzer.

Technical Field

The present application relates to microstructured materials having enhanced functional properties and/or durability. More particularly, the present application relates to novel catalytic materials with improved performance characteristics that can be used in a variety of applications, such as sustainable power generation, pollution treatment, production of coarse and fine chemicals, and the like.

Background

Functional materials are utilized in many different applications as catalytic materials at the barriers between the substrate and the pore network. Typically, such functional materials need to contact the material of interest (e.g., reactant, analyte, etc.) in an active state.

Disclosure of Invention

Disclosed herein are porous catalytic materials having enhanced reactivity and durability and methods of making these porous catalytic materials. The porous catalytic material may have nanoparticles or other functional materials disposed at the interface between the substrate and the network of pores or channels. Additional properties and functions of the porous catalytic materials and methods for their production are also disclosed herein.

According to some embodiments, catalytic materials and methods of making catalytic materials are described. The catalytic material includes an interconnected matrix material defining a network of interconnected channels and a plurality of catalytic nanoparticles having proximal and distal portions. In some embodiments, the nanoparticles are partially embedded in the matrix material such that a proximal portion of the nanoparticles is embedded in the matrix material and a distal portion of the nanoparticles is exposed to the interconnecting channel.

According to some embodiments, the proximal portion of the nanoparticle is at least partially physically bonded to the matrix material.

According to some embodiments, the proximal portion is at least partially rougher than the distal portion.

According to some embodiments, the proximal portion is chemically bonded to the matrix material at least in part at an interface of the matrix material and the catalytic nanoparticle.

According to some embodiments, the proximal portion is chemically bound at said interface at least in part by covalent interaction, ionic binding, by forming: oxides, mixed oxides, oxometalates, aluminates, mixed aluminates, silicates, mixed silicates, aluminosilicates, titanates, mixed titanates, stannates, mixed stannates, stannous salts, mixed stannous salts, ceria oxides, mixed ceria oxides, vanadia oxides, mixed vanadia oxides, boron oxides, zirconia oxides, mixed zirconia oxides, hafnia oxides, mixed hafnia oxides, yttria oxides, mixed yttria oxides, niobium oxide, mixed niobium oxide, iron oxides, mixed iron oxides, tin oxides, mixed tin oxides, cobalt oxides, mixed cobalt oxides, indium oxides, mixed indium oxides, scandium oxides, mixed scandium oxides, rare earth oxides, uranium oxides, thorium oxides, one or more of formula I, formula II, formula III, or a combination thereof, II. Mixed oxides of group III, IV, V, VI elements, heteropolyacids, zeolites, carbides, metal alloys, intermetallic compounds, organometallic compounds, coordination compounds, organic compounds, synthetic or natural polymers, inorganic compounds or combinations thereof. In some embodiments, the compound comprises a local oxidation and/or reduction of the interconnected matrix material and/or catalytic nanoparticles proximate the proximal portion between the matrix material and the catalytic nanoparticles.

According to some embodiments, chemical binding to the support results in a different catalytic species than unmodified catalytic nanoparticles.

According to some embodiments, the distal portion is chemically modified at the interface between the interconnecting channel and the catalytic nanoparticle.

According to some embodiments, the distal portion is physically modified to produce a roughened distal portion or a faceted distal portion.

According to some embodiments, the perimeter of the catalytic nanoparticle is chemically modified at the interface between the matrix material, the catalytic nanoparticle, and the interconnecting channel.

According to some embodiments, the interface between the matrix material and the interconnect channel is chemically modified. In some embodiments, the chemical modification at the interface between the base material and the interconnect channel comprises an interface material deposited on the surface of the base material. In some embodiments, the interface material is a catalytic material. In some embodiments, the chemical modification at the interface between the substrate material and the interconnect channels comprises an interface material deposited on the surface of the template material prior to assembly and substrate saturation. In some embodiments, the interface material is a catalytic material. In some embodiments, the interface material is deposited as one or more layers of film, one or more islands, or as a plurality of particles. In some embodiments, the interface material is further deposited at an interface between the catalytic nanoparticle and the interconnecting channel.

According to some embodiments, the proximal portion and the distal portion have different chemical compositions.

According to some embodiments, the proximal and distal portions have at least one of the following differences: different crystallinity, different crystal structure, or different density.

According to some embodiments, the proximal portion of the catalytic nanoparticle and the portion of the matrix material at its interface with the catalytic nanoparticle comprise oppositely charged species.

According to some embodiments, the catalytic nanoparticle comprises a metal.

According to some embodiments, the catalytic nanoparticle comprises two or more metals. In some embodiments, the nanoparticles are bimetallic or polymetallic. In some embodiments, the nanoparticles of the two or more metals comprise at least some nanoparticles of a first metal and at least some nanoparticles of a second metal. In some embodiments, the proximal portion comprises a first atomic distribution or chemical composition of two or more metals and the distal portion comprises a second atomic distribution or chemical composition of two or more metals, and the first atomic distribution or chemical composition is different from the second atomic distribution or chemical composition. In some embodiments, one of the proximal portions is partially oxidized relative to the distal portion or the distal portion is partially oxidized relative to the proximal portion. In some embodiments, the distal portion further comprises an outer shell or shell of a metal or metal alloy different from the NP body.

According to some embodiments, the matrix material further comprises a second network of channels smaller than the network of interconnecting channels.

According to some embodiments, the matrix material is chemically strengthened.

According to some embodiments, the matrix material is roughened.

According to some embodiments, the matrix material further comprises functional moieties on its surface. In some embodiments, the functional moiety alters the surface energy of the base material or serves as a recognition unit for attracting the target moiety.

According to some embodiments, the matrix material further comprises ions from an ion exchange process.

According to some embodiments, the matrix material further comprises a modified oxidation state from a redox process.

According to some embodiments, the matrix material further comprises a wettability gradient on its surface.

According to some embodiments, the proximal portion comprises a first configuration and the distal portion comprises a second configuration having a different number of facets than the first configuration. In some embodiments, the second form has a greater number of facets than the first form.

According to some embodiments, the interconnect base material comprises silicon dioxide, aluminum oxide, titanium dioxide, cerium dioxide, boron oxide, zirconium oxide, hafnium oxide, yttrium oxide, vanadium oxide, niobium oxide, tantalum oxide, iron oxide, cobalt oxide, tin oxide, indium oxide, scandium oxide, rare earth oxide, uranium oxide, thorium oxide, one or more of items I, II, III, IV, V, mixed oxides of group VI elements, mixtures of oxides of one or more group I, II, III, IV, V, VI elements, aluminates, mixed aluminates, silicates, mixed silicates, aluminosilicates, titanates, mixed titanates, stannates, mixed stannates, stannous salts, mixed stannous salts, oxometalates, heteropolyacids, zeolites, synthetic or natural polymers, metals, alloys and mixtures and combinations thereof.

According to some embodiments, the catalytic nanoparticles comprise a metal, a metal oxide, a mixed metal oxide, a metal sulfide, a metal pnictide, a bimetallic salt, a complex metal salt, an organic acid metal salt, an inorganic acid metal salt, a complex metal salt, a base, an acid, a metal alloy, a multimetallic substance, an intermetallic compound, an organometallic compound, a coordination compound, one or more platinum group metals, one or more platinum group metal oxides, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, an iron oxide, a cobalt oxide, a nickel oxide, a ruthenium oxide, a rhodium oxide, a palladium oxide, an osmium oxide, an iridium oxide, a platinum oxide, a copper oxide, a silver oxide, a gold oxide, a vanadium oxide, a niobium oxide, a tantalum oxide, a chromium oxide, a molybdenum oxide, a tungsten oxide, a scandium oxide, a vanadium oxide, a niobium oxide, a chromium oxide, Yttrium oxide, lanthanum oxide, rare earth metal oxide, any of the foregoing in single crystal polymorphous form, any of the foregoing providing specific crystal planes to the channel, and combinations thereof.

According to some embodiments, the catalytic material catalyzes a chemical reaction with an ignition temperature that is at least lower than the ignition temperature of the same reaction catalyzed with a conventional catalytic material of the same composition

According to some embodiments, the catalytic nanoparticles are mechanically stable in the matrix material when subjected to a temperature of 150 ℃ for a period of more than six months.

According to some embodiments, the nanoparticles grow no more than 1-10% of their original size when subjected to reaction conditions of 150 ℃, no more than 1-20% of their original size when subjected to 500 ℃, and no more than 1-40% of their original size when subjected to 800 ℃.

According to some embodiments, the catalytic material comprises a reduced amount of catalytic NP compared to conventional catalytic materials, but exhibits at least equivalent catalytic activity to conventional catalytic materials under the same conditions.

According to some embodiments, the catalytic material is used as a coating.

According to some embodiments, the catalytic material is applied to at least a portion of a surface of the device. In some embodiments, the apparatus is one of: indoor air heaters, air conditioners, vents, HVAC ducting, fans, blowers, air purifiers, humidifiers, dehumidifiers, indoor electrical equipment, indoor lighting, walls, roofs, and furniture.

According to some embodiments, a method of making a catalytic material is described. In some embodiments, the method comprises attaching a plurality of catalytic nanoparticles to a surface of a template component to obtain an NP-decorated template component, the plurality of catalytic nanoparticles having proximal and distal portions. In some embodiments, the method comprises arranging the modified templating composition into an interconnected templating composition, wherein the interstices of the interconnected templating composition are filled with a filler material. In some embodiments, the method includes at least partially removing the templating component such that the filler material forms an interconnecting matrix material defining a network of interconnecting channels. In some embodiments, the catalytic nanoparticles are partially embedded in a matrix material such that a proximal portion of the catalytic nanoparticles are embedded in the matrix material and a distal portion of the catalytic nanoparticles are exposed to the interconnecting channels.

According to some embodiments, the method includes at least partially removing the template component, and further includes treating the template material, catalytic nanoparticles, and interconnecting template component under annealing or calcining conditions by one of selective dissolution, etching, and sublimation.

According to some embodiments, the method comprises locally oxidizing the matrix material and/or the catalytic nanoparticles in the vicinity of an interface between the matrix material and the catalytic nanoparticles.

According to some embodiments, the method comprises locally reducing the matrix material and/or the catalytic nanoparticles in the vicinity of the interface between the matrix material and the catalytic nanoparticles.

According to some embodiments, the matrix material further comprises a second material on a surface thereof.

According to some embodiments, the second material is a catalytic material different from the material of the catalytic nanoparticle.

According to some embodiments, the surface of the interconnecting channel comprises a deposit of a templating component and/or a deposit of residual material formed by partially removing the templating component.

According to some embodiments, the deposit of template components or residual material is in the form of non-continuous, or partitioned nanoparticles.

According to some embodiments, the interface between the interconnecting channels and the catalytic nanoparticles comprises a deposit of a templating component or a deposit of residual material formed by partial removal of the templating component.

According to some embodiments, the deposit or residue is a catalytic material.

According to some embodiments, the deposits or residues are formed by incomplete combustion or chemical removal of the template material.

According to some embodiments, the deposit is one of activated carbon, a condensed carbon-rich material, a metal, or a metal oxide.

According to some embodiments, the template material is a composite template material.

According to some embodiments, the deposit is a non-catalytic material.

According to some embodiments, the method comprises subjecting the matrix material and catalytic nanoparticles to a heat treatment to modify the catalytic nanoparticles. In some embodiments, the proximal portion of the modified catalytic nanoparticle has a first chemical composition and the distal portion has a second chemical composition. In some embodiments, the first chemical composition is different from the second chemical composition. In some embodiments, the first portion and the second portion have different crystallinities or densities.

According to some embodiments, the nanoparticle comprises a material made from a single metal.

According to some embodiments, the catalytic nanoparticle is a multi-metallic nanoparticle comprising two or more metals. In some embodiments, the method includes heating a base material and a multi-metallic nanoparticle to modify the multi-metallic nanoparticle, wherein the proximal portion comprises a first distribution of atoms of two or more metals, and the distal portion comprises a second distribution of atoms of two or more metals, and the first distribution of atoms is different from the second distribution of atoms. In some embodiments, the distal portion is partially oxidized relative to the proximal portion or the proximal portion is partially oxidized relative to the distal portion.

According to some embodiments, the distal portion comprises a housing. In some embodiments, the method includes forming the housing by one of deposition from solution, etching, and doping by exposure to a salt. In some embodiments, the method comprises forming the shell by reducing or oxidizing conditions. In some embodiments, the method comprises forming the housing by: exposing the catalytic material to a solution containing a metal shell generating precursor, and selectively growing the metal shell on a distal portion of the catalytic nanoparticle. In some embodiments, the proximal portion and the distal portion have different chemical compositions.

According to some embodiments, the method comprises subjecting the matrix material and the catalytic nanoparticles to calcination to modify the catalytic nanoparticles. In some embodiments, the proximal portion comprises a metal ion and the distal portion comprises an oxide of the metal ion.

According to some embodiments, the method includes subjecting the matrix material, catalytic nanoparticles, and interconnect template component to thermal treatment or etching conditions to modify the catalytic nanoparticles. In some embodiments, the proximal portion comprises a first configuration and the distal portion comprises a second configuration, and the second configuration has a greater roughness than the first configuration.

According to some embodiments, the method includes subjecting the matrix material, catalytic nanoparticles, and interconnect template component to thermal treatment or etching conditions to modify the catalytic nanoparticles. In some embodiments, the proximal portion comprises a first crystallinity and the distal portion comprises a second crystallinity, and the second crystallinity is different from the first crystallinity.

According to some embodiments, the method includes subjecting the matrix material, catalytic nanoparticles, and interconnect template component to a heat treatment to alter the crystallinity of the portion of the matrix material at the interface between the catalytic nanoparticles and the matrix material. In some embodiments, the matrix material has a first crystallinity and a portion of the matrix material at the interface between the catalytic nanoparticle and the matrix material has a second crystallinity, and the second crystallinity is different from the first crystallinity.

According to some embodiments, the method includes subjecting the matrix material, catalytic nanoparticles, and interconnect template component to a thermal treatment to alter the crystal structure of portions of the matrix material at the interface between the catalytic nanoparticles and the matrix material. In some embodiments, the matrix material network has a first crystal structure and a portion of the matrix material at the interface between the catalytic nanoparticle and the matrix material has a second crystal structure, and the second crystal structure is different from the first crystal structure.

According to some embodiments, the method includes subjecting the matrix material network, the catalytic nanoparticles, and the interconnecting template component to a heat treatment to alter the roughness of portions of the matrix material at the interface between the catalytic nanoparticles and the matrix material. In some embodiments, the matrix material network has a first roughness and the portion of the matrix material at the interface between the catalytic nanoparticle and the matrix material has a second roughness, and the second roughness is different from the first roughness.

According to some embodiments, the matrix material has a first phase, the portion of the matrix material at the interface between the catalytic nanoparticle and the matrix material has a second phase, and the second phase is different from the first phase. In some embodiments, the first phase or the second phase is amorphous, crystalline, or quasi-crystalline.

According to some embodiments, the method comprises coating the exterior of the modified template material with a material prior to arranging the modified template material. In some embodiments, the material is a catalytic material.

According to some embodiments, the method comprises modifying the embedded nanoparticles. In some embodiments, modifying the embedded catalytic nanoparticle comprises growing or depositing an outer shell on a surface of a distal portion of the catalytic nanoparticle. In some embodiments, modifying the embedded catalytic nanoparticle comprises electroplating displacement. In some embodiments, modifying the embedded catalytic nanoparticle comprises inducing a phase change by heating the catalytic nanoparticle.

According to some embodiments, the method comprises modifying the substrate material after removing the template material. In some embodiments, modifying the base material comprises heating the base material to induce a phase change in the base material or to roughen a surface of the base material. In some embodiments, modifying the matrix material comprises selectively etching the matrix material to create a second network of channels. In some embodiments, modifying the matrix material comprises chemically transforming the matrix material to maintain the shape of the matrix material. In some embodiments, modifying the base material comprises depositing a functional moiety onto the surface of the base material, and in some embodiments, the functional moiety alters the surface energy of the base material or serves as a recognition unit for attracting a target moiety. In some embodiments, modifying the matrix material further comprises chemically converting the matrix material. In some embodiments, the chemical conversion comprises ion-exchanging the matrix material. In some embodiments, the chemical conversion comprises performing a redox process on the matrix material. In some embodiments, modifying the matrix material further comprises forming a wettability gradient on the surface of the matrix material.

According to some embodiments, the catalytic nanoparticle is selected from one of: gold, silver, platinum, palladium, ruthenium, rhodium, cobalt, iron, nickel, osmium, iridium, rhenium, copper, chromium, and combinations thereof.

According to some embodiments, the catalytic nanoparticle is selected from one of: metals, metal alloys, semiconductors, metal oxides, mixed metal oxides, metal sulfides, and combinations thereof.

According to some embodiments, the two or more metals of the catalytic nanoparticles are selected from gold, silver, platinum, palladium, ruthenium, rhodium, cobalt, iron, nickel, osmium, iridium, rhenium, copper, and chromium.

According to some embodiments, the matrix material is selected from one of the following: silica, titania, inorganic sol-gel derived oxides, polymers, and combinations thereof.

According to some embodiments, the set of templates is selected from one of: polymers, random copolymers, biopolymers, organometallic compounds, supramolecular polymers, and combinations thereof.

According to some embodiments, the catalytic material is used as a catalytic coating. In some embodiments, the catalytic coating is applied to a surface of a device. In some embodiments, the apparatus is one of: indoor air heaters, air conditioners, vents, HVAC ducting, fans, blowers, air purifiers, humidifiers, dehumidifiers, indoor electrical equipment, indoor lighting, walls, roofs, and furniture.

According to some embodiments, a method of making a catalytic material is described herein. In some embodiments, the method includes providing a template material having ligands with an affinity for metal ions, and a substrate precursor. In some embodiments, the method includes mixing the template material, metal ions, and a matrix precursor, whereby the metal ions form a plurality of catalytic nanoparticles on the template material, the plurality of catalytic nanoparticles having proximal portions and distal portions. In some embodiments, the method includes arranging the template material into interconnected template components such that the matrix precursor fills interstices of the interconnected template components. In some embodiments, the method includes at least partially removing the templating component, whereby the filler material forms an interconnecting matrix material defining a network of interconnecting channels. In some embodiments, the catalytic nanoparticles are partially embedded in a matrix material such that a proximal portion of the catalytic nanoparticles are embedded in the matrix material and a distal portion of the catalytic nanoparticles are exposed to the interconnecting channels. According to some embodiments, the metal ion is one of: ca. Mg, Ni, Cu, Fe, or a combination thereof. According to some embodiments, the ligand is polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP).

According to some embodiments, a method of making a catalytic material is described herein. In some embodiments, the method includes providing a template component having nanoparticle precursors therein. In some embodiments, the method includes arranging the templating composition into interconnected templating compositions such that the matrix precursor fills the interstices of the interconnected templating compositions. In some embodiments, the method includes arranging the templating composition into an interconnected templating composition such that the filler material fills the interstices of the interconnected templating composition. In some embodiments, the method includes at least partially removing the template component such that the filler material forms an interconnected matrix material defining a network of interconnected channels, thereby forming a plurality of catalytic nanoparticles having proximal and distal portions. In some embodiments, the formed catalytic nanoparticles are partially embedded in the matrix material such that a proximal portion of the catalytic nanoparticles is embedded in the matrix material and a distal portion of the catalytic nanoparticles is exposed to the interconnecting channels.

According to some embodiments, a method of making a hierarchical porous material is described. In some embodiments, the method comprises providing a porous macro-monolithic substrate having a first porosity and a first average pore size. In some embodiments, the method comprises applying a co-assembly mixture comprising a template sacrificial material and a matrix precursor material into the pores of the monolithic substrate. In some embodiments, the method comprises removing the templating sacrificial material to form a Templated Porous Coating (TPC) within a porous monolithic substrate, wherein the TPC has a second porosity and a second average pore size, and wherein the second average pore size is less than the first average pore size.

According to some embodiments, the porous monolithic substrate is ceramic, cordierite, mullite, zeolite, natural or synthetic clay.

According to some embodiments, the porous monolithic substrate comprises an electrically conductive material.

According to some embodiments, the porous monolithic substrate is a metal, metal alloy, stainless steel, ferritic steel, austenitic steel, copper, nickel, brass, gold, silver, titanium, tungsten, aluminum, palladium, platinum, graphite, electrically conductive carbon material, electrically conductive inorganic material, electrically conductive organic material, or combinations thereof.

In accordance with some embodiments, a monolithic porous substrate having the catalytic material of some embodiments is disclosed herein. In some embodiments, the monolithic porous substrate of claim 110 is described, wherein the monolithic porous substrate is used in a catalytic converter. In some embodiments, the monolithic porous substrate is used in a fuel cell. In some embodiments, the monolithic porous matrix is used in an electrolyzer.

Drawings

The above and other objects and advantages of the present invention will become apparent upon consideration of the following detailed description, taken in conjunction with the accompanying drawings, in which like reference characters refer to like parts throughout, and in which:

fig. 1A-B are schematic depictions of nanoparticles according to some embodiments.

FIG. 1A schematically depicts an example of a catalytic material that may be characterized by its design properties according to some embodiments.

Fig. 1B schematically depicts an example of partial embedding in a matrix material resulting in strong particle-bound Nanoparticles (NPs) according to some embodiments, wherein the strong particle-binding results in a substantial increase in the mechanical, thermal, and chemical stability of the enhanced catalyst.

FIG. 2 schematically depicts an example of a method of producing a composite catalytic material according to some embodiments. View a schematically depicts an example of a method for producing a composite catalytic material using a templating method featuring a plurality of partially embedded catalytic NPs of the same type, according to some embodiments. View B schematically depicts an example of a method for producing a composite catalytic material using a templating method featuring a plurality of partially embedded catalytic NPs of different types, according to some embodiments.

FIG. 3 schematically depicts an example of process-induced changes at the proximal interface between the NP and the matrix material that enhance the thermal and mechanical robustness of the catalytic structure, according to some embodiments. View A schematically depicts the process-induced formation of a chemical linkage between the NP and the matrix material at the proximal interface, resulting in the formation of a new compound, according to some embodiments. View B schematically depicts the phase inversion of the matrix material induced by the treatment at the proximal interface, including crystallinity, poly-crystalline state, domain size, according to some embodiments. View C schematically depicts the formation of catalytically relevant ionic species at the proximal interface induced by the treatment, in accordance with some embodiments. View D schematically depicts proximal interface roughening induced by treatment according to some embodiments.

Figure 4 schematically depicts an example of process-induced changes at a distal interface between an NP and a network of interconnected channels, according to some embodiments. View a schematically depicts distal surface roughening induced by treatment according to some embodiments. View B schematically depicts planarization of the distal surface induced by the treatment, in accordance with some embodiments. View C schematically depicts the generation of porosity in the NP induced by the treatment according to some embodiments.

Figure 5 schematically depicts an example of NP content rearrangement and/or redistribution induced by treatment to alter catalytic activity according to some embodiments. View a schematically depicts atomic redistribution of NP content induced by treatment according to some embodiments. View B schematically depicts the remodeling of the distal surface induced by the treatment, e.g., forming a shell or outer shell, according to some embodiments. View C schematically depicts an example of rearrangement with NP atoms, according to some embodiments.

Fig. 6A schematically depicts an example of treatment-induced deposition of additional catalytically relevant species at the substrate-channel and NP-channel (distal) interfaces, according to some embodiments.

Fig. 6B schematically depicts an example of treatment-induced deposition of additional catalytically relevant species at the substrate-channel and NP-substrate (proximal) interfaces, according to some embodiments.

Fig. 7 is a schematic depiction and representative image of an exemplary templating process for producing an enhanced catalytic material without (view a, upper row) and with (view B, lower row) partially embedded functional NPs at a matrix-channel interface according to some embodiments.

The schematic depiction and representative Transmission Electron Microscope (TEM) image of fig. 8 shows NPs with different embedding depths within the matrix according to some embodiments.

The schematic depiction and representative image of fig. 9 is an exemplary template method of producing catalytic material with different functional NPs located at the matrix-channel interface according to some embodiments. View A schematically depicts a universal template method for producing porous materials with different functional NPs located at the matrix-channel interface, according to some embodiments. View B is a schematic graphical representation of two examples of such methods according to some embodiments, where NP-decorated colloidal particles are used as template materials, giving two sets of graphs, each set containing schematic and representative Scanning Electron Microscope (SEM) and scanning transmission electron microscope-energy-dispersive X-ray spectroscopy (STEM-EDS) elemental composition distribution enlargements of the formed catalytic material with multiple types of pores at the matrix-pore interface, e.g., with different functional NPs in different pores (left graph) or multiple types of NPs loaded in each pore (right graph).

Fig. 10 is a schematic comparing the thermal stability of Au NPs grown by conventional methods in a preformed silica porous structure (the so-called inverse opal-IO structure) (top row) and those incorporated into silica IO using the templating method shown in fig. 2 (bottom row) according to some embodiments, showing significant aggregation and growth of the NPs in the typical method, without variation in particle size in the catalytic material of the embodiments disclosed herein.

Figure 11 gives TEM images of NPs prepared as such free standing according to some embodiments (views a-C) and the same NPs incorporated into the porous structure and subjected to shape change (e.g., planarization) at the distal end portion (views D-F).

FIG. 12 is a graph showing 1% Pd/SiO according to some embodiments using the colloidal templating method shown in FIG. 7 (View B, bottom row)₂Long term stability of the catalyst in the conversion of isopropanol to carbon dioxide at high temperatures with continuous flow of reactants. The experiments leading to the results were carried out under the following reaction conditions: flow rate at 450 deg.C of 150ml/min, 3 mol% isopropyl alcohol and 22 mol% O in He₂。

FIG. 13 is a graph showing the templated SiO using colloids₂AgAu from methanol to methyl formate (MF, box) and carbon dioxide (CO)₂Circle) steady state rotationRate of formation and long-term stability of selectivity to methyl formate (triangles). The experiments leading to the results were carried out under the following reaction conditions: flow rate 150ml/min at 150 deg.C, 6 mol% methanol and 20 mol% O in He₂。

FIG. 14 is a graph comparing the use of commercially available 1 w% Pt/Al₂O₃Complete combustion of methanol to CO with catalysts and enhanced catalysts prepared according to some embodiments with the same NP loading of-1 w% Pt₂Showing a decrease in reaction temperatureThe experiments leading to the results were carried out under the following reaction conditions: the flow rate was 50ml/min and 7.5 mol% methanol and 22 mol% O in He₂。

FIG. 15 is a graph comparing the use of commercially available 1 w% Pd/Al₂O₃Complete combustion of methanol to CO with enhanced catalyst prepared according to some embodiments with the same NP loading of-1 w% Pd₂Showing the ability to reduce the reaction temperature by-90 ℃ and carry out the reaction at room temperature. The experiments leading to the results were carried out under the following reaction conditions: the flow rate was 50ml/min and 7.5 mol% methanol and 22 mol% O in He₂。

FIG. 17 is a graph comparing the use of commercially available 1 w% Pt/Al₂O₃Catalysts and catalyst prepared according to some embodiments with reduced Pt-0.5 w% Pt/Al₂O₃When the catalyst is strengthened, the methanol is completely combusted into CO₂It was shown that the reaction temperature decreased by-50 ℃ even at half the NP loading. The experiments leading to the results were carried out under the following reaction conditions: flow rate of 50ml/min at He contains 7.5 mol% of methanol and 22 mol% of O₂。

FIG. 18 is a graph comparing the use of commercially available 1 w% Pt/Al₂O₃Catalysts and catalyst prepared according to some embodiments with reduced Pt-0.05 w% Pt/Al₂O₃When the catalyst is strengthened, the methanol is completely combusted into CO₂It was shown that the reaction temperature decreased by-25 ℃ when the NP loading was reduced by 95%. The experiments leading to the results were carried out under the following reaction conditions: the flow rate was 50ml/min and 7.5 mol% methanol and 22 mol% O in He₂。

FIG. 19 is a graph comparing the use of commercially available 1 w% Pd/Al₂O₃Catalysts and catalyst prepared according to some embodiments with reduced Pd-0.1 w% Pd/Al₂O₃When the catalyst is strengthened, the methanol is completely combusted into CO₂It was shown that the reaction temperature decreased by-60 ℃ when the NP loading was reduced by 90%. The experiments leading to the results were carried out under the following reaction conditions: the flow rate was 50ml/min and 7.5 mol% methanol and 22 mol% O in He₂。

FIG. 20 is a graph comparing the use of commercially available 1 w% Pt/Al₂O₃Catalysts and catalyst prepared according to some embodiments with reduced Pt-0.1 w% Pt/Al₂O₃When the catalyst is strengthened, the toluene is completely combusted into CO₂It was shown that the reaction temperature decreased to-30 ℃ when the NP loading was reduced by 90%. The experiments leading to the results were carried out under the following reaction conditions: the flow rate was 50ml/min and 0.35 mol% toluene and 22 mol% O in He₂。

Fig. 21 is a schematic and graph comparing catalytic performance of colloidal-templated porous silica containing bimetallic AuAg nanoparticles according to some embodiments when the templated colloid is removed by thermal treatment (view D) or chemical dissolution (view E), respectively. View A depicts the conversion of methanol to methyl formate (MF, box) and carbon dioxide (CO) using thermal template colloid removal according to some embodiments₂Circles) conversion and selectivity to methyl formate (diamonds); view B corresponds to a sample prepared using template colloid chemical dissolution according to some embodiments; view C corresponds to according to some embodimentsSamples prepared by chemical dissolution of the template colloid and subsequent heat treatment of the material were used. The experiments that produced the results described in views A-C were performed under the following reaction conditions: a flow rate of 50ml/min at 423K, 6 mol% methanol and 20 mol% O in He₂. All samples contained 10 w% metal NP.

Fig. 22 is a graph comparing the conversion of methanol to methyl formate using a catalyst comprising porous silica decorated with bimetallic AuPd nanoparticles prepared according to some embodiments. The solid boxes correspond to samples prepared by applying a heat treatment in the presence of template colloids (fig. 21, view D), while the open boxes correspond to samples prepared by applying a chemical dissolution of the template colloids followed by a heat treatment of the catalytic material. The experiments leading to the results were carried out under the following reaction conditions: flow rate at 150 ℃ of 50ml/min, 6 mol% methanol and 20 mol% O in He₂。

The schematic and graph of fig. 23 depict catalytic materials and results according to some embodiments. View A schematically depicts the formation of a catalytic material using a co-assembly process that results in substantial amounts of NPs being fully embedded in the matrix and unavailable for catalytic reactions, according to some embodiments. Panel B shows methanol to methyl formate (MF, cross squares) and carbon dioxide (CO) using a catalyst comprising porous silica containing bimetallic AuAg nanoparticles prepared using the embodiment shown in Panel A₂Cross circles) and selectivity to methyl formate (cross diamonds). The experiments leading to the results were carried out under the following reaction conditions: flow rate at 150 ℃ of 50ml/min, 6 mol% methanol and 20 mol% O in He₂。

Fig. 24 is a schematic depiction, image, and graph of catalytic materials and results according to some embodiments. The schematic depiction, image and graph of view a present the formation of catalytic material using a non-templated approach, wherein the NPs are not uniformly distributed and the material has reduced catalytic activity, according to some embodiments. The schematic depiction, image and graph of panel B show the formation of catalytic material using the template method of figure 2, where NPs are uniformly distributed and the material shows significantly enhanced catalytic activity compared to the results shown in panel a, according to some embodiments.

Fig. 25 presents a combination of various exemplary protocols and corresponding experimental data, in accordance with some embodiments, depicting different post-modification options for catalytic materials produced using the template method shown in fig. 2.

Fig. 26 presents a schematic and corresponding SEM of different macroscopic forms of catalytic material, according to some embodiments.

Fig. 27 is an SEM, TEM, and elemental composition mapping image and schematic of an interconnected porous catalytic microstructure using different types of decorative colloids as templates according to some embodiments.

Fig. 28 is a schematic, image, and graphical result of incorporation of transition metal salts into catalytic materials by in situ binding of ions to capping ligands of template colloids and their assembly, according to some embodiments.

Fig. 29 is a schematic diagram and corresponding SEM and FFT analysis of controlled disorder of pore distribution, for example, by varying the size of NPs decorating template colloids, according to some embodiments.

FIG. 30 is a graph of template colloids terminated with polyethylene glycol (PEG) and different concentrations of CO (NO) in an assembly mixture, according to some embodiments₃)₂Schematic representation of ion-induced controlled disorder in silica IO and corresponding SEM and FFT analysis.

Fig. 31 is a graphical illustration of an example of materials in the form of thin films and photonic spheres (PB) prepared from different metal oxides (MOx) using the template method shown in fig. 2, according to some embodiments.

Fig. 32 is an SEM, STEM, and photomicrograph of a hybrid silica-titania inverse opal, according to some embodiments.

Fig. 33 is an SEM image, EDS scan, and schematic depiction of catalytic materials formed from different metal oxides according to some embodiments.

Fig. 34 is a schematic of photocatalytic PB prepared from titanium dioxide and templated with platinum NP-decorated colloid according to some embodiments (a), surface area normalized rate constant map of methylene blue decomposition (B), and SEM image (large field view-C; high magnification view-D). The inset of view D is a TEM image showing partial embedding of Pt NPs in the titania wall, according to some embodiments.

Fig. 35 schematically depicts a catalytic system design 3500 incorporating exemplary degrees of freedom according to some embodiments.

Fig. 36 schematically depicts a non-limiting, exemplary list of various types of devices having forced air circulation and/or heater elements that can be used for indoor air purification by incorporating a catalytically active coating in their design, according to some embodiments.

FIG. 37 is a schematic illustration of the air purification behavior of a catalytic coating produced according to some embodiments and applied in an HVAC system (top panel), and a non-limiting example of an HVAC system surface to which such a catalytic coating may be applied (bottom panel).

Fig. 38 views a-C are a series of schematic views of a hierarchical porous material obtained by coating a pre-existing porous macroscopic substrate with a catalytic porous template material, according to some embodiments.

FIG. 39 schematically depicts a method of producing a hierarchical porous catalytic material by applying the catalytic porous material described in some embodiments as a coating onto a macroscopic porous substrate (such as cordierite, polyurethane or other polymeric foams, carbon-based porous substrates, and metal substrates).

Fig. 40 is an image of an exemplary catalytic level porous material obtained by coating a cordierite substrate with catalytic porous template material described herein, according to some embodiments. View A is a macroscopic sample of cordierite according to some embodiments, and view B includes Pt/SiO according to some embodiments₂、Pd/SiO₂And Pt/Al₂O₃Series SEM images of the coated sample of (a).

Fig. 41 is an image that shows an exemplary catalytic level cellular material obtained by coating a polyurethane substrate with a catalytic porous template material described herein, according to some embodiments. View A is a graph of Au/SiO according to some embodiments₂A macroscopic sample of the coated polyurethane foam, and view B is a series of SEM images of the same sample.

Fig. 42 is an image that illustrates an exemplary catalytic porous material obtained by coating an electrically conductive substrate with a catalytic porous template material described herein, according to some embodiments. Examples include coatings on metal (FeCrAl) substrates, indium tin oxide coated on polyethylene terephthalate (PET) substrates, and carbon paper.

FIG. 43 is a coating of Pt/Al disclosed herein applied to a cordierite substrate according to some embodiments₂O₃Complete oxidation of methanol and isopropanol obtained from the catalytic material to CO₂And examples of experimental results for water.

FIG. 44 illustrates the application of the Pt/Al disclosed herein coated on cordierite substrates according to some embodiments₂O₃Complete oxidation of methanol and isopropanol obtained from the catalytic material to CO₂And examples of experimental results for water.

FIG. 45 is a graphical representation of a Pt/Al coating as disclosed herein applied to a cordierite substrate in accordance with certain embodiments₂O₃Complete oxidation of methanol and isopropanol obtained from the catalytic material to CO₂And examples of experimental results for water.

Detailed Description

The design of advanced catalytic systems is of great importance for e.g. the development of sustainable ways to produce energy, the treatment of pollutants and the production of raw materials and fine chemicals for several sectors including agriculture, construction, medicine, chemical and pharmaceutical industries and transportation. For example, catalysts are used to produce synthetic fuels such as gasoline, aviation and diesel fuels, kerosene, methane, biofuels derived from renewable resources (e.g., biomass) and non-renewable resources (natural gas, coal, and shale oil). Examples of catalytic processes include coal and natural gas liquefaction, hydrogenation, dehydrogenation, synthesis gas synthesis, fischer-tropsch processes, methanol synthesis, ammonia synthesis, sulfur dioxide oxidation, ammonia oxidation, terephthalic acid synthesis, and petroleum extraction processes (e.g., hydropyrolysis and cracking). Catalysts are key elements in the synthesis of hydrogen using processes such as catalytic partial oxidation, steam reforming, renewable fuel reforming, electrolysis processes, and photoelectrochemical hydrolysis. The catalyst is widely applied to the processes of fluid catalytic cracking, hydrocracking, hydrotreating, alkylation, isomerization, catalytic reforming and the like in polymer synthesis, oil refining and recycling industries. The catalysts are used in energy conversion (fuel cells), green processes (production of chemicals, textiles and leather, pulp and paper and food processing) and air and water pollution abatement applications (e.g. treatment of emissions from power plants and automobiles, etc.). In some embodiments, the catalytic materials disclosed herein may be used in any of these applications.

Optimizing catalytic reactions for such a wide range of applications and situations remains one of the most challenging technical and scientific goals of the present generation. This is due to a number of reasons, including the various catalytic and support materials involved, their different properties, availability, lifetime, cost contribution, recyclability and disposal costs. Typical catalyst technology has a number of disadvantages. For example, they typically require relatively high loadings of precious catalysts such as platinum group metals, so-called Platinum Group Metals (PGM) (Pt, Pd, Rh, Ir, Ru and Os) and high operating temperatures (typically 100-. The selectivity, efficiency, stability and lifetime of these catalysts are not optimal and need to be improved. Many catalytic technologies are being developed when feedstock limitations, energy costs and environmental issues are different than those currently being developed.

Incorporating metal Nanoparticles (NPs) into porous structures can introduce some desirable properties, such as optical, inductive, and catalytic properties. The catalyst immobilization process involves combining preformed nanoparticles, depositing a metal precursor onto a substrate followed by a reduction step to form the nanoparticles, and a one-pot process to simultaneously synthesize catalytic NPs and their supporting substrates. Control of one parameter often comes at the expense of control of other parameters. As discussed below, fusing catalyst particles into a pre-assembled porous matrix (e.g., by adsorption or deposition of metal NPs) creates extremely accessible catalytic sites; however, NP binding is loose and often unstable, leading to their sintering and melting, especially in high temperature catalytic reactions. Other methods produce porous matrix metal on the substrate only or primarily at the air/solid interface of the interconnect structure.

In some embodiments, catalysts are disclosed that can provide the following benefits:

1. greater selectivity and higher yield, enabling the producer to reduce waste and energy consumption, minimizing raw material costs or facilitating replacement with new raw materials.

2. The clearer structure/function relationship makes it possible to better predict and control catalyst performance indexes and reduce the time to market for new products and processes.

3. Minimizing pollution and reducing pollution costs.

4. Improved separation, recovery and recycling.

5. Reducing the loading of precious catalysts such as platinum group metals, or replacing them with more abundant elements.

6. Improving the long-term stability under the reaction conditions.

7. Can be operated at lower temperature and pressure, saving energy.

8. It is possible to control the catalyst poisoning and the catalyst deactivation.

9. Sintering and agglomeration of catalytic particles, which typically results in catalyst deactivation and reduced life, is minimized.

In some embodiments, improvements in efficiency, selectivity, operating temperature, particle deactivation, thermal and mechanical stability, catalyst loading are discussed. In addition, in some embodiments, active sites can be integrated into a multi-scale, multi-functional material facility designed to control mass transfer, reactive coupling, conduction or dissipation of heat or light, and provide long-term stability under reaction conditions, among other things. In addition, for successful industrial applications, in some embodiments, the manufacture of catalytic materials can be carried out in a scalable manner using economical materials and in a form that facilitates their integration into larger systems, whether supported on a substrate or dispersed in a medium, for example. While certain porous structures such as zeolites, carbon-based systems, and metal-organic frameworks can provide large reaction surfaces and allow for engineered mass transfer, many other factors are difficult to control in combination. To radically advance the art, disclosed herein are comprehensive synthetic strategies for tailoring the effects of a variety of material characteristics, such as the distribution of one or more types of active sites on a bulk matrix, the geometry of pores/channels, their size, arrangement, and connectivity, and the mechanical and optical properties of the system.

In some embodiments, different methods of forming the catalytic structure may include combining the catalyst support directly with the active catalyst precursor (e.g., as a slurry), or fusing the catalyst into a preformed support structure. The present invention provides nanoscale active sites that can be localized on mesoscale entities, and the self-organization of mesoscale particles within a matrix can further mediate the formation of a variety of macroscopic hierarchical structures comprising a network of precisely structured catalytic sites.

In some embodiments, mesoscale template materials such as polymeric colloids and/or fibers (e.g., about 10 nanometers to 100 micrometers in size) containing catalyst on their surface are co-assembled with metal oxide matrix precursors to form, upon removal of the template sacrificial material, a highly interconnected network of channels or pores with precisely located catalyst. The terms "network of interconnected channels", "network of interconnected pores" and "network of interconnected pores" are used interchangeably in this specification to denote a three-dimensional interconnected space that serves as a reactant channel. In addition, as described herein, the terms "pore" and "channel" are used interchangeably (e.g., the use of "pore" also refers to the use of "channel"), and the pore also refers specifically to the inverse opal structure. In some embodiments, the strategy enables independent specification of reaction components, matrix and template properties, allowing near independent design of the physical, chemical and structural properties of the catalytic material, including composition, surface area, porosity, interconnectivity and tortuosity, at multiple length scales, from molecular to nanometer and micrometer scale, and finally to macroscopic (e.g., 10 micrometers and above). Here, the contribution of each of these parameters and exemplary functional advantages of the resulting catalytic structure are described in some embodiments.

In some embodiments, the three-dimensional porous structure may have various structures, such as inverse opals, gyros, double gyros, lincoln logarithmic structures, sponge structures, structures assembled from fibers, assemblies of random irregular objects, combinations thereof, and the like. In some embodiments, the three-dimensional porous structure may be highly ordered and partially disordered. In some embodiments, the three-dimensional porous structure has an inverse opal structure that is both highly ordered and partially disordered. In some embodiments, the three-dimensional porous structure has a gyroscopic structure that is both highly ordered and partially disordered. In some embodiments, the three-dimensional porous structure has a double-gyroscope structure that is both highly ordered and partially disordered. In some embodiments, the three-dimensional porous structure has a lincoln logarithmic structure that is both highly ordered and partially disordered.

In some embodiments, this is a disclosed configuration according to this principle for designing a multipurpose synthetic framework for a hierarchical organic-inorganic catalytic structure with multiple degrees of freedom (e.g., as shown in fig. 35). As shown in fig. 35, in some embodiments, structural and compositional freedom is provided by the disclosed methods for designing improved catalysts. In some embodiments, the system is fine-tuned from molecular (surface modification and matrix composition), through nanoscale (composition, size and location of catalytic nanoparticles and matrix dopants), microscale (pore size, shape and connectivity), to macroscale (bulk shape and macroscopic mode) to produce the desired functional structure. For example, disclosed herein is a catalytic system design 3500 for selecting one or more degrees of freedom including substrate composition, substrate dopant, pore size, pore shape, pore connectivity, pore arrangement, pore order, pore surface modification, nanoparticle size, nanoparticle composition, nanoparticle loading, and nanoparticle location to achieve a desired functional structure.

As disclosed herein, section I describes the interfacial properties between catalytic nanoparticles and the matrix, between catalytic nanoparticles and the channels or pore network, and between the matrix and the channels or pore network, according to some embodiments. Section II describes exemplary methods of controlling the interface morphology and chemistry, according to some embodiments. Section III describes exemplary applications of catalytic materials according to some embodiments. Section IV describes various materials that may be used in some embodiments. In some embodiments, the disclosure of each section may be combined with the teachings of the other section disclosures to produce additional porous catalytic structures with combined or additional functionality. By way of non-limiting example, embodiments disclosed in sections I-III can be made using the materials of section IV, or embodiments of section I can be implemented using the methods and concepts of sections II and III.

I. Design features for enhanced catalytic materials

In various embodiments, the features disclosed below may be included alone, or in combination with other features disclosed herein.

In some embodiments, disclosed herein and schematically presented in fig. 1A is a versatile synthetic framework for designing a reinforced catalytic structure 100, wherein catalytic Nanoparticles (NPs) 101 are strategically placed at the interface between a matrix material 102 and a network of interconnected channels 103. In some embodiments, the NPs are described as being partially embedded, buried, implanted, or embedded in or within the matrix material. For the purposes of this application, these terms are used interchangeably and their intended meanings and quantitative indicators are as follows. As demonstrated in some embodiments of the invention, this partial encapsulation of catalytic NPs provides a number of previously unavailable advantages, such as: (i) excellent mechanical stability against coalescence and sintering, resulting in enhanced catalyst activity and lifetime, (ii) excellent thermal stability, particularly under high temperature reaction conditions; and (iii) in some embodiments, also in connection with catalyst performance enhancement due to modulation of the chemistry of the NPs or their interface with the substrate and channels and formation of additional promoter species.

Particles that are partially embedded, implanted or embedded in or within the matrix material refer to particles that are present in the following manner: with respect to the adjacent surface of the substrate, a portion thereof (referred to as the proximal NP portion 104) is encapsulated by the substrate material 102, forming a proximal interface 106 between the NP and the substrate, while the remaining portion (referred to as the distal NP portion 105) is not encapsulated by the substrate and is exposed to the channel 103, forming a distal NP-to-channel interface 108. The two interfaces intersect to form a ternary interface 107 between the NP-matrix material-channel, referred to in some embodiments as the "circumferential", "equatorial", "peripheral", "three-phase contact line", "matrix-channel interface at the nanoparticle periphery". The term "partially embedded" means that there is some defined ratio between the depth of the proximal or embedded portion 104 of the nanoparticle and the height of the distal or exposed portion 105 of the nanoparticle. These concepts may also be illustrated by reference to fig. 1B, which shows several possible exemplary arrangements of differently shaped nanoparticles 100 (the catalytic material 100 of fig. 1B has a similar structure to the unlabeled catalytic material 100 of fig. 1A, e.g., the nanoparticles 101 of fig. 1B have corresponding proximal 104, distal 105, proximal 106, peripheral 107, and distal 108 end interfaces). In some embodiments, the proximal interface of the embedded particle may be smooth, curved, planar, rough, or wrinkled, while the NP-matrix attachment is continuous, conformal, or discontinuous and multi-point. The terms circumferential, equatorial, peripheral, three-phase contact line, matrix-channel interface at the nanoparticle periphery apply to any one of the possible shapes of NP including, for example, spherical, ellipsoidal, elongated, rod-like, polyhedral, planar, arbitrary curved surface shapes, with corrugations, jagged profiles, any shape in between the above, and any combination of a plurality of these shapes, and not just spherical nanoparticles.

For the purposes of this application, the absolute depth to which such NPs are partially embedded, buried, or embedded in the matrix material is characterized by the distance between the location of the matrix-channel interface at the nanoparticle periphery and the location of the deepest point of the proximal portion of the corresponding nanoparticle, as shown in the embodiment of fig. 1B. In addition, the degree of embedding is defined by the ratio between the depth of the proximal portion of the nanoparticle shown at P in FIG. 1B (described by the plane of the deepest point of the proximal interface 120 and the perimeter 121) and the height of the distal portion of the nanoparticle shown at D in FIG. 1B (described by the farthest point 122 of the distal interface and the perimeter plane), which is referred to as the P: D ratio. While the P: D ratio can vary over a wide range, in some embodiments, no less than one atomic layer of catalytic material is embedded into the matrix material to achieve significant binding of the nanoparticles to the matrix to achieve enhanced catalytic activity as described herein. The P: D ratio of some embodiments is explained below.

In some embodiments, the lower P: D ratio limit is estimated for spherical gold nanoparticles having diameters of 1-20nm (encompassing the typical size range of catalytic nanoparticles). Under the above assumptions, no less than one atomic layer of gold (0.288 nm based on 144pm metallic gold atomic radius) should be embedded in the matrix, with a lower calculated P: D ratio limit of-29% to-1.4% for spherical gold nanoparticles with diameters D1 nm to D20 nm.

In some embodiments, the lower P: D ratio limit is also estimated for square gold nanoparticles with sides of 1-20nm (covering the typical size range of catalytic nanoparticles). Under the above assumptions, no less than one atomic layer of gold (0.288 nm based on 144pm metallic gold atomic radius) should be embedded in the matrix, with the lower limit of the calculated P: D ratio being the same value-29% to-1.4% for square gold nanoparticles embedded with sides 1nm to 20nm and parallel to their faces.

In some embodiments, the lower P: D ratio limit is also estimated for rod-shaped gold nanoparticles oriented perpendicular to the matrix interface and having lengths of 10nm, 20nm, and 50nm, respectively (encompassing the typical size range of catalytic nanorods). Under the above assumptions, no less than one atomic layer of gold (0.288 nm based on 144pm of metal radius of gold atom) should be embedded in the matrix, and the lower limits of the calculated P: D ratios for these rod-shaped gold nanoparticles are-2.9%, -1.4%, and-0.6%, respectively.

It will be apparent to those skilled in the art that similar calculations and estimates can be made for different NP materials, different shapes of nanoparticles, their different orientations relative to the nanoparticle perimeter plane embedded in the matrix, and the volume ratios of their proximal and distal portions. In some embodiments, at least one atomic layer of catalytically active material should be exposed to the channels, thereby avoiding the complete particle encapsulation and formation of the enhanced catalyst of the present invention with catalytic NPs exposed to the porous network, and therefore the methods above for estimating the lower limit are equally applicable to the upper embedding limit.

To achieve the beneficial results described herein, in some embodiments, the proximal portion of the catalytic NP may vary from 0.5 to 99.5%, and the exposed distal portion of the catalytic NP may vary from 99.5 to 0.5%. More specifically, in some embodiments, the P: D ratio as defined herein includes the following P: D ratio: 0.5:99.5, 1:99, 2:98, 3:97, 4:96, 5:95, 6:94, 7:93, 8:92, 9:91, 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 91:9, 92:2, 93:7, 94:6, 95:5, 96:4, 97:3, 98:2, 99:1 and 99.5: 0.5.

In some embodiments, the P: D ratio of different NPs in the same catalytic material may be varied such that a large number of NPs, particularly those with higher entrapment ratios, are present in different P: D ranges to ensure high mechanical and thermal stability (as shown in fig. 8). For example, fig. 8 shows nanoparticles 802 embedded in a matrix material 803 and exposed to a channel 801. The nanoparticle has a perimeter 820, a proximal interface 805, and a distal interface 806. The catalytic material also has a matrix/channel interface 804. In some embodiments, the nanoparticles are embedded to varying degrees. In some embodiments, it is desirable to have a larger proportion of nanoparticles (e.g., greater than 50%) only slightly embedded (i.e., with a low P: D ratio) in order to maximize the amount of exposed catalytic material. In this embodiment, the nanoparticles are not considered to be embedded in the matrix material. Examples of nanoparticles are depicted in fig. 8, views a and D. In some embodiments, it is desirable to have a large proportion of nanoparticles (e.g., greater than 30%, 40%, 50%, 60%, 70%, 80%, 90% according to some embodiments) significantly embedded (i.e., having a high P: D ratio) in order to maximize the mechanical and thermal stability of the catalytic material. Examples of such nanoparticles are depicted in fig. 8, views C and E-F. In some embodiments, it is desirable to have a larger proportion of nanoparticles (e.g., greater than 50%) with substantially equal proximal and distal portions (i.e., with a P: D ratio near 1) to achieve high mechanical thermal stability and high exposure of the catalytic material for catalysis. An example of such a nanoparticle is depicted in view B of fig. 8. It has been found that the systems and methods disclosed herein are capable of producing a large number of nanoparticles embedded in a matrix material, e.g., not just touching or contacting the surface.

In some embodiments, the catalytic nanoparticles include a metal, a transition metal, a main group metal, a metal oxide, a mixed metal oxide, any one or more metals from groups 1-16 of the main and transition series or alternative nomenclature, groups I, II, III, IV, V, VI, VII, VIII, the main and transition series or alternative nomenclature, any one or more metal oxides from groups 1-16 of the main and transition series or alternative nomenclature, a metal oxide, a metal sulfide, a metal pnictide, a metal carbide, a bimetallic salt, a complex metal salt, an organic metal salt, an inorganic metal salt, a complex metal salt, a base, an acid, a metal alloy, a multimetallic species, an intermetallic compound, a non-stoichiometric phase, an organometallic compound, a coordination compound, one or more platinum group metals, a complex metal salt, an organic metal salt, an inorganic metal salt, a complex metal salt, a base, an acid, a metal alloy, a multimetallic species, an intermetallic compound, a non, One or more platinum group metal oxides, carbon, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, iron oxides, cobalt oxides, nickel oxides, ruthenium oxides, rhodium oxides, palladium oxides, osmium oxides, iridium oxides, platinum oxides, copper oxides, silver oxides, gold oxides, titanium oxides, zirconium oxides, hafnium oxides, vanadium oxides, niobium oxides, tantalum oxides, chromium oxides, molybdenum oxides, tungsten oxides, manganese oxides, rhenium oxides, scandium oxides, yttrium oxides, lanthanum oxides, rare earth metal oxides, single crystal polymorphs, or any of the foregoing of several polymorphs, any of the foregoing that provides a particular crystal plane to a channel, any of the foregoing in amorphous form, and combinations thereof.

In some embodiments, composite catalytic materials and methods of their formation are described that feature a plurality of catalytic nanoparticles loaded with functional and/or catalytic species. The material includes catalytic Nanoparticles (NPs) partially embedded within a carrier matrix of a three-dimensional porous structure. In some embodiments, the NPs are bound by means of an interconnecting network of interconnecting template components. The NP experiences unique asymmetric conditions during processing of the composite precursor. In some embodiments, due to this very specific local chemical environment, the treatment (e.g., thermal, light, microwave, plasma, and chemical treatment; under oxygen, other gases, etc.) may result in the formation of functionally (e.g., catalytically or co-catalytically) related chemical and structural/morphological species or features at the NP-substrate, NP-pore, and substrate-pore interfaces. The treated or final material has enhanced properties relative to the untreated material.

In some embodiments, the final catalytic material has one or more of the following characteristics:

enhanced mechanical and thermal stability, preventing particle coalescence and diffusion due to strong particle bonding caused by partial embedding of the NPs within the carrier matrix;

additional mechanical and thermal strengthening that prevents particle coalescence and diffusion due to process-induced chemical bonding (e.g., metal oxides, metal silicates, alloys, etc.) at the proximal interface between the NP and the substrate;

formation of catalytically relevant ionic species (i.e. ions and radicals such as ag (II), au (iii), Pd (II, IV), Pt (II, IV)) predominantly at the NP-substrate interface;

treatment-induced deposition of catalytically (or co-catalytically) active species (such as carbon or polycyclic/condensed carbon-rich species) occurs predominantly at the matrix-pore interface due to incomplete removal or chemical conversion of the interconnecting template component (which comprises, for example, organometallic NP, organometallic or oxide phases);

treatment-induced deposition of catalytically (or co-catalytically) active species (such as metals, metal oxides, metal or metal oxide nanoparticles) occurs primarily at the NP-pore interface as a result of combustion of the composite template material;

the NP content is redistributed (for example in the case of multi-metallic NPs a heterogeneous distribution of different metal atoms is obtained) due to the presence of certain species induced mainly at the interface and/or the temperature gradient that promotes this conversion;

treatment induces shape changes (e.g. faceting, roughening, and stretching) of the loaded NPs due to specific and asymmetric chemical conditions, thermal gradients, etc. at the different interfaces;

-forming different catalytically relevant phase transitions within the matrix material, mainly at the proximal NP-matrix interface and the matrix-template component interface;

the appearance or modification of the porosity of the NP itself;

and other chemical, structural and mechanical transformations taking place at the proximal, distal and matrix-channel interfaces.

According to some embodiments, the above-described changes in anchoring, chemical and mechanical bonding, and the presence of additional catalytic species within the catalytic material result in unprecedented improvements in catalytic performance, including but not limited to one or more of the following: significant reduction in catalyst loading, reduction in reaction temperature, improved selectivity, improved lifetime, reduction in catalyst poisoning and deactivation. More specific features are discussed below.

In some embodiments, as shown in fig. 1, the final material is characterized by increased mechanical and thermal stability due to the partial embedding of the NPs within the carrier matrix. In some embodiments, as shown in the example given in fig. 10, the final material is characterized by enhanced bonding to the matrix (e.g., the matrix material) and, therefore, stability against migration, agglomeration, and sintering, which would otherwise result in premature deactivation or reduced activity of the catalyst. Specifically, FIG. 10 compares the thermal stability of Au NPs grown in preformed pure IOs (1001- & 1006) and those incorporated into silica IOs using NP-decorated template method (1007- & 1012) according to some embodiments. 1001 and diagram 1002 give SEM images of silica IO with Au NPs grown on the surface before heat treatment. 1003 gives a TEM image of the IO fragment shown in view 1001. The particle size at this stage was 9. + -.3 nm. 1004 and schematic 1005 give SEM images of the IO shown in view 1001 after heat treatment at 600 ℃. The average particle size at this stage was 28 ± 9nm (> 200% increase), as shown in 1006 TEM images of IO fragments after heat treatment. Since an increase in the size of the catalytic particles significantly reduces their activity, the (conventional) catalyst will show a continuously decreasing activity as the particles diffuse and grow after heat treatment. In contrast, according to some embodiments, 1007 and scheme 1008 give TEM images of NP-decorated particles composed of polystyrene colloids modified with Au NPs (5 ± 1nm) according to some embodiments. 1009 and schematic 1010 show SEM images of IO prepared using the colloid shown in 1007 according to some embodiments. 1011 and scheme 1012 give TEM images of the IO as shown at 1009, showing that the Au NP diameter does not change significantly (6. + -.1 nm, 20% increase) after calcination at 600 ℃. The absence of growth results in a high degree of thermal stability and long-term functionality of the catalyst. This result is confirmed, for example, in FIGS. 12-13.

Enhancing the thermal stability of the incorporated NPs is of high practical importance because it affects the operating conditions and service life limits of the catalytic device (e.g., catalytic converter, reformer, or fuel cell). The catalysts described herein are non-limiting examples that provide systems in which NPs are significantly stable at high temperatures without diffusion and sintering. The stabilizing effect may be of varying degrees for different reaction conditions and different catalysts. In some embodiments, NP growth may be increased by 1-2%, 2-5%, 5-10%, 10-20%, 20-40%, and over 40% in the systems disclosed herein as compared to conventional systems, while the increase in NP size of the corresponding conventional catalysts under the same conditions will correspond to 5-10%, 10-20%, 20-30%, 40-60%, 60-80%, 80-100%, and over 100%.

In some embodiments, such as schematically represented in fig. 3, the final material is characterized by additional mechanical reinforcement or strengthening due to the chemical bonds formed induced by the treatment between the NP and the matrix. As non-limiting examples, for metal-catalyzed NPs embedded in various matrix materials, the heat treatment described herein may result in the formation of metal oxides, metal silicates, metal aluminates, or, more generally, nanoparticles having proximal portions chemically attached at an interface with the matrix material by covalent interactions, ionic bonding, by the formation of oxides, mixed oxides, oxometalates, aluminates, mixed aluminates, silicates, mixed silicates, aluminosilicates, titanates, mixed titanates, stannates, mixed stannates, stannous salts, mixed stannous salts, rare earth oxides, mixed rare earth oxides, carbides, metal alloys, intermetallics, organometallic compounds, coordination compounds, organic compounds, inorganic compounds, or combinations thereof.

In some embodiments, the final material is characterized by the formation of catalytic related species, neutral or ionic species, primarily at the NP-matrix and NP-pore interfaces (see, e.g., fig. 3-6). As a non-limiting example, for metal-catalyzed NPs embedded in various matrix materials, the process-induced changes described herein can lead to the formation of, for example, ions and free radicals, such as Ag (II), Au (III), Pd (II, IV), Pt (II, IV), Rh (I, II, III), Ru (II, III), each of which can contribute additional enhanced catalytic benefits to the performance of the catalytic NP.

In some embodiments, the final material is characterized by treatment of catalytically (or co-catalytically) active species resulting from incomplete removal or chemical conversion of the interconnecting template component induces deposition, primarily at the matrix-pore interface, as schematically represented in fig. 6 and 2B. By way of non-limiting example, incomplete thermal removal of the organic sacrificial template will result in the deposition of carbon or polycyclic/condensed carbon-rich species that contribute to NP catalytic activity. Likewise, chemical or thermal removal of the composite template material containing the organometallic species or impregnated with the metal or metal oxide phase will result in deposition of metal or metal oxide NPs or films at the substrate-pore interface.

In some embodiments, the final material is characterized by redistribution of NP content or composition due to anisotropy in the environment in which the NPs are embedded, such that differences in the chemical environment of the substrate and template sides after thermal or chemical treatment create a chemical composition gradient and result in the accumulation of different species at the distal and proximal interfaces, active species are drawn to the distal interface, and/or a temperature gradient contributes to this transition. As a non-limiting example, fig. 5, panels a and C, show the process-induced uneven distribution of different metal atoms within a bi-metallic or multi-metallic NP in the case of a bi-metallic or multi-metallic NP.

In some embodiments, as shown in figure 4, view C, the final material is characterized by porosity, cracks, or channels within the NPs. This porosity results in enhanced catalytic activity due to the localized reduction in effective NP size. Another consequence of this creation or alteration of the porosity of the catalytic NP is that the proximal NP-matrix material interface is accessible to the reactants and thus has additional catalytic activity present.

In some embodiments, the final material is characterized by process-induced changes in the shape of the supported NPs (e.g., faceting, roughness, and elongation; an exemplary system is shown in FIG. 4) due to specific and asymmetric chemical conditions, thermal gradients, etc. experienced at the distal and proximal interfaces of the NPs during formation of the catalytic material.

In some embodiments, the final material is characterized by a shell or shell induced by treatment at the distal (NP-pore) interface (fig. 5 view B). In some embodiments, the shell is comprised of a type of metal that is different from the remainder of the NP. In some embodiments, the shell is composed of a different type of metal (e.g., metal alloy) that forms a hybrid shell than the remaining NPs. In some embodiments, such an outer shell or shell provides improved mechanical stability (e.g., resistance to sintering or material evaporation), chemical stability (e.g., resistance to poisoning), catalytic activity, and selectivity.

In some embodiments, the final material is characterized by the formation of different catalytically related phase transitions within the matrix material at the proximal (NP-matrix) interface (see, e.g., fig. 3 view AB).

In some embodiments, such as shown in fig. 9, different nanoparticles may be used to provide various catalytic functions. For example, figure 9 view a shows the process of decorating 908 a template material 901 (as shown by the different patterns in the figure) with different types of catalytic NPs 902 to produce a decorated template material 903. The decorated template material 903 self-assembles and bonds with the substrate precursor 904 to form an interconnect carrier substrate material 905, an interconnect template component 906, and the catalytic NP 902 is embedded in the substrate material 905. Post-formation treatment 909 is performed to remove the interconnect template component 906 resulting in catalytic nanoparticles 902 remaining embedded in the carrier substrate 905 at the interface between the carrier substrate 905 and the network of interconnected channels 907 as a result of the removal of the interconnect template material 906. Two specific examples of this approach are given in panel B, where NP decorated colloidal particles are used as template material. A representative Scanning Electron Microscope (SEM) image of 911 shows Au and Pt NPs embedded in a silica matrix material according to some embodiments, as shown in schematic 910. Au and Pt NPs were uniformly dispersed in the matrix material and contained at the same pore/matrix interface as shown by the scanning transmission electron microscope-energy-dispersive X-ray spectroscopy (STEM-EDS) elemental composition map in 912. That is, a plurality of nanoparticles are contained in a local region. 914 is a representative Scanning Electron Microscope (SEM) image showing Au and Pd NPs decorated on a separate template material according to some embodiments, as schematically shown in 913. Since the Au and Pd NPs were included on separate template plates, they were contained in different holes and located in different areas, as shown in the STEM-EDS image of 915. This approach allows for various NP configurations and combinations in the porous structure, which are particularly relevant for coupling and partitioning reactions catalyzed with different metals. For example, as shown in fig. 9A-B, IO may be generated with different metal NPs in different wells or with multiple metal NPs within a single well. NP-decorated template particles and IO final wells bearing multiple types of NPs on their surface (fig. 9B, 910-. These configurations are particularly suitable for multi-step reactions because the different catalysts can be distributed in the matrix in pre-designed concentrations and distances from each other. In some embodiments, a mixture of multiple NP-decorated template particles each coated with a single metal NP of one type is applied, creating an IO in which each individual well contains one or the other type of NP, allowing different chemical processes to be performed simultaneously in adjacent wells (fig. 9B, 913-. In some embodiments, the geometry of the pores and the openings between them is highly regular, and thus the diffusion characteristics of the reactants in such systems can be predicted and used to design the reaction sequence.

In some embodiments, the treatment results in a porous structure in which the matrix, metal composition, macroscopic pattern, and gradients of reactivity and fluid properties are all varied.

Process II

Figure 2, view a, schematically depicts a method for forming a composite catalytic material characterized by a plurality of catalytic nanoparticles (labeled "catalytic NPs") 202 located primarily at the interface between two interconnected structures (labeled "support substrate" 205 and "interconnecting template component" 203), according to some embodiments. For example, according to some embodiments, the formation process 209 may remove the interconnected template component 203 to form an interconnected porous network 207. This method is similar to that described above with respect to fig. 9, and in some embodiments includes one or more nanoparticle species. Fig. 2, view B, shows another example of an alternative method of producing a catalytic material similar to the method of view a of fig. 2, according to some embodiments. In the case B, the precursors 211 of the future catalytic nanoparticles 202 are embedded within or as part of the template material 210, which decompose to form the catalytic NPs 202 after processing. The template material 210 self-assembles, and combines with the substrate precursor 204 to produce a carrier substrate 205 and an interconnected template component 212 having the nanoparticle precursor 211 disposed therein. During the post-formation treatment 209, the interconnecting template component 212 is removed, leaving the catalytic nanoparticles 202 partially embedded in the support matrix 202.

As shown in fig. 3, panels a and D, the template porous structure shown in fig. 1A may be treated, according to some embodiments, to provide a desired modification at or near the proximal interface region between the catalytic nanoparticle 303 and the "support matrix" 301, as shown by the modified NP-matrix interface 304. For example, according to some embodiments, treatment-induced formation of chemical linkages 304 between the NP and the substrate may enhance the thermal and mechanical stability of the catalytic NP. In some embodiments, a chemical connection may be formed between the NP303 and the substrate 301. In some embodiments, the treatment may result in roughening of the proximal interface and a corresponding increase in contact area between the NP and the substrate 308. In some embodiments, the high concentration of hydroxyl groups in the sol-gel matrix may promote the formation of a large number of metal oxide (M-O) bonds (e.g., 304) with the catalytic NPs. For example, SiO₂The Ag NP in the matrix, after calcination, can oxidize and form Si-O-Ag bonds. As a result of the increased contact area and the formation of chemical bonds (covalent and/or ionic character), a system can be obtained that is highly stable (thermal, mechanical and chemical) to various deactivation mechanisms, including decomposition, NP sintering and poisoning, and has NPs that are highly accessible to the reactants.

In some embodiments, the chemical linkage between the NP and the substrate is covalent. In some embodiments, the chemical linkage between the NP and the substrate is ionic.

Figure 3, panel C, shows the induction of formation of catalytic NPs 303 with charged (e.g., ionic) species 305 and the charged attractive interaction between the catalytic NPs 303 and the substrate 301, according to some embodiments. By changing the physical (temperature) of the sacrificial material (e.g. template component such as 203) to be removedTemperature and temperature rise) or chemical (combustion atmosphere, dissolution medium) conditions, can locally control the formation of oxidizing and reducing species (on the (sub) nanometer scale) within the catalytic NP 303. In some embodiments, due to the unique asymmetric "sandwich" environment in which the NPs 303 are located (i.e., the NPs 303 are "sandwiched" between the carrier matrix 301 and a templating component, such as templating component 203), different charged species may be formed on a given NP303 (or within the matrix near the proximal interface with the NPs 106). For example, if the catalytic NPs 303 are formed of a metal, localized oxidation of the metal due to the formation of complex or mixed oxides or salts (e.g., silicates, titanates, aluminates) may generate cations primarily at the matrix-NP interface, and retention of the reduced metal state may occur primarily at the NP-pore interface due to the presence of reducing (organic sacrificial) species primarily at the NP-template component interface. In addition to providing coulombic attractive interactions resulting from the generation of charged species, certain ions may have the advantage of providing a promoting function. As a non-limiting example, for catalysis with metallic gold NPs implanted with a metal oxide matrix material, thermal treatment and chemical interaction with the matrix can produce Au³⁺Oxometalates, produce gold ion species known to be active in most chemical reactions catalyzed by metallic Au NPs, thereby increasing the overall catalytic activity of the system.

Figure 6 view a shows deposition 604 and 605 of a catalytically relevant species primarily at the substrate-pore and/or distal NP-pore interface, according to some embodiments. In some embodiments, the deposition may occur by incomplete combustion of interconnected template components (e.g., template component 203), resulting in the formation of catalysis-related species 605 primarily at the matrix-pore and/or NP-pore interfaces. For example, the interconnect template component (e.g., template component 203) may be made partially or entirely of materials such as organic polymers, biological materials, and inorganic compounds (e.g., metals and metal oxides or nanoparticles). As one illustrative example, carbon may be deposited at the substrate-pore and/or NP-pore interfaces to perform a catalytic or promoting function. In some embodiments, the deposition may form a continuous layer or discrete islands. In some embodiments, in addition to (co) catalytic activity, the deposits may also alter the surface energy of the substrate 601 and/or NPs 603 (e.g., carbon deposition renders the surface hydrophobic). In some embodiments, atoms originating from the template component may diffuse and form substitutional defects within the substrate 601 and/or NPs 603, thereby creating additional (co-) catalytic centers. In some embodiments, the catalysis-related species 605 may coat only the interface between the substrate 601 and the interconnected porous network 602. In some embodiments, the catalysis-related substance 605 may coat only the interface between the pores 602 and the NPs 603. Likewise, the combination of the two coating modes can also take place in the same catalytic material, leading to a modified and/or enhanced catalytic activity.

In some embodiments, the sacrificial template material decorated with nanoparticles (e.g., 203) may be further coated with a second material prior to assembly and substrate infiltration (e.g., 204). This additional coating results in the formation of a continuous or discontinuous layer covering the matrix channel interface and the proximal NP-substrate interface, leaving the distal interface unchanged (as shown in fig. 6B). As one non-limiting example, a template material decorated with NP may be coated with titania and then assembled and impregnated with a sol-gel matrix precursor to form a silica matrix. In this case the reactants would be exposed to catalytic NP and titania, taking advantage of this dual catalytic system, but the catalytically inactive silica would provide the advantage of a bulk matrix which is cheap and easy to prepare.

Figure 5 shows a treatment-induced NP content redistribution 503 that alters catalytic activity according to some embodiments. In some embodiments, material that is not laterally demarcated from the NP can induce redistribution of NP content. For example, bimetallic or multi-metallic particles may undergo different reconfiguration processes such that the atoms are homogeneously mixed (e.g., alloyed) and/or certain types of metals are preferentially relocated to the surface of the NP. An example of atom redistribution is shown in figure 5, view C. The degree of mixing or phase separation may depend on the surrounding environment, i.e., the chemical potential of the matrix 501 and/or the interconnect template components. In addition, partial chemical changes may affect one or more of the bimetallic or polymetallic components of the NP, resulting in the formation of a "shell" composed of metal oxide at the distal NP-pore interface. In some embodiments, changes in NP composition may occur. For example, in a bimetallic AuAg NP, Ag atoms can diffuse to the NP surface and form an atomic distribution within the Au. This behavior greatly increases the activity of gold in catalyzing selective oxidation reactions.

Figures 4 and 11 schematically show treatment-induced modifications in the shape and/or morphology of NPs 401 experimentally observed according to some embodiments. In some embodiments, such as shown in figure 4, view a, the asymmetric chemical environment may produce a change in the surface morphology of NP401 by roughening 404 the surface. For example, in conjunction with interfacial strain between the lattices of the NP401 and the substrate 402, adsorbate-induced surface reconstruction, where adsorbate may originate from the template component during processing, may result in mass transport within the particles, resulting in such changes in surface morphology as roughening 404 (fig. 4 view a) and new facets 405 (fig. 4 view B) occurs. An example of such a transition is shown in fig. 11. The effect of the asymmetric chemical environment can be clearly seen in fig. 11, views D, E and F, where the NPs remain spherical at the proximal interface and form perfect facets at the distal interface when compared to the synthetic nanoparticles shown in views A, B and C, respectively. In some embodiments, forming the facets creates more catalytically active edges that increase catalytic performance.

Fig. 3A and 3B show treatment-induced changes to a matrix material 301 according to some embodiments. In some embodiments, the NPs 303 may induce a phase transition in the carrier matrix 301. For example, the NPs 303 may cause crystallographic changes in the matrix 307 or other phase transitions in the proximal interface 306.

Thus, embodiments provided herein are for composite catalytic materials comprising NPs that are predominantly partially embedded at the interface between a support matrix and an interconnected porous network, with enhanced properties resulting from functional (e.g., catalytic or co-catalytic) related chemical and structural/morphological species or features that are process induced to form at the NP-matrix, NP-pores, and matrix-pore interfaces. The invention also provides methods for forming the composite catalytic material. This approach allows decoupling the assembly process requirements for the catalytic material (before processing) from the requirements for the final composition and geometry of the processed catalytic material.

In some embodiments, and at least in part as discussed above, the enhanced catalytic properties result from the unique arrangement of the three interfaces when the NP is sandwiched between the substrate and the template. The resulting porous catalytic material has many advantageous properties and catalytic properties. Non-limiting examples of enhanced catalytic properties include one or a combination of the following:

1.and (4) stability.The partial embedding of the NP portion into the matrix results in improved mechanical and chemical stability for sintering. As shown by examples in fig. 8, 10, 12 and 13, this stabilization results in improved service life, stable activity and selectivity for long term operation of the catalyst.

2.Thermal stability under reaction conditions.Diffusion and deactivation of the catalyst at high temperatures is a serious problem that is overcome by the catalyst design disclosed herein. As shown in FIG. 12, which shows the application of 1% Pd/SiO₂Stable conversion of isopropanol to CO at 450 deg.C₂。

3.PGM is effectively applied.As shown in the exemplary systems shown in fig. 7, 9B, 10, 24B and 27, the controlled/preset/rational placement of NPs at the substrate/pore interface results in materials with uniformly distributed and accessible NPs. This in turn optimizes the noble metal application to be a more cost effective catalyst. Uniform distribution of NPs is a very important requirement for uniform heat distribution and uniform catalytic performance, and is difficult to achieve. The exemplary systems shown in fig. 17, 18, 19, 20 demonstrate that our process results in PGM-reduced catalysts that do not impair the performance of the catalysts, and in some embodiments even improve their performance.

4.Improved reactant and product diffusion.As described in some embodiments and demonstrated in fig. 29, 30, the proposed method produces a porous material with controlled pore geometry, size, shape, interconnectivity and arrangement. In some embodiments, control of these parameters is important for catalytic performance because it affects the mass diffusion, thermal and optical properties of the reactants in the catalytic and photocatalytic systems. For example, bimetallic AuAg NPs carried on colloidal templated porous silica with a network of fully interconnected pores have been demonstrated in useUnder the reaction conditions, the selective oxidation of methanol to methyl formate does not present a mass transfer limitation. The catalytic performance of this sample is demonstrated in fig. 13. In some embodiments, rational design of the porous material can result in well-defined porous networks with highly regular diffusion paths (e.g., for simulation and rational design of the catalyst) or increased tortuosity for longer residence time of reactants within the catalytic material. Additionally, in some embodiments, the pore arrangement/structure provides specific mechanical properties to the catalyst. For example, a material with randomly distributed pores may have greater mechanical stability than a brittle crystal arrangement in which lattice planes are susceptible to brittle fracture.

5.Lower ignition temperature. In some embodiments, forming the above-described composite catalytic material with multiple catalytic species may increase catalytic activity, resulting in lower light-off temperatures. FIGS. 14-20 provide non-limiting examples of such unprecedented reaction temperature reductions, wherein the performance of catalysts achieved using the catalysts disclosed herein are compared to the performance of corresponding commercially available catalysts.

6.Increase in catalyst Activity. The enhanced catalytic performance results from the unique arrangement of three interfaces where the NPs are sandwiched between the substrate and the template. As demonstrated in the exemplary systems shown in fig. 21-24, only catalysts prepared with NPs located between the substrate and the template material followed by thermal removal of the sacrificial substrate yielded enhanced catalyst arrangements that demonstrated high selectivity and activity.

7.Multifunctional catalyst. In some embodiments, the template approach combined with controlling NP location allows for multiple NP configurations and combinations within the porous structure, which are particularly relevant for coupling and partitioning reactions catalyzed by different metals (fig. 9 and 27). In some embodiments, as shown in fig. 9 and 27, a reasonable catalyst design allows for different NPs to be placed in different partitions, or different NPs to be placed in all partitions.

In some embodiments, the above advantages may be achieved in combination by combining various features. By way of non-limiting example, the multifunctional catalyst may be combined with various methods to increase stability or control pore geometry and channel network tortuosity.

FIG. 12 illustrates the use of a high temperature at high temperature according to some embodiments1% Pd/SiO in the conversion of isopropanol to carbon dioxide with continuous flow of reactants₂Long term stability of the catalyst. The catalyst activity was measured using a conventional fixed bed reactor. The sample was loaded into a quartz reaction tube and pre-treated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any water and air, then cooled to-30 ℃. At 50ml/min containing 22 mol% O₂And 3 mol% isopropanol, the reactor temperature was raised back to 450 ℃ at a rate of 10 ℃/min, and then held at 450 ℃ for 120 h. Detection of isopropanol to CO by GC-MS₂The conversion of (a). Consistent with this stable catalytic performance, no changes in morphology (e.g., size and distribution of NPs) or composition were detected after catalysis using SEM, TEM, and ICP-MS.

FIG. 13 shows the application of colloid-templated SiO₂AgAu from methanol to methyl formate (MF, Square) and carbon dioxide (CO)₂Circles) and long-term stability towards selectivity to methyl formate (triangles). The sample was tested for 1/2 years, but showed no degradation in performance. The catalyst activity was measured using a conventional fixed bed reactor. The sample was loaded into a quartz reaction tube and pre-treated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any water and air, then cooled to-30 ℃. At 50ml/min containing 22 mol% O₂And 6 mol% methanol at a rate of 10 deg.C/min, the reactor temperature was raised back to 150 deg.C and then held at 150 deg.C until the reaction reached steady state conversion. The catalyst sample was maintained under reaction conditions for at least 24 h. The long-term stability was confirmed by evaluating the activity by repeated measurements over a period of 6 months. Although samples were occasionally taken from the reactor and exposed to ambient conditions, the same selectivity and activity were restored under the reaction conditions after re-addition to the reactor. Detection of isopropanol to CO by GC-MS₂The conversion of (a). Consistent with this stable catalytic performance, SEM was used after catalysis,No changes in morphology (such as size and distribution of NPs) or composition were detected by TEM and ICP-MS.

Reducing the light-off temperature of the catalytic reaction results in a corresponding energy savings. The catalysts described herein are non-limiting examples of systems that provide significant reductions in light-off temperature. This reduction may be of varying degrees for different chemical reactions and catalysts. According to some embodiments, the ignition temperature reduction of the enhanced catalytic materials disclosed herein can be achieved at 1-2 ℃, 2-5 ℃, 5-10 ℃, 10-20 ℃, 20-40 ℃, 40-60 ℃, 60-80 ℃, 80-100 ℃ and greater than 100 ℃. As a non-limiting example, the catalytic materials disclosed herein (the properties of which are shown in schematic figures 14-20) demonstrate a reduction in the light-off temperature of oxidation reactions when used in catalytic converters, air purifiers and catalytic coatings, which is particularly important in emission control and air purification. The non-limiting reduction in light-off temperature achieved in some embodiments allows one to operate the air purification device at lower temperatures down to room temperature.

FIG. 14 compares the use of commercially available Pt/Al₂O₃Complete combustion of methanol to CO with catalysts and enhanced catalysts prepared according to some embodiments with the same platinum NP loading of-1 w% Pt₂The reaction temperature was shown to decrease by 55 ℃. The catalyst activity was measured using a conventional fixed bed reactor. The sample was loaded into a quartz reaction tube and pre-treated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any water and air, then cooled to-25 ℃. At 50ml/min containing 22 mol% O₂And He flow of 7.5 mol% methanol the reactor temperature was raised back to 150 ℃ at a rate of 10 ℃/min. The reaction conditions were kept constant for 1 hour for every 10 ℃ rise to allow the catalyst to reach a stable conversion. Detection of methanol to CO by GC-MS as a function of temperature₂The conversion of (a). Consistent with this stable catalytic performance, no changes in morphology (e.g., size and distribution of NPs) or composition were detected after catalysis using SEM, TEM, and ICP-MS. The reduction in light-off temperature (i.e., the temperature at which conversion rises sharply) is substantial and this suggests that complete conversion of methanol to carbon dioxide can be achieved at much lower temperatures than one would normally expect for this process, making room temperature operation possible. This propertyThe entire possible range of applications in low-temperature air purification and emission control is opened up, which is not possible with commercially available catalysts whose specific activity is to be achieved at significantly higher temperatures. Section III and FIGS. 36 and 37 give a non-limiting description of such applications.

FIG. 15 compares the use of commercially available Pd/Al₂O₃Complete combustion of methanol to CO with enhanced catalyst prepared according to some embodiments with the same NP loading of-1 w% Pd₂It shows that the reaction temperature is reduced by-90 ℃ and the reaction can be carried out at room temperature. The catalyst activity was measured using a conventional fixed bed reactor. The sample was loaded into a quartz reaction tube and pre-treated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any water and air, then cooled to-25 ℃. At 50ml/min containing 22 mol% O₂And He flow of 7.5 mol% methanol the reactor temperature was raised back to 150 ℃ at a rate of 10 ℃/min. The reaction conditions were kept constant for 1 hour for every 10 ℃ rise to allow the catalyst to reach a stable conversion. Detection of methanol to CO by GC-MS as a function of temperature₂The conversion of (a). Consistent with this stable catalytic performance, no changes in morphology (e.g., size and distribution of NPs) or composition were detected after catalysis using SEM, TEM, and ICP-MS. As can be seen from a comparison of FIGS. 14 and 15, FIG. 15 shows the results for 1 w% Pd/Al₂O₃The catalyst demonstrated a drop in light-off temperature even greater than for 1 w% Pt/Al₂O₃Catalyst-demonstrated light-off temperature drop, and use of Pd/Al prepared according to some embodiments₂O₃The absolute value of the light-off temperature achievable by the catalyst is close to room temperature. This clearly demonstrates that the catalyst performance improvement is qualitative rather than incremental when prepared in accordance with some embodiments disclosed herein.

FIG. 16 compares the use of commercially available Pt/Al₂O₃Catalyst and enhanced catalyst Pt/TiO prepared according to some embodiments with the same NP loading of-1 w% Pt₂When methanol is completely combusted into CO₂The reaction temperature was shown to decrease by 55 ℃. The catalyst activity was measured using a conventional fixed bed reactor. The samples were loaded into a quartz reaction tube and He flow at 25ml/min at 150 deg.CHeat for 30min to remove any water and air, then cool to-25 ℃. At 50ml/min containing 22 mol% O₂And He flow of 7.5 mol% methanol the reactor temperature was raised back to 150 ℃ at a rate of 10 ℃/min. The reaction conditions were kept constant for 1 hour for every 10 ℃ rise to allow the catalyst to reach a stable conversion. Detection of methanol to CO by GC-MS as a function of temperature₂The conversion of (a). Consistent with this stable catalytic performance, no changes in morphology (e.g., size and distribution of NPs) or composition were detected after catalysis using SEM, TEM, and ICP-MS. The improvement in catalytic performance demonstrated in this and the above examples also demonstrates that the catalyst material preparation process disclosed in the embodiments presented herein is highly modular compared to conventional catalysts, which will provide significant freedom and allow one to obtain enhanced catalytic performance.

A reduction in the noble metal loading of the catalyst can result in significant cost savings. In addition, precious metals are a limited resource, which makes cost and availability important considerations. The catalysts described herein are non-limiting examples of systems that provide comparable or better performance, including lower light-off temperatures at significantly lower noble metal loadings. According to some embodiments, the precious metal loading of the enhanced catalytic materials disclosed herein may be reduced by 1-2%, 2-5%, 5-10%, 10-20%, 20-40%, 40-60%, 60-80%, 80-90%, 90-99%, 99-99.9%. By way of non-limiting example, the catalytic materials disclosed herein (whose performance is shown in schematic figures 17-20) demonstrate up to a 95% reduction in catalyst loading in oxidation reactions when compared to conventional commercially available catalysts comprising the same base material and the same noble metal.

FIG. 17 compares the use of commercially available 1 w% Pt/Al₂O₃Catalyst and catalyst prepared according to some embodiments with reduced Pt-0.5 w% Pt/Al₂O₃When the catalyst is strengthened, the methanol is completely combusted into CO₂It was shown that the reaction temperature decreased by-50 ℃ even at half the NP load. The catalyst activity was measured using a conventional fixed bed reactor. The samples were loaded into a quartz reaction tube and pretreated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any waterAnd air, then cooled to-25 ℃. At 50ml/min containing 22 mol% O₂And He flow of 7.5 mol% methanol the reactor temperature was raised back to 150 ℃ at a rate of 10 ℃/min. The reaction conditions were kept constant for 1 hour for every 10 ℃ rise to allow the catalyst to reach a stable conversion. Detection of methanol to CO by GC-MS as a function of temperature₂The conversion of (a). Consistent with this stable catalytic performance, no changes in morphology (e.g., size and distribution of NPs) or composition were detected after catalysis using SEM, TEM, and ICP-MS.

FIG. 18 compares the use of commercially available 1 w% Pt/Al₂O₃Catalyst and catalyst prepared according to some embodiments with reduced Pt-0.05 w% Pt/Al₂O₃When the catalyst is strengthened, the methanol is completely combusted into CO₂Showing a decrease in reaction temperature of-25 ℃ with 95% decrease in NP loading. The catalyst activity was measured using a conventional fixed bed reactor. The sample was loaded into a quartz reaction tube and pre-treated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any water and air, then cooled to-25 ℃. At 50ml/min containing 22 mol% O₂And He flow of 7.5 mol% methanol the reactor temperature was raised back to 150 ℃ at a rate of 10 ℃/min. The reaction conditions were kept constant for 1 hour for every 10 ℃ rise to allow the catalyst to reach a stable conversion. Detection of methanol to CO by GC-MS as a function of temperature₂The conversion of (a). Consistent with this stable catalytic performance, no changes in morphology (e.g., size and distribution of NPs) or composition were detected after catalysis using SEM, TEM, and ICP-MS.

FIG. 19 compares the use of commercially available 1 w% Pd/Al₂O₃Catalysts and catalysts prepared according to some embodiments with reduced Pd-0.1 w% Pd/Al₂O₃When the catalyst is strengthened, the methanol is completely combusted into CO₂Showing a reduction in reaction temperature of-60 ℃ at 90% reduction in NP loading. The catalyst activity was measured using a conventional fixed bed reactor. The sample was loaded into a quartz reaction tube and pre-treated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any water and air, then cooled to-25 ℃. At 50ml/min containing 22 mol% O₂And He flow of 7.5 mol% methanol was added to the reactor at a rate of 10 deg.C/min back to 150 deg.C. The reaction conditions were kept constant for 1 hour for every 10 ℃ rise to allow the catalyst to reach a stable conversion. Detection of methanol to CO by GC-MS as a function of temperature₂The conversion of (a). Consistent with this stable catalytic performance, no changes in morphology (e.g., size and distribution of NPs) or composition were detected after catalysis using SEM, TEM, and ICP-MS.

FIG. 20 compares the use of commercially available 1 w% Pt/Al₂O₃Catalyst and catalyst prepared according to some embodiments with reduced Pt-0.1 w% Pt/Al₂O₃When the catalyst is strengthened, the toluene is completely combusted into CO₂The reaction temperature was shown to decrease by-40 ℃ with 90% decrease in NP loading. The catalyst activity was measured using a conventional fixed bed reactor. The sample was loaded into a quartz reaction tube and pre-treated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any water and air, then cooled to-25 ℃. At 50ml/min containing 22 mol% O₂And 0.35 mol% toluene at a rate of 10 deg.C/min to bring the reactor temperature back to 325 deg.C. The reaction conditions were kept constant for 1 hour for every 10 ℃ rise to allow the catalyst to reach a stable conversion. Detection of toluene to CO by GC-MS as a function of temperature₂The conversion of (a). Consistent with this stable catalytic performance, no changes in morphology (e.g., size and distribution of NPs) or composition were detected after catalysis using SEM, TEM, and ICP-MS.

Fig. 21 compares the catalytic activity of three exemplary catalysts consisting of silica supported bimetallic AuAg NPs prepared by a colloidal templating method, according to some embodiments, by heat treatment or dissolution (view D or view E) when the templating colloid is removed. FIG. 21, Panel A, depicts methanol to methyl formate (MF, square) and carbon dioxide (CO) using a thermal release template colloid (Panel D, 2101 to 2102)₂Circles) conversion and selectivity to methyl formate (diamonds). Fig. 21, view B, corresponds to samples prepared by chemically dissolving the template colloid (views D, 2101 to 2103). Fig. 21 view C corresponds to a sample prepared by chemically dissolving the template colloid and subsequently heat treating the material (views D, 2101 to 2103b to 2104). The catalyst prepared by thermal removal of the template colloid proved to have a higher conversion of methyl formate: (32%) and high selectivity (fig. 21 view a). In contrast, both catalysts prepared by dissolving the template colloid exhibited a decrease in efficiency when methanol was converted to MF, as shown in fig. 21 view B (corresponding to 2103) and fig. 21 view C (corresponding to 2104). An additional example of improved catalytic activity for selective oxidation of methanol is shown in fig. 22. The AuPd-silica catalyst (2201) prepared by thermal removal of the template colloid demonstrated higher activity (-21%) for methyl formate formation than the same catalyst (2202) prepared by colloidal dissolution and then thermal treatment. All samples described in FIGS. 21-22 were measured under the same experimental conditions and contained the same amount of NP (. about.5 w%). The catalyst activity was measured using a conventional fixed bed reactor. The sample was loaded into a quartz reaction tube and pre-treated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any water and air, then cooled to-30 ℃. At 50ml/min containing 22 mol% O₂And 6 mol% methanol at a He flow rate of 10 ℃/min to raise the reactor temperature back to 150 ℃, and then held at 150 ℃ until the reaction reaches steady state conversion. The catalyst sample was maintained under reaction conditions for at least 24 h. These results demonstrate that catalytic activity is enhanced when NPs are sandwiched between a template material and a substrate precursor prior to thermal pretreatment, according to some embodiments.

Figure 23, panel a, schematically depicts the formation of a catalytic material using a co-assembly process 2310 that results in a substantial amount of NPs 2302 being fully embedded into the substrate (formed from precursor 2303) and unavailable for catalytic reaction after removal of the template material 2301 (as shown in 2304 to 2305, e.g., by thermal removal 2320). Fig. 23, panel B, shows methanol to methyl formate (MF, cross squares) and carbon dioxide (CO) using the catalyst comprising porous silica containing bimetallic AuAg nanoparticles prepared by the method shown in fig. 23, panel a₂Cross circles) and selectivity to methyl formate (cross diamonds). This sample was measured under the same experimental conditions and contained the same amount of NP (. about.5 w%), as described in FIGS. 21-22. The catalyst activity was measured using a conventional fixed bed reactor. The sample was loaded into a quartz reaction tube and pre-treated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any water and air, then cooled to-30 ℃. At 50ml/min containing 22mol％O₂And 6 mol% methanol at a He flow rate of 10 ℃/min to raise the reactor temperature back to 150 ℃, and then held at 150 ℃ until the reaction reaches steady state conversion. The catalyst sample was maintained under reaction conditions for at least 24 h. The random distribution of NPs throughout the matrix and the lack of accessibility significantly reduces the selectivity of the catalyst for MF formation.

The schematic depiction and image of view a of fig. 24 shows the formation of a catalytic material using a non-templating method, in which NPs 2401 are combined with a matrix precursor 2402 without a template colloid. The material 2403 is then heat treated to give 2404 (image in 2405). According to some embodiments, the NPs 2401 are unevenly distributed and the resulting material has reduced catalytic activity (as shown by the methanol to methyl formate conversion plot 2406) upon combination with the matrix precursor 2402. The schematic depiction and image of view B of fig. 24 shows that the template method shown in fig. 2 is applied to form a catalytic material with a uniform distribution of NPs, according to some embodiments, and that the material demonstrates significantly enhanced catalytic activity (as shown by plot 2411) compared to the results shown in view a of fig. 24. The conversion efficiency was significantly reduced compared to the template sample in view B of fig. 24 (5% conversion vs. 32%). Samples 2404 and 2409 were measured under the same experimental conditions (as shown in FIGS. 21-23) and contained the same amount of NP (. about.5 w%). The catalyst activity was measured using a conventional fixed bed reactor. The sample was loaded into a quartz reaction tube and pre-treated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any water and air, then cooled to-30 ℃. At 50ml/min containing 22 mol% O₂And 6 mol% methanol at a He flow rate of 10 ℃/min to raise the reactor temperature back to 150 ℃, and then held at 150 ℃ until the reaction reaches steady state conversion. The catalyst sample was maintained under reaction conditions for at least 24 h. The method depicted in figure 24, panel a, does not allow control over NP location and the resulting material has a larger NP size distribution and decreased NP accessibility. As can be seen from TEM image 2405, the NPs vary widely in size and are randomly distributed within the matrix. In contrast, NPs bound by templating methods (fig. 24, view B) proved to be more uniform in size and uniformly distributed throughout the substrate (TEM image 2410).

The method additionally provides embodiments for strengthening a composite catalytic material characterized by mechanical strengthening or strengthening, formation of catalytically relevant ionic species at the NP-matrix and NP-pore interfaces, deposition of catalytically (or co-catalytically) active species at the matrix-pore interfaces, redistribution of the content of NPs, modification of the shape of the supported NPs, and/or formation of different catalytically relevant phase transitions within the matrix material at the NP-matrix interface and the matrix-template component interface.

Production of porous structures with functional materials

Catalysis is a complex field of material research, and in some embodiments includes a variety of materials and a variety of phenomena occurring over a variety of lengths and time scales. In some embodiments, the development of a generic framework for complex catalytic systems through independent (or quasi-independent) optimization of various structural and compositional features may result in catalysts that can be widely used, for example, for global energy and environmental challenges. To achieve this goal, in some embodiments, disclosed herein is a modular platform in which a sacrificial template component bearing catalytic nanoparticles on its surface self-assembles with a matrix precursor while structuring the resulting porous network, fine-tuning the position of the catalyst particles, and introducing reactants capable of affecting the chemistry at and near the catalytic sites through a subsequent modification step. Such a strategy may allow for combinatorial changes in the material blocks and their organization, thereby providing multiple degrees of freedom for optimizing the functional properties of the material, e.g., from nano-scale to macro-scale. In some embodiments, the platform disclosed herein enables systematic study and design of efficient and robust systems for a variety of catalytic and photocatalytic reactions and their integration into industrial and other real life environments.

In some embodiments, a three-dimensional porous structure may be synthesized by removing the interconnecting template component, thereby providing a network of interconnected pores having a high surface area. In some embodiments, such structures may be used for applications such as industrial catalysis, catalytic conversion, emission control, photocatalysis, sensing, separation and purification, protective coatings (possessing specific, usually pre-designed thermal and/or mechanical and/or chemical properties), and for forming multifunctional systems combining chemical, optical, electrical, magnetic, and other input/output combinations.

Discussed in sections iii.1-iii.6 below are exemplary embodiments of various techniques to implement the catalytic system design 3500 as shown in fig. 35. In some embodiments, the embodiments and techniques disclosed below may be combined to form a catalytic system design 3500.

1. Co-assembly of porous structures

As schematically depicted in fig. 7, the embodiment described herein is a particular manifestation of the general method shown in fig. 2, wherein the template material is spherical polymer colloidal particles. The present embodiment describes a colloidal co-assembly method in which template colloidal particles with a diameter of 20nm to several micrometers can self-assemble with sol-gel or nanoparticle precursors used as background matrices by evaporation induced self-assembly (EISA). During EISA, the solvent (usually water) evaporates creating convective forces that push the particles towards the air-water interface. In the case of co-assembly 702, such as shown in fig. 7 view a, after providing colloids 721 and mixing them with substrate precursors 722 in step 701, they may template to form a background substrate within their interstices as the colloids are drawn toward the substrate and close to each other by capillary and loss forces during co-assembly 702 (see, e.g., 703). In some embodiments, the matrix precursor in the assembly mixture may serve as an amorphous viscoelastic medium to both contain stress and prevent cracking, so that a long-range (millimeter-scale) defect-free colloidal grid may be obtained. Once the template colloid is removed, e.g. by calcination or dissolution, a highly interconnected porous network, the so-called Inverse Opal (IO) structure, is left (704-.

Figure 7, panel B, represents a schematic and representative image of a templating method for producing porous structures in which catalytic NPs 723 are partially embedded within the walls of the matrix material, e.g., functional Nanoparticles (NPs), primarily at the interface between the matrix and the channels (or pores), according to some embodiments. The upper row a represents the assembly of pure colloids, and the lower row B represents the assembly of template colloids 721 decorated with catalytic particles 723, e.g. NPs or ions, in the pre-assembly step 708. 701 depicts the gel 721 prior to co-assembly. 703 and 710 describe assembled composite opal structures. 704 and 711 describe IO structures that result from pores created by removing colloids 721, e.g., by calcination or dissolution. 705 and 712 depict SEMs of embodiments of an IO having pores 221 produced in this manner, where silica is used as the matrix material 725, and an exemplary IO has pores 724, with gold NP723 primarily bonded at the pore interface with the silica matrix material.

As described herein, the forces involved in the co-assembly can produce a highly versatile system for controlling pore size and connectivity and for incorporating the catalyst into a variety of matrix structures and compositions, particularly when the catalyst is associated with and introduced using colloids (e.g., as shown in fig. 7 view B.) in both bare colloids 721 (as shown in fig. 7 view 701) and in some embodiments where the colloids are pre-associated with functional particles 709, the pore size is determined by the size of the template colloid 701, while the pore shape can be controlled by template removal conditions.

As shown in fig. 26, in some embodiments, the macroscopic shape of the colloidal template porous structure can be designed by limiting the co-assembly reaction to different geometries. For example, high quality substrate-attached IO films, dispersible structural tints and design shapes (SHARDS), and dispersible photonic spheres (PB) can be prepared by performing EISA on flat or templated substrates or within droplets, respectively. For example, fig. 26 depicts the formation of different macroscopic forms of IO, in accordance with some embodiments. View a depicts a film on a smooth substrate/flat surface (e.g., film 2610) according to some embodiments, view B depicts dispersible IO cubes (e.g., photonic block 2620) obtained according to some embodiments, e.g., using a patterned sacrificial template, and view C depicts dispersible IO microspheres (e.g., photonic spheres 2630, PB) produced, e.g., by co-assembly of droplet confinement. Each view is schematic (upper left part of views a-C) and includes representative optical images (upper right part of views a-C) and SEM images (lower part of views a-C). For example, the membrane 2610 can be formed by suspending the matrix vertically inside an assembly mixture, e.g., for co-assembly with a silica precursor. As previously described, high quality IO-PB 2630 can be prepared, for example, by a microfluidic emulsification process using a microfluidic device consisting of two inlet channels that intersect to form a crossover point, thereby emulsifying an aqueous dispersion of polystyrene colloid and metal oxide precursor in a continuous fluorocarbon oil phase containing a surfactant. The shrinkage of the droplets during evaporation can produce spherical gel elements.

2. Controlled positioning of catalytic sites

The catalyst immobilization strategy includes: attaching preformed NPs, depositing a metal precursor onto the substrate and then performing a reduction step to form the NPs, and one-pot simultaneous synthesis of the catalytic NPs and their support matrix. Control of one parameter often comes at the expense of control of other parameters. The fusion of catalyst particles into a pre-assembled porous matrix, for example by adsorption or deposition of metallic NPs, can produce highly accessible catalytic sites, but the NPs can be loosely bound and unstable, leading to their sintering and fusion, particularly in high temperature catalytic reactions. These methods may also be subject to complex synthetic procedures that may lead to surface blocking or passivation of the NPs. Both complications lead to a decrease in catalytic activity over time.

Alternative methods based on some embodiments of template-free synthesis of catalysts from mixtures of NPs and matrix precursors can produce stably embedded NPs. However, with this approach, most NPs are excluded from participating in the catalytic process due to poor control of pore size and connectivity and random distribution of NPs throughout the background matrix such that they are mostly fully encapsulated and thus inaccessible to reactants. In some embodiments, the heterogeneity of NP distribution and size resulting from these methods can lead to hot spots in the catalytic process and compromise control of temperature and concentration distribution, which in turn can reduce reaction efficiency and selectivity and system stability.

The dynamic co-assembly strategy described in the exemplary embodiments herein overcomes most of these problems by applying sacrificial colloids to modulate the assembly of the catalyst and pores, resulting in a high degree of control over the location, composition, partitioning, and overall structure of the nanoparticles.

2.1 NP-decorated colloids

As disclosed in embodiments herein, NP-modified template materials (e.g., mesoscale colloids with nanoparticles bound to their surfaces) introduce multiple levels of freedom for the synthesis and introduction of one or more types of catalytic NPs, as shown in fig. 27. As disclosed herein, when the template material is spherical colloidal particles, the resulting NP-decorative material is commonly referred to as "raspberry" particles. The terms "raspberry particle" and "NP-decorated particle" are used interchangeably throughout and represent a particular case of NP-decorated colloids. Disclosed herein are the design and manufacture of these composite colloids with various morphologies and tailored physical and chemical properties. In addition, according to some embodiments, these colloids may provide an effective way to stabilize inorganic nanoparticles in a dispersion. NP-decorated template materials are suitable for a variety of applications, including stimuli-responsive materials and actuators, sensors and SERS substrates, hydrophobic and hydrophilic coatings, catalysis, biochemistry and light and magnetic resonance nanoengineering. The use of NP-decorated template materials as nanocomposite template materials for the preparation of catalytically active porous functional structures has not been realized.

In some embodiments, the formation of IO with NP decorated colloid provides independent control of NP composition, location and loading. Prior to co-assembly (pre-assembly step in fig. 7), NPs are stably associated with colloids whose diameters are tailored to achieve the desired pore size. For example, this approach is applicable to a wide selection of NPs including both monometallic and polymetallic compositions, which may have uniform or compartmentalized (e.g., core-shell) structures. NP-decorated template particles (or impregnated assemblies of such particles) are co-assembled with the matrix precursor, and then the NPs are primarily positioned at the interface between the colloid and the matrix. Once de-gelled, the NPs are partially embedded in the pore walls, optimizing their thermal and mechanical stability, while being largely exposed inside the pores, maximizing their availability for catalysis. For example, fig. 27 depicts the results of this method using Au, Ag, Pd, and Pt, as well as bimetallic particles. SEM images further show that the metal NPs are very uniformly distributed along the IO pore surface, which can provide consistent catalytic performance through uniform distribution of temperature and chemical concentration.

FIG. 27 depicts the formation of an interconnected porous microstructure using different types of NP-decorated template particles. View A depicts template particles, each capped with a single type of NP (as shown on the image). If desired, multiple types of colloids can be applied in various combinations to produce IOs that bind different types of NPs exposed in different wells. That is, view a depicts the formation of IOs using NP-decorated template colloidal particles having Au NPs formed thereon and NP-decorated template colloidal particles having Pt NPs formed thereon, wherein some of the pores bind the Au NPs and others bind the Pt NPs. View B depicts the attachment of different types of NPs (e.g., Au and Pd) on the same colloid, resulting in an IO containing multiple NPs in each well. View C depicts attachment of a multi-metal particle (e.g., AgAu NP) on the same or different colloid, resulting in an IO that binds to the multi-metal catalytic site. In views a-C, the first two columns 2701 and 2702 of the left image contain TEM images 2701 and Scanning Transmission Electron Microscope (STEM) elemental composition maps 2702 of an exemplary polystyrene colloid decorated with metal NPs for assembling an IO system. The corresponding NP-terminated colloid 2710 is schematically shown between image columns 2702 and 2703, followed by the right three columns 2703 and 2705, which contain (from left to right) SEM images and a schematic (built-in) STEM-EDX elemental mapping image 2705 of 2703, TEM 2704 and the system formed.

In an exemplary embodiment, in addition to arranging NPs primarily at the matrix-pore interface, the NP-decorated template approach has the advantage of allowing multiple NP structures and combinations within the porous structure, which is particularly relevant for different metal-catalyzed coupling and zoning reactions. For example, as shown in fig. 27, IO may be generated from different metal NPs in different wells or multiple metal NPs in a single well. In some embodiments, a mixture of multiple NP-decorated template colloidal particles is applied, where each particle is coated with one type of single metal NP, resulting in an IO where each individual well contains one or the other type of NP (fig. 27, view a), which allows different chemistries to be performed simultaneously in adjacent wells. In other embodiments, the final wells of NP-decorated template colloidal particles and IO carry multiple types of NPs on their surface (fig. 27, view B), allowing multiple reactions to be performed sequentially within a single well. For example, these structures may be well suited for multi-step reactions because different catalysts may be distributed in the matrix at pre-designed concentrations and distances from each other. Since the pore geometry and the openings between them are very regular, the diffusion characteristics of the reactants in such a system can be predicted and used to design the reaction sequence. In some embodiments, the template material may be provided with a ratio of one or more different types of catalytic nanoparticles to provide enhanced functionality, e.g., 0.01-99.99% for one type of NP, 0.01-99.99% for another type of NP, and 0.01-99.99% for the other type of NP, with the sum of all NPs being 100%. As non-limiting examples, the first template material may be decorated with 25% Au nanoparticles and 75% Pt nanoparticles, and the second template material may be decorated with 75% Au particles and 25% Pt nanoparticles.

In addition to IOs containing Au and Pd NPs exposed to the same or different pore surfaces (see, e.g., SEM images in fig. 27, views a and B), in some embodiments IO comprising bimetallic NPs are disclosed (AgAu, see fig. 27, view C). Due to the synergistic relationship between different metal components, multi-metal catalysts may have greatly enhanced catalytic performance over their components. As described herein, in some embodiments, the methods of obtaining a multi-metallic catalytic material enable the synthesis of a variety of template colloids with different NP decorations, and their use as needed to form IO specific to the targeted catalytic use. The NP-decorated template colloid approach may reduce the complexity of designing a controlled IO synthesis approach, particularly compared to approaches involving multi-component co-deposition (e.g., mixing bare colloid and NP with matrix precursors), which requires careful consideration of the chemistry of all species involved and their interparticle interactions.

The enhanced efficiency of the modular approach described herein for binding multi-metal particles is possible by applying NP-decorated template colloidal particles to form, for example, silica IO scaffolds decorated with AgAu NPs and performing the oxidative coupling of methanol to methyl formate as a simulated reaction. In some embodiments, the structure demonstrates uniform distribution of the AgAu NPs throughout the structure, primarily along the pore interface (fig. 4 view C). NP loading primarily at the matrix-pore interface can be determined by their density on the sacrificial colloid surface and is directly related to catalytic activity. In some embodiments, the reactivity and selectivity of such systems is comparable to that of an unsupported nanoporous AgAu catalyst (which is a stand-alone structure that is a highly selective and robust catalyst for coupling, for example, alcohols to form esters), but the amount of noble metal is much lower in the cases described in the embodiments herein. In some embodiments, the AgAu-silica structure exhibits high conversion, selectivity, and long-term stability, and no mass transfer limitations under the reaction conditions applied.

Another exemplary advantage of the NP-decorated template colloid method of some embodiments is that the formed IO system is very stable to thermal processing, which is important in an industrial environment, which solves the common problems of NP diffusion and coalescence under reaction conditions that commonly occur in other systems. For example, for silica IOs containing Au NPs generated using NP-decorated particle templates, this stability can be demonstrated by comparing the NPs before and after heat treatment at 600 ℃ with those combined by the more conventional method according to which small (2nm) Au NPs are deposited on the surface of a pre-fabricated IO and then grown (FIG. 10). Silica IO systems incorporating Au NPs by deposition may be characterized by poor NP anchoring, these NPs tend to migrate at the pore surface and coalesce with other particles at high temperatures. In the example shown, the movement of the NPs results in a change in size from 9nm to 28nm after heat treatment (an increase of more than 200%, FIG. 10, view 1001-1006). In contrast, according to some embodiments, silica IOs introduced into Au NPs through NP-decorated templates retain the same NP size (. about.6 nm) and morphology before and after calcination at 600 ℃ due to the partial embedding of the NPs in the silica matrix (FIG. 10, View 1007-1011).

For example, FIG. 10 compares the thermal stability of Au NP grown in pre-fabricated pure IO (1001- "1006) with Au NP introduced into silica IO (1007-" 1012) using NP-decorated template. 1001 and diagram 1002 give SEM images of silica IO with Au NPs grown on the surface before heat treatment. 1003 gives a TEM image of the IO fragment shown in view 1001. The particle size at this stage was 9. + -.3 nm. 1004 and schematic 1005 show SEM images of the IO of view 1001 after heat treatment at 600 c. The average particle size at this stage was 28 ± 9nm (> 200% increase) as shown by TEM images of IO fragments after heat treatment in 1006. Since an increase in the size of the catalyst particles significantly reduces their activity, the (conventional) catalysts formed will exhibit a continuously decreasing activity, since diffusion and growth of the particles occurs after heat treatment. In contrast, 1008 and scheme 1009, according to some embodiments, give TEM images of NP-decorated particles composed of polystyrene colloids modified with Au NPs (5 ± 1nm), according to some embodiments. 1010 and schematic 1010 show SEM images of IO prepared using the colloid shown 1008 according to some embodiments. 1012 gave TEM images of the IO as indicated by 1009 showing that the Au NP diameter did not change much (6. + -.1 nm, 20% increase) after calcination at 600 ℃. The absence of NP growth will result in a great improvement in catalyst thermal stability and its long-term function.

2.2 Raspberry granules

In some embodiments, the freedom to control catalyst distribution and system functionality is further extended by the introduction of ionic species in the assembly mixture, such as schematically depicted in fig. 28. In some embodiments, instead of pre-synthesized metallic NPs bound to colloids to form NP-decorated particles, ionic species may be bound in situ and deposited on the surface of the colloid appropriately functionalized. As an illustrative example, cobalt, which is a bright blue colored additive in glass and a fischer-tropsch catalyst for the production of synthetic fuels, may be used. Disclosed herein are silica-supported cobalt catalysts prepared using a sol-gel process and methods for increasing the surface area of cobalt and other metal oxide catalysts. According to some embodiments, other salts, including Ca, Mg, Ni, Cu, and Fe, may be used in addition to CO to form similar systems. In some embodiments, forming the raw raspberry particles in situ may require fewer synthetic steps than assembling the pre-made NP-decorated particles, which is actually a more beneficial result. However, in some embodiments, the presence of ions or other surface modifiers in the assembly mixture can complicate the self-organization process and lead to uncontrolled deposition. In addition, in some embodiments, during post-modification, the presence of charged species and metal ions can greatly affect the chemistry of the interface in its vicinity (i.e., catalytic NP and support metal oxide), resulting in a change in catalytic performance.

In some embodiments, altering the affinity between the metal cation and the colloidal capping ligand may provide a means to modulate the distribution of catalytic species in the IO structure (see, e.g., figure 28, view a). High affinity may result in the formation of raspberry-like colloids in situ, which may be referred to as 'raw raspberry' particles. In some embodiments, since the time scale of raw raspberry formation is generally much shorter than colloid and matrix assembly, ionic species are introduced and specifically accumulate at the colloid surface and later on after calcination are mainly at the pore interface, similar to pre-synthesized NP-decorated particles. In some embodiments, the low affinity between the ions and the ligands may result in the ions being uniformly dispersed throughout the matrix, including at the interface and in the bulk. Such uniform distribution may be useful, for example, when the salt provides an additional promoting or non-catalytic function as a chemically isolating dopant embedded within the matrix. For example, in photocatalytic reactions, such dopants may be used either to assist or primarily for light absorption and light-induced energy or electron transfer, or they may increase the refractive index of the background matrix for additional photonic effects. In some embodiments, protoraspberries are preferred when the dopant is actively involved in catalysis because of their accessibility to reactants flowing within the pores, and protoraspberries are also preferred when short path distances are required to minimize the possibility of photoinduced electron/hole pair charge recombination. In some embodiments, the ability to determine the distribution of ions within a matrix allows systematic tuning of the catalytic and photonic effects of a given species.

FIG. 28 schematically depicts the introduction of transition metal salts into IO by in situ binding of ions to capping ligands of the template colloid and their assembly. View (a) is a schematic formation of IO structures and the effect of ion/ligand affinity on final ion distribution using a raw raspberry template according to some embodiments. Template colloid 2810, bearing ligand 2803 capable of coordinating with metal ion 2820, is exposed to ion 2807, resulting in complexation and formation of protoraspberry template particles 2830. Their co-assembly 2840 with metal oxide precursor 2805 produces compound structure 2850, which is converted to the reverse structure 2870 after calcination 2860. View (C) depicts a STEM elemental map of the same sample in view (B) showing a uniform distribution of ions in the silica matrix, according to some embodiments. View (D) depicts an X-ray photo-electron spectrum (XPS) of IO synthesized at different HCl loadings in a co-assembly mixture, according to some embodiments.

In some embodiments, the binding of the ionic species to the colloid may be achieved by specific or electrostatic interactions. When synthesized, polyethylene glycol (PEG) or polyvinylpyrrolidone (PVP) functionalized colloids not only have steric stability, but also have a significant amount of surface charge, measured as zeta potential (40 + -10 mV), sometimes comparable to carboxylate or sulfonate terminated colloids. These colloids remain stable even at ion concentrations above the millimolar level due to steric repulsion, where the surface charge is substantially masked or neutralized. In contrast, pure electrostatically stabilized colloids containing sulfonate or carboxylate ligands may become unstable, leading to flocculation and uncontrolled deposit formation, even at lower ion concentrations. As shown in fig. 28, views B-C, the use of PEG-and PVP-terminated colloids, according to some embodiments, allows the formation of high quality IO with a uniform distribution of CO within the silica matrix. In addition, as shown in fig. 28, views B and C, the binding of cobalt ions to ligands such as PEG on the surface of the colloid locally promoted the kinetics of the sol-gel process, resulting in the formation of a cobalt-containing silica shell around the template colloid, resulting in the appearance of a closed array of hollow spheres. In principle, such an array of rigid hollow spheres with isolated spherical chambers can affect catalytic performance. However, as disclosed in the exemplary embodiments herein, the conditions and rate of the calcination step may promote softening and fusing of the individual spheres and the formation of openings therebetween, thereby forming an interconnected porous network prior to complete condensation thereof due to the flowability of the silica sol-gel matrix. In some embodiments, catalysts of different compositions (metal NPs and metal oxide matrices) require special consideration of the heat treatment sequence, which may also be different for catalysts having the same composition but manufactured for a particular purpose. In general, a thermal processing sequence may include multiple steps of heating (at a particular rate), maintaining the same temperature, and cooling (also at a particular rate). To optimize the fusion process of certain embodiments, it is important to have sufficient time for the softened material to flow and reform before cooling or transitioning to the annealing temperature. In some embodiments, it is also important to have sufficiently slow heating and cooling rates to avoid defects caused by thermal shock. The term annealing refers to a process (e.g., by heating, drying, or exposure to specific redox conditions) used to alter the microstructure (e.g., crystallinity, roughness, and redox state) of a material.

In some embodiments, the assembly mixture should be adjusted to produce ions with a particular coordination number, since ion size and direct environment affect its final distribution in IO. In the case of CO, excess HCl may favor the tetrahedral rather than the octahedral coordination form of CO (ii), while moderately acidic conditions (e.g., 0.03M HCl) may result in a heterogeneous IO film containing black cobalt oxide in the silica matrix. At high concentrations of HCl (e.g., 0.63M), a uniform blue cobalt silicate matrix can be obtained, possibly due to the formation of tetrahedral cobalt chloride, which facilitates its incorporation into the tetrahedral silica matrix during condensation of Tetraethylorthosilicate (TEOS). In some embodiments, X-ray photo-electron spectroscopy (XPS) surface analysis (fig. 28 view D) gives a shift of the silicon and oxygen peaks to higher binding energies when the atomic cobalt to HCl ratio is 1:4, indicating the direct interaction between cobalt and silica and the importance of HCl in this synthesis.

3. Controlling connectivity and disorder of pores using NP-decorative particles and ionic additives

In some embodiments, in addition to controlling catalyst location, the colloidal co-assembly system may provide additional degrees of freedom, as the catalyst particles can adjust the matrix structure. According to some embodiments, each of the forms discussed above-raspberry (i.e., NP-decorated template colloid) and protoraspberry particles and ionic species in solution-can provide a mechanism to modulate colloid-colloid and colloid-matrix interactions, resulting in fine-tuning of the self-assembly process and crystallinity of the IO structures formed. The order in which the IOs are assembled determines the organization, connectivity and tortuosity of the porous network and thus, for example, the optical, mechanical and transport properties of the catalytic material. Due to the force-dependent delicate balance of self-assembly into a lattice, the introduction of metal NPs and ions may affect the EISA process, potentially destroying the colloidal structure, resulting in a polycrystalline or amorphous structure. Disclosed in embodiments herein are techniques to avoid or form polycrystalline or amorphous structures. In some embodiments, fcc may be used as the lattice.

The microstructure of the IO (including periodicity, distribution and connectivity between pores) is very important in terms of catalytic performance because it can affect mass transfer, thermal and photonic properties in catalytic and photocatalytic systems. According to some embodiments, both high order and disorder may be beneficial in different situations. For example, the ability to produce crystalline IO assemblies is important for the formation of well-defined porous networks with highly regular diffusion paths, which can be quantitatively measured and modeled for catalytic structure design. In addition, disorder can lead to degradation of certain beneficial properties, for example, when it suppresses slow light effects that enhance light absorption for photocatalytic applications. On the other hand, in some embodiments, catalytic systems may benefit from disorder, for example, enhancing photo-species interactions for improving photocatalytic performance when increased tortuosity is required for longer residence time of reactants within the catalytic material, or when multiple scattering in a disordered structure causes light propagation to transition from a ballistic region to a scattering region, even to a photo-location. In addition, disordered materials are more mechanically stable than brittle crystals whose lattice planes are themselves prone to cracking.

3.1 Regulation of disorder with NP-decorated template particles

According to some embodiments, the co-assembly of NP-decorated sacrificial template materials represents a unique strategy to achieve controlled crystallinity. In some embodiments, EISA that is monodisperse spherical colloids (polydispersity index, PDI < 5%) may produce highly ordered fcc domains when dried, while polydisperse or non-spherical colloids may introduce varying degrees of disorder in the structure. In some embodiments, different sized colloids or permanent and sacrificial colloids are combined to reduce the crystallinity of opals. This method of causing disorder may result in non-uniformity or different sizes of pores and changes in their arrangement. In other embodiments, co-assembly of NP-decorated particles can systematically control the degree of disorder simply by varying the size of the NPs on the surface, since in this case the overall size of all template particles is the same, the formed IO is not heterogeneously introduced into the NPs, the pore size distribution is not large, and there is no phase separation. In some embodiments, NPs on the surface of the colloid can cause systematic disordering by interfering with electrostatic stabilization during self-assembly and by controllably perturbing the sphericity of the template colloid.

Fig. 29 depicts controlled disorder achieved by varying NP size on a template NP-decorated colloid, according to some embodiments. The template particles were polystyrene colloids pre-assembled with gold seeds (2nm (view a), 5nm (view B) and 12nm (view C)). The images in views A-C are, from left to right: TEM 2901 and schematic 2902 of the template particles, SEM 2903 of the resulting IO and built-in magnified schematic 704 of the SEM, and Radial Distribution Function (RDF)2905 calculated from the IO.

As shown in fig. 29, polystyrene colloids modified with 2nm NP (view a) resulted in highly ordered IO, while increasing NP size to 5nm (view B) and 12nm (view C) resulted in increasing degrees of disorder and deviation from the fcc lattice. For example, the degree of disorder is quantified by the Radial Distribution Function (RDF)2905, which is a measure of the number of particles within a structure that are located in a spherical shell of infinite small thickness at a given distance from any individual particle. For a perfect lattice, RDF is given as a function of the distance corresponding to its lattice spacing. For practical systems with limited size, the function becomes a peak with limited height and width. Also, these peaks widen and become smaller in amplitude as the system deviates from perfect periodicity. In fact, for NP seeds of 2nm size, IO has a fcc lattice, and RDF shows many well-defined peaks (view a). The first peak corresponds to the shortest repeat distance, i.e., the center-to-center spacing of the holes or the size of an individual hole. The second peak is a double peak, which corresponds to the distance between two different pairs of lattice planes of the fcc lattice, which are very close in magnitude. When the size of the Au seeds decorating the NP-decorated particles was increased to 5nm (view B), approximately 5 peaks were still visible compared to the control results, although their amplitude was significantly reduced and the second double peak was unlikely to be resolved. For a 12nm seed, only three clearly discernable peaks remain (view C). The fact that the peak intensity decays rapidly with distance indicates that the long range order is reduced compared to the crystal arrangement. In some embodiments, in addition to the advantage of controlling the degree of disorder, the uniformity of disordered structure produced by this method also facilitates a quantitative understanding of how deviation from order affects various aspects of catalysis and photocatalysis without additional confounding factors. In some embodiments, the ratio of template colloid to NP size determines the degree of order in the formed system. When the size of the NPs is at the 0-2% level of the template colloid (typical sizes of template colloids used in the system under study are in the range of 200-350 nm), the system will retain a high degree of order (i.e. a single domain has more than 20 repeat units), 2-5% will result in a medium degree of order (i.e. a single domain has up to 10 repeat units), while a size of more than 5% of the NPs will result in a low degree of order (i.e. a single domain typically has 5 repeat units or less).

3.2 use of original Raspberry particles to control disorder

Similar to metal NPs on colloidal surfaces, in some embodiments, other species present in the assembly solution, such as ions and surfactants, can be used to perturb the self-organization process, providing a unique or complementary route for controlling disorder. As described in section 2.2, according to some embodiments, the introduction of ions into the assembly solution can result in rapid destabilization of the colloidal suspension due to changes in ionic strength, while the use of sterically stabilized colloids allows the formation of protoraspberry particles and avoids such destabilization. Increasing the concentration of these ions in the assembly mixture will result in a higher degree of disorder, but the degree can be well controlled as described in the embodiments herein.

FIG. 30 depicts the use of polyethylene glycol (PEG) -terminated template colloids 3011 and varying concentrations of CO (NO) in an assembly mixture according to some embodiments₃)₂3011 ion-induced controlled disorder in silica IO. According to some embodiments, view (A) gives results at a concentration of 0mM and view (B) gives results at a concentration of 0.64mM (or relative to SiO in the assembly solution)₂Results for 10 mol% precursor, and view (C) gives a concentration of 1.28mM (or relative to SiO in the assembly solution)₂Precursor 20 mol%) results. For each of views a-C, a schematic of the assembly 3001, a large field view SEM 3002 (with built-in schematic) of the formed IO, a magnification 803 of the SEM, and RDF and fast fourier transform (FFT, built-in inset) 3004 calculated from the large field view SEM image are given in columns from left to right.

As shown in FIG. 30, when CO (NO) in the mixture was assembled₃)₂3010 concentration of the composition to SiO in the assembly solution₂The degree of order gradually decreased as the 0 mol% (FIG. 30 view A) of the precursor increased to 10 mol% (FIG. 30 view B) and 20 mol% (FIG. 30 view C), characterized by broadening of the peak and loss of intensity in the RDF plot in 3004. This increase in disorder is attributed to the growth of negatively charged silica on the cationic cluster, resulting in increased colloidal polydispersity and reduced stability by the ligands, as well as electrostatic shielding and possible flocculation events due to the complexing of metal ions with the exposed ligands on the different colloids. This behavior was demonstrated for PVP and PEG coated colloids, which were stabilized by steric and electrostatic interactions. Andin contrast, in some embodiments, while colloids terminated with carboxylate, sulfonate, and amine groups may also be disordered, the degree of disorder is not dependent on the loading of the metal ion and cannot be adjusted. In some embodiments, for such non-sterically stabilized colloids, the electrostatic shielding brought about by the metal cations may induce order/disorder dichotomy rather than an adjustable gradient.

In some embodiments, the methods described herein allow decoupling the structure and composition of the IO in a modular fashion. In some embodiments, ions may be introduced into the final IO, while in other embodiments, ions may be used only as a structuring agent and removed prior to calcination. For example, a polar organic solvent such as isopropanol may dissolve cobalt salts from the assembled structure prior to calcination, resulting in pure silica IO having a desired degree of order. In some embodiments, dissolution results only in part in a matrix having a particular degree of "doping". In other embodiments, the particular ions may be deposited within the structure (rather than being removed) prior to calcination. All of this affects the chemistry of the matrix-pore and matrix-NP interfaces of the catalyst and thus the catalyst characteristics.

In addition to the aspects already discussed, modular control of the material, size and surface chemistry of NPs and colloids can create higher-order regions of catalytic domains within the structure, as shown in figure 9. Specifically, for example, according to some embodiments, two sets of the same size colloids modified by different NPs (e.g., having different associated properties due to specific interactions between the colloids) may form regions of different reactivity. In some embodiments, this provides an additional level of control for specifying reactive coupling, mass transfer, and heat transfer and dissipation. In some embodiments, selecting NP-decorated particles with different sized colloids and different NPs may react differently in specifically designed pore sizes. As an example, one skilled in the art would expect that similar to size exclusion chromatography, selectivities such as oxidation, reduction (e.g., hydrogenation or hydrogenolysis), cleavage reactions can be achieved between components of a mixture of larger and smaller sized polymer or oligomer molecules (natural or synthetic) containing the same or similar reactive groups. In addition, the size and interconnectivity of the individual pores affects the time interval during which reactants reside in the vicinity of a particular chemical microenvironment and/or catalytic center. Thus, in some embodiments, pore size and interconnectivity may be applied to enhance selectivity to particular products by size exclusion/allowance or preferential residence in a predetermined microenvironment.

Co-assembly of NP-decorated particles with multiple transition metal oxide precursors

In the example of the catalytic IO structure described above, the matrix material is, for example, amorphous silica, which may provide an inert, stable structural scaffold. In some embodiments, metal oxides other than silica (MOx), particularly in combination with catalytic NPs and other techniques discussed herein, can be incorporated with the ability to create composite structures by performing functions such as adsorption of reactive species, direct participation in redox chemistry, influencing mechanical and thermal stability, and adjusting their optical properties.

4.1 Synthesis of IO Using transition Metal oxides

Formation of high quality IO using sol-gel based transitional MOx precursors can be challenging because densification during hydrolysis, drying, and calcination can produce a cracked structure. The synthesis methods described herein in some embodiments employ precursors having nanocrystalline and amorphous phases to achieve a balance between viscoelastic forces and minimal volume shrinkage during EISA. Methods developed to assemble high quality IO materials in thin film and PB form using various transition metal oxides are discussed herein in some embodiments. In some embodiments, examples of such metal oxides include titania, alumina, and zirconia structures as shown in fig. 31. IO structures with macroscopically crack-free ordered domains are important for photocatalytic applications, particularly those that rely on photon enhancement provided by slow light. High quality structures may also provide a good test platform to describe the effects of catalytic contributing complications such as diffusion and dissipation, as they may minimize the number of variables and make systematic comparisons between different systems with defined characteristics.

FIG. 31 shows IOs in the form of thin films and photonic spheres (PB) made from different metal oxide (MOx) materials. Views A-C give electron microscope images of the thin film IO of titanium dioxide (view A), aluminum oxide (view B) and zirconium oxide (view C). The top row 3110 of views a-C shows low magnification SEM images showing large area crack-free films according to some embodiments. The lower row of images 3120 of views a-C shows an enlarged SEM of the pore structure on the left and a TEM image of each nanocrystal precursor on the right. Views D-F give SEM images (top row 3130) of a set of PBs made from silica (view D), titania (view E) and alumina (view F) and enlarged views of their porous networks (bottom row 3140).

In some embodiments, the physical and chemical properties of the structure can be further tailored by introducing multiple MOx materials simultaneously in addition to a single MOx composition. For example, in some embodiments, a hybrid sample of silica-titania may be prepared by pre-hydrolyzing the silica and titania precursors separately before adding them to the colloid and performing co-assembly, allowing for consideration of the relative kinetics of the sol-gel transition and EISA of the matrix precursors (fig. 32). FIG. 32 shows hybrid silica-titania inverse opals. View (a) gives SEM images of different mixtures (ratio is the molar ratio of titanium dioxide to silicon dioxide precursor), indicating that increasing the silicon dioxide content results in a film with higher uniformity (scale bar 20 μm). The inset shows a higher magnification SEM image at a scale bar of 500 nm. View (B) shows STEM images (scale bar 500nm) of silica-titania hybrid IO. The inset shows the X-ray spectral EDS scans of different elements (O, Ti, Si) taken along the indicated lines in the STEM image. View (C) gives an optical micrograph (scale bar 50 μm) comparing the IO color of pure silica, titania and silica-titania hybrids in air (upper row 3210) and after soaking in water (lower row 3220). As shown by compositional analysis performed by energy dispersive X-ray spectroscopy (EDS) line scanning and Scanning Transmission Electron Microscope (STEM) imaging (view B of fig. 32), the titanium dioxide and silicon dioxide phases were uniformly dispersed in nano-crystalline domains throughout the matrix. An advantage of the synthesis strategy described herein for producing hybrid background matrices in some embodiments is the formation of crack-free IO, provided that the assembly comprises at least 25 mol% of a silica precursor that provides structural integrity to the assembled hybrid material, which is not possible with sol-gel synthesis of titania alone, because the less reactive silica precursor moderates the more reactive titania precursor.

In some embodiments, different combinations of matrix materials and NPs enable tuning of properties, including light-induced charge separation and recombination, thermal expansion, heat transfer, and mechanical response, to enhance various catalytic chemical reactions. For example, in some embodiments, the Refractive Index (RI) in a silica-titania hybrid is controlled to range from silica (RI 1.4) to anatase titania (RI 2.4) by varying the relative concentrations of the two materials in the IO (FIG. 32 view A). RI can affect several optical properties associated with photocatalysis, such as the location of the photonic bandgap, which in turn can affect the efficiency of light absorption, as discussed briefly in the sections below. Additionally, in some embodiments, the increased RI of the silica-titania hybrid matrix upon saturation with a liquid may provide the ability to maintain optical contrast (fig. 32 view C), which in some embodiments is critical for solution-phase photocatalysis (note that no or only highly suppressed photonic properties are observed in a liquid medium due to negligible RI contrast between the pure silica matrix and the bulk liquid). For example, as shown in view C, TiO-containing₂In contrast to SiO, which retains their color when soaked in water due to the high contrast of RI between the matrix and the pores₂The color of the IO disappears. Additionally, in some embodiments, the uniformly dispersed silica phase may be selectively etched away from the titania matrix, resulting in the formation of two levels of porosity in the remaining titania phase.

In some embodiments, these synthetic strategies make it possible to introduce in combination a wide range of NPs into an IO composed of a single or hybrid MOx matrix material, thereby creating a catalytic structure library comprising both thin film and PB forms in various combinations. Examples of titania and alumina membranes containing Au and Pt NPs are shown in fig. 33, and examples of titania PB containing Au NPs are discussed in the next section.

Fig. 33 shows NP-decorated IO films formed from different metal oxides according to some embodiments. Views A and B show titania films containing Au (view A) and Pt (view B) NPs. Views C and D show aluminum oxide films containing Au (view C) and Pt (view D) NPs. Each of views a-D contains a schematic of the pore portion indicating the matrix and NP materials (top left of views a-D), SEM of the film (top right of views a-D), and EDS scan of the film (bottom of views a-D) to confirm the composition of the different samples. In all cases, a strong silicon signal was observed in the EDS due to the IO grown on the silicon substrate.

4.2 Modular Process for designing NP-decorative template-photocatalyst in Photonic sphere form

In some embodiments, the multi-level degrees of freedom disclosed herein for tailoring catalytic material structure and composition can create a platform for synthesizing highly complex photocatalytic systems. On a macroscopic scale, for example, the sphere of the PB is chosen (fig. 34 view a) to make the photon response independent of the illumination angle, which in some embodiments is important to maintain a continuous response, for example, when the particles are free floating in solution and thus rotating. As discussed, in some embodiments, the pore shape and size determined by the template colloidal particles and the calcination conditions are selected to affect mass transfer and photonic effects. In some embodiments, the composition of the background matrix may be selected to determine the photoactivity, catalytic properties, thermal and mechanical properties, and RI, and thus the intensity and wavelength dependence of the photonic effect. Indeed, fig. 34, view B, shows an embodiment in which the photoactivity is higher with PB prepared from titania than with the standard nanocrystalline titania photocatalyst P25 over a wide pore size range. In some embodiments, higher photoactivity may be attributed to increased light absorption efficiency through multiple scattering and slow light effects as well as spatial limitations, as all of these extend the catalyst reactant interaction time. In some embodiments, these parameters disclosed herein are used as a basis for selecting various parameters that affect catalytic activity.

In addition, these parameters provide a ramp for optimizing the various photocatalytic reactions of application-tailored photocatalytic IO containing functional metal NPs. In some embodiments, it is desirable to incorporate metallic NPs into photoactive materials because they can provide many benefits in photocatalytic reactions. For example, the motivation for including these NPs is to extend light absorption into the visible region. In some embodiments, various types of moxs, including titanium dioxide, can be selected or avoided because they are wide band gap semiconductors that can only absorb light in the UV region. In some embodiments, plasmonic metal NPs such as gold or silver may be chosen to overcome this limitation because they are capable of absorbing visible light, the generated "hot electrons" can then be transferred to MOx to facilitate the oxidation/reduction reaction. Such enhanced light absorption is particularly beneficial for embodiments such as practical applications where the utilization of a large portion of the solar spectrum is critical. Another advantage of metallic NPs in some embodiments is that they may be reactive in nature, which may enhance photocatalysis occurring through the background matrix, or allow for new reactions to occur in conjunction with the background matrix. In addition, plasmonic metal NPs are excellent photo-thermal converters and, in some embodiments, can be used in processes that require localized heating, effectively contributing thermal energy to the reaction. The NP-decorated template approach provides a natural route to incorporate these metallic NPs into the IO with photoactive background matrix, as shown for the case of titanium dioxide in views C and D of fig. 34. Any of these concepts can be selected, alone or in combination, to achieve the desired catalytic activity for a particular application.

FIG. 34 shows the photocatalytic effect of PB using colloid and NP-decorated particles as templates. The schematic of view (a) gives the general principles and advantages of photocatalyst design using PB according to some embodiments. The uniformity of catalytic macroparticle size results in efficient material utilization, uniform mass transfer, and optical performance. In some embodiments, the matrix may be selected to be photoactive. In some embodiments, control of pore size and its periodicity results in optimized fluid flow and optical properties such as slow photon effects. In some embodiments, the composition of the metal nanoparticles and their location determine the efficiency of the photocatalytic performance. View (B) gives experimental measurements of methylene blue degradation and specific surface area-normalized rate constants for different sizes of titanium dioxide PB (pore size in nanometers as measured by SEM is given on the x-axis) and compared to commercially available and synthesized titanium dioxide nanocrystals P25 and NC, respectively. The error is given in standard deviation. The Y-axis is the observed rate constant extracted from the kinetic data. View (C) gives an SEM image of titania PB incorporating Au NP. (D) The view gives an enlarged SEM image of the designated area showing that the gold nanoparticles are partially embedded within the titania matrix, mainly at the pore interface, as evidenced by the built-in TEM image. As discussed above, partially implanted particles are particularly stable in structure and heat.

5. Post-modification of catalytic structures

In some embodiments, each designed template catalytic structure may further serve as a basis for creating a library of catalytic materials for a system in which new substrates and metal compositions as well as macroscopic patterns, reactivity gradients, and fluid properties are introduced by applying a post-modification strategy, such as shown in fig. 25. In some embodiments, incorporating post-modification strategies may increase the freedom of all preparation stages by decoupling the requirements of the co-assembly process (i.e., the choice of components applied in the co-assembly process, the overall assembly structure, and the location of incorporation of NPs) from the final composition and fine geometry of the template catalytic structure.

Fig. 25 presents a schematic and experimental data describing different post-modification options for the template catalytic structure. View (a) schematically shows the matrix-pore interface formed by the decorative template particle (top right) 2501 and the raw raspberry (bottom left) 2502 templates. The round spheres 2503 in 2501 are metal nanoparticles, the round spheres in 2505 are ions, and the shaded upper left portion (2504) of each of 2501 and 2502 is a background matrix. The arrows in view a point to examples of various post-modification schemes that may be used with the catalytic system. VisionPanel (B) shows NP post-modification options including solution/vapor growth of NPs and deposition of shells, electrochemical displacement, and thermally induced phase transition, according to some embodiments. View (C) gives an experimental example of the thermally induced phase transformation schematically represented in view B (bottom) according to some embodiments, including SEM2521 of 20 mol% cobalt-silica IO after heat treatment at 900 ℃ and indicating the formation of two cobalt species CO₃O₄And CO₂SiO₄XPS spectrum 2522. Built-in inset shows CO embedded into IO wall₃O₄The TEM 2523 of the nanocrystals characterized by a lattice spacing of 0.246nm (confirmed by FFT 2524). (D) The figures present schematic diagrams of patterned surface modifications, in accordance with some embodiments. Line 2525 represents the chemical functionalization of the pore surface in selected areas, allowing local wetting by the growth solution and patterned growth of NPs upon soaking. (E) The figure gives an experimental demonstration of selective particle growth schematically represented in figure (D), giving an optical image of patterned Au NP-containing silica IO with locally grown Au NPs upon saturation with an Au growth solution according to some embodiments (the regions with additional grown particles are darker in color compared to the unaltered regions functionalized after with hydrophobic ligands). The difference in size of the NP in different regions can be seen in TEM images taken of the corresponding regions. View (F) gives an SEM picture of the vertical gradient of particle size, with the NPs tapering from top to bottom due to the slow diffusion of the growth solution relative to the reduction kinetics. View (G) gives a schematic depiction of post-modifications that may be used for the substrate, including thermally induced phase transitions, selective etching, and conformal chemical transformations. View (H) gives an experimental example of the conformal chemical transformation shown in view (G). According to some embodiments, SEM (left column) and TEM (right column) images of the original silica IO (top) and the material in which the reaction conversion was performed are given.

5.1 post-modification of the catalytic centers

In some embodiments, NPs may be further grown by liquid phase reaction, A L D or CVD to produce larger particles of single or multiple metal compositions with a core-shell or uniform structure (FIG. 25, view B.) in some embodiments, this will be achieved when growth conditions are selected such that the rate of metal deposition on the NPs exceeds their deposition on the background matrix material.

The size of NPs on the NP-decorated colloid can be selected to have a significant impact on colloid assembly, determining whether the final IO has a highly ordered crystalline structure or a random distribution of pores, as discussed in section 3. According to some embodiments, the ability to vary the size and composition of NPs after an assembly step allows for the formation of NPs with specific catalytic and structural properties to be decoupled from the co-assembly process. In some embodiments, this may provide the opportunity to achieve a controlled degree of order by, for example, applying template colloidal particles decorated with small NPs and subsequently growing the NPs to the desired size.

In the case of the protoraspberry, in some embodiments, the ionic species introduced can also be adjusted after co-assembly, again decoupling their catalytic activity, distribution, crystallinity, and particle size from their effect on structure. Specifically, in some embodiments, the heat treatment may induce a phase change of catalytic centers distributed at the surface of the pores. For example, as shown in view C, calcination at 900 ℃ results in the formation of crystalline cobalt oxide NPs embedded at the surface of the pores of the silica matrix. In some embodiments, the ions preferentially diffuse to the pore interface where, upon contact with air, they deposit as cobalt oxide nanocrystals. View C shows the SEM2521 after IO heat treatment formed, along with TEM 2523, FFT 2524, and XPS 2522 of representative nanocrystals. Direct observation and confirmation by FFT analysis correspond to CO₃O₄Has a lattice spacing ofXPS surface analysis indicated that cobalt exists in two oxidation states (II and III, view C). The CO 2p peaks at 779 and 789ev are CO³⁺Evidence of (1) with pure CO₃O₄The measurements for the control samples were consistent. The strong peaks with corresponding satellite peaks at 782ev and 798ev were identified asCO₂SiO₄Tetrahedral CO of the form₂ ⁺。

5.2 chemical post-modification of the pore surface

In some embodiments, different chemical functional groups may be bound to the pore surfaces of the IO, resulting in engineered surface energy or specific reactive species binding, respectively modulating the kinetics and specificity of liquid saturation and movement or reaction throughout the structure (fig. 25, view D). In some embodiments, patterns of wettability and catalytic activity, both horizontally across the IO (fig. 25 view E) and vertically across its depth (fig. 25 view F), may be achieved by chemical functionalization to allow for engineered IO systems with controlled hydrodynamics and defined region-dependent catalytic performance. In some embodiments, the wettability gradient can also enable patterning of NP post-modifications by creating selective regions where the growth solution can penetrate into the porous network. Such gradients are valuable for establishing macroscopic catalytic systems in which multiple reactions run in parallel or sequentially, as well as microfluidic and chip experimental devices.

5.3 post-modification of the base Material

In some embodiments, post-modification of background matrix composition, crystallinity, roughness, and porosity provides additional degrees of freedom to design the functional range of IO (fig. 25 view G). According to some embodiments, methods such as thermal treatment, selective deposition, selective etching, and conformal chemical conversion may be applied to achieve these modifications. For example, in some embodiments, thermal treatment of titanium dioxide IO may be applied to adjust crystal size, thereby adjusting surface roughness and phases of the material (including amorphous, anatase, or rutile). In some embodiments, specific components in an IO multi-material background matrix can be selectively etched to engineer IO with hierarchical porosity, remove impurities, or simplify synthesis complexity, where one material is used as a structuring agent and the other material is a catalytic species or a species of other practical importance, such as described above in the case of hybrid silica-titania IO or ion incorporation into a silica matrix.

In some embodiments, another of the substrates is modifiedThe opportunity is to apply a conformal chemical transformation from a material that has already established a co-assembly to another material that is either not feasible (e.g., due to high cost) or elusive (e.g., due to lack of available precursors). In some embodiments, redox and ion exchange reactions can be used to convert 3D silica structures with micron and submicron features into many other materials (fig. 25 view H), including porous silicon, magnesium oxide (MgO), titanium dioxide, titanium oxyfluoride (TiOF)₂) And the like. For example, for catalysis, a biologically produced TiOF of silica diatom frustules may be employed in some embodiments₂A replica. Also, in some embodiments, Si may be applied as a photocathode by itself or in combination with other materials. In this case, the microstructure of the silicon brings the silicon surface close to the light absorption sites, thereby minimizing the common problem of recombination of photogenerated electron/hole pairs in bulk Si before they can reach the reaction surface.

6. Modification of macroscopical industry-related substrates

Porous materials are widely used in the scientific and engineering fields. The specific combination of pore size, geometry, interconnectivity and their surface chemistry determines the unique properties of the porous material. According to the classification of the International Union of Pure Application Chemistry (IUPAC), materials with pore sizes less than 2nm are defined as micropores; the material with the pore diameter between 2nm and 50nm is mesopores; and the material with the pore diameter larger than 50nm is macroporous. Micropores and mesopores can be used to obtain high specific surface area within the material, while mesopores and macropores can reduce tortuosity and promote mass transfer within or through the material. Porous materials with high specific surface area and easy diffusion are required for various application fields. Their preparation remains challenging.

The design and fabrication of hierarchical ordered porous materials containing pores of multiple length scales (from sub-nanometers to millimeters) is beneficial for a variety of uses, including adsorption, separation, energy conversion and storage, catalysis, sensing, electronics, construction, drug delivery, and tissue engineering. These materials may include a wide range of pore sizes, such as nanometers, tens of nanometers, hundreds of nanometers, microns, tens of microns, and/or hundreds of microns. Industrially important devices such as catalytic converters and supports, filters, membranes, reactors, foams and certain types of cells, fuel cells and photovoltaic cells, generally rely on macroscopic porous monolithic structures (also referred to herein as "monoliths"). Porous monolith structures (e.g., for use in flow-through catalytic or separation systems) have lower back pressures, higher permeabilities, and better performance than packed beds. In addition, the porous monolithic structures have high mechanical, chemical and thermal stability. In many cases, the use of monolithic structures requires their modification.

The surface of the macroporous monolith can be modified with a nanostructured or microstructured coating in order to increase its surface area and/or incorporate functional materials (e.g., metal or metal oxide nanoparticles) into the macroporous monolith. Such modified monoliths are generally more efficient and cost effective than other porous forms such as powders or pellets. Methods of modifying the bulk surface may include wash coating, impregnation, deposition of metal oxide nanoparticles, and growth of carbon nanofibers. Methods of modifying monoliths have a number of disadvantages, including: 1) difficulty in producing rationally designed systems with well-defined structure, composition, and geometric characteristics, including porosity, uniformity, and degree of order; and 2) difficulty in controlling the incorporation of functional components such as metal nanoparticles, including their location, geometry, and composition.

In some embodiments, the ability to rationally design complex porous functional materials, such as catalytic supports, by modeling and evaluating their physical properties and reactivity, is highly desirable for the development and optimization of practical systems. Despite their potential advantages, it remains challenging to produce a hierarchically structured macroscopic monolithic material while controlling its composition and multimodal porosity.

In some embodiments, colloidal-based porous materials (CBPMs) have many advantages in terms of controllability of their composition and porosity, including but not limited to, micropores, mesopores, and macropores. Additionally, in some embodiments, the preparation of CBPMs allows for the tuning of the functional properties of porous materials by selecting a matrix material (e.g., silica, titania, alumina, mixtures thereof, etc.) using sol-gel methods or nanocrystal precursors, and by incorporating additional components (e.g., functional nanoparticles).

According to some embodiments of the present invention, the catalytically active species and/or other functional components may be independently selected and controllably introduced in desired amounts and locations within the porous structure. In addition, the modularity of the porous structure obtained using the methods described in the embodiments herein allows for the introduction of multiple types of functional components, thereby allowing for the rational design of complex catalytic systems or other functional systems.

In some embodiments, CBPM formation is generally self-organizing driven by sub-micron polymer colloids, the use of a matrix precursor material to fill the voids between the colloid particles, and the subsequent removal of the particles to form an interconnected porous structure. The formation of CBPM may be carried out stepwise, in a single step, by backfilling a pre-assembled colloidal film or by co-assembling the colloid with a matrix precursor material. CBPMs are typically prepared in thin film form on flat substrates, bodies, or powders, which have limited practical application in applications such as catalysis and filtration. In addition, the manufacture of CBPM-based materials on an industrially relevant scale is often impractical, since the process is time consuming and expensive, and the resulting structures have only moderate mechanical strength.

The method of forming CBPM thin films by the co-assembly method allows for the production of thin films on substantially flat and smooth substrates. In some embodiments, these methods are ineffective for creating porous membranes within the three-dimensional network of the macroscopic porous monolith due to factors such as geometric limitations, surface tension of the colloidal dispersion, capillary forces, non-uniformity of surface energy, and roughness of the matrix. Thus, the porous coating either fails to grow or "caps" the pore openings of the underlying porous substrate.

According to some embodiments, a method of making a hierarchical porous material includes providing a porous macro monolithic substrate having a first porosity and a first average pore size. A co-assembly mixture containing colloidal particles of NP-decorated template material and matrix precursor material is applied to the pores of a porous monolithic substrate. The NP-decorated template material is removed to form a Catalytically Templated Porous Coating (CTPC) within the porous monolithic substrate. The CTPC may have a second porosity and a second average pore size, and the second average pore size is smaller than the first average pore size. Removal of the interconnect template component provides a network of interconnected pores. The removal of the template colloidal particles may be performed by heat treatment, solvent dissolution and/or etching.

Embodiments of the present invention include the preparation of macroscopic-scale porous hybrid materials (also referred to as monoliths) supported on macroscopic porous substrates, including a wide pore size range from nanometers to millimeters, wherein a co-assembly process is applied to form catalytic-templated porous coatings (CTPCs) by modifying the porous monolith with a templating sacrificial material (also referred to herein as a "colloid"). The resulting structure combines the benefits of macro-porous materials of large dimensions (e.g., on the order of centimeters and above) with the advantages provided by CBPM. These include high specific surface area compared to pure CBPM systems, interconnected porosity, well-defined structure, controlled composition, easy fluid flow within the porous structure, and mechanical stability of the overall hybrid structure.

In some embodiments, the porous monolithic substrate may be a ceramic such as cordierite and/or include at least one of mullite, zeolite, natural clay, and synthetic clay.

In some embodiments, the porous monolithic substrate comprises at least one of a metal and a metal alloy, examples of which include stainless steel, ferritic steel (e.g., iron-chromium alloy), austenitic steel (inconel), copper, nickel, brass, gold, silver, titanium, tungsten, aluminum, palladium, and platinum.

In some embodiments, the porous monolithic substrate comprises at least one of a metal salt or a metal oxide, examples of which include silica, alumina, iron oxides, zinc oxides, tin oxides, alumina silicates, aluminum titanate, beryllium oxide, noble metal oxides, platinum group metal oxides, titania, zirconia, hafnia, molybdenum oxides, tungsten oxides, rhenium oxides, tantalum oxides, niobium oxides, vanadium oxides, chromium oxides, scandium oxides, yttrium oxides, lanthanum oxides, cerium oxides, thorium oxides, uranium oxides, and rare earth oxides.

In some embodiments, the porous monolithic substrate comprises a combination of a composite metal and a metal oxide, such as a cermet.

In some embodiments, the porous monolithic substrate comprises a polymer, such as polyurethane, and/or comprises at least one of: polystyrene, poly (methyl methacrylate), polyacrylates, polyalkylacrylates, substituted polyalkylacrylates, polystyrene, poly (divinylbenzene), polyvinylpyrrolidone, poly (vinyl alcohol), polyacrylamide, poly (ethylene oxide), polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, other halogenated polymers, hydrogels, organogels, chitin, chitosan, random and block copolymers, branched, star and dendritic polymers and supramolecular polymers.

In some embodiments, the porous monolithic substrate comprises a semiconductor comprising at least one of: silicon carbide, silicon, germanium, tin, silicon doped with a group III element, silicon doped with a group V element, germanium doped with a group III element, germanium doped with a group V element, tin doped with a group III element, tin doped with a group V element, and transition metal oxides.

In other embodiments, the porous monolithic substrate is electrically conductive.

In some embodiments, the porous monolith substrate comprises a natural material, for example comprising at least one of cellulose, natural rubber (e.g., latex), wool, cotton, silk, flax, hemp, flax fibers, and feather fibers.

In some embodiments, the CTPC comprises at least one of: oxides, metals, semiconductors, metal sulfides, metal chalcogenides, metal nitrides, metal pnictides, organometallic compounds, organic materials, natural materials, polymers, and combinations thereof.

In some embodiments, the CTPC comprises at least one of: silicon dioxide, aluminum oxide, titanium dioxide, zirconium oxide, cerium oxide, hafnium oxide, vanadium oxide, beryllium oxide, noble metal oxides, platinum group metal oxides, titanium dioxide, tin oxides, molybdenum oxides, tungsten oxides, rhenium oxides, tantalum oxides, niobium oxides, chromium oxides, scandium oxides, yttrium oxides, lanthanum oxides, thorium oxides, uranium oxides, and rare earth oxides.

In some embodiments, the method further comprises pretreating the porous monolithic substrate prior to forming the CTPC. The pretreatment may include applying an adhesion promoter to the porous monolithic substrate, and/or activating a surface of the porous monolithic substrate.

In some embodiments, the co-assembly mixture further comprises a functional component. For example, the functional component may include at least one of: metal nanoparticles, metal alloy nanoparticles, semiconductor nanoparticles, metal oxide nanoparticles, mixed metal oxide nanoparticles, metal sulfide nanoparticles, and combinations thereof. In some embodiments, the functional component is a biologically derived material, such as an enzyme or protein.

In some embodiments, the co-assembly mixture further comprises nanoparticles, which may include, for example, at least one of: metal nanoparticles, metal alloy nanoparticles, semiconductor nanoparticles, metal oxide nanoparticles, mixed metal oxide nanoparticles, metal sulfide nanoparticles, and combinations thereof. In some embodiments, the nanoparticles are introduced by decorating the template material with functional nanoparticles prior to applying the co-assembly mixture. In other embodiments, the nanoparticles are introduced during at least one of the following: applying a co-assembly mixture; and subsequent modification of CTPC.

In some embodiments, the co-assembly mixture further comprises a metal salt.

In some embodiments, the co-assembly mixture further comprises a complex salt with at least one of: alkali metal, alkaline earth metal, group (III) metal, and transition metal salts.

In some embodiments, the co-assembly mixture further comprises a biomaterial.

In some embodiments, the matrix precursor material comprises a sol-gel precursor.

In some embodiments, the template material is a colloidal particle comprising at least one of: polymers, colloids, biopolymer colloids, organometallic compounds, supramolecular self-assembled colloids, and combinations thereof. In other embodiments, the colloidal particles comprise at least one of: random copolymers, block copolymers, branched polymers, star polymers, dendrimers, supramolecular polymers, and combinations thereof. In other embodiments, the colloidal particles comprise at least one of: metal organic frameworks, inorganic polymers, organometallic complexes, and combinations thereof. In other embodiments, the colloidal particles comprise at least one of: polymeric fibers, biopolymer fibers, fibers containing organometallic compositions, supramolecular self-assembled fibers, and combinations thereof. In other embodiments, the colloidal particles comprise at least one of: spherical particles, elongated particles, concave particles, amorphous particles, polyhedral particles, and combinations thereof.

In some embodiments, the method further comprises modifying the CTPC with a functional component.

In some embodiments, the hierarchical porous materials can be used in the manufacture of sensors, photocatalysed, photocatalytic degradation of gas and liquid phase contaminants, coherent scattering media, luminophores, random laser or other optical applications, such as smart displays or other electrochromic materials, the preparation of cosmetics, the preparation of pharmaceuticals and food, drug delivery, fluidic devices, tissue engineering, membranes, filtration, adsorption/desorption, support media, as a catalytic media or support, catalytic reactions such as oxidation, hydrogenation, dehydrogenation, hydration, dehydration, isomerization, oxidative coupling, dehydrocoupling, hydrosilylation, amination, hydroamination, C-H activation, intercalation, decomposition, redox or polymerization/depolymerization reactions, selective catalytic reactions, energy storage, batteries or fuel cells, acoustic devices, and/or patterned structures.

In some embodiments, the hierarchical porous materials may be used for multiple catalytic reactions within the same structure, such that activation of a cascade or multi-step catalytic reaction may be achieved.

In some embodiments, the hierarchical porous material comprises a three-dimensional macroporous matrix having a first porosity of 10 microns to 1 centimeter, and comprising a network of interconnected pores extending throughout the thickness; and a porous membrane deposited on at least 30% of the combined surface area of the pores of the macroporous matrix, the porous membrane having a thickness of 50 nanometers to 500 micrometers, and a second porosity of 0.5 nanometers to 2 micrometers. The macroporous matrix may comprise a ceramic such as cordierite. In some embodiments, the macroporous matrix comprises at least one of: metals, metal alloys, metal salts, metal oxides, semiconductors, synthetic polymers, biopolymers, and natural materials.

In some embodiments, the porous membrane comprises one of: oxides, metals, semiconductors, metal sulfides, metal chalcogenides, metal nitrides, metal pnictides, organometallic compounds, organic materials, natural materials, polymers, and combinations thereof. In other embodiments, the porous membrane comprises one of: silica, alumina, titania, zirconia, ceria, hafnia, vanadia, beryllia, noble metal oxides, platinum group metal oxides, titania, tin oxides, molybdenum oxides, tungsten oxides, rhenium oxides, tantalum oxides, niobium oxides, chromium oxides, scandium oxides, yttrium oxides, lanthanum oxides, thorium oxides, uranium oxides, other rare earth oxides, and combinations thereof.

In some embodiments, the hierarchical porous material further comprises a functional component, which may include one of: metal cations, metal salts, metal oxides, and organometallic complexes. In some embodiments, the functional component is a nanoparticle. In some embodiments, the functional component is a biologically derived material, such as an enzyme or protein.

In some embodiments, the functional component is introduced by decorating the template material with nanoparticles prior to applying the co-assembly mixture. In other embodiments, the functional component is introduced during at least one of the following: applying a co-assembly mixture; and subsequent modification of CTPC.

In some embodiments, the hierarchical porous material exhibits catalytic activity. The catalytic activity may include forming at least one of: methanol and ammonia; oxidizing at least one of: volatile organic compounds and carbon monoxide; oxidation-reduction reaction of nitrogen oxides; oxidation of sulfur oxides; the breakdown of particles and microbial particles such as bacteria, viruses, dust mite allergens, mold and fungal spores; and the decomposition of ozone.

In some embodiments, the sensor comprises a hierarchical porous material. The hierarchical porous material may include: a three-dimensional macroporous matrix having a first porosity of 10 microns to 1 cm, and comprising a network of interconnected pores extending through the thickness; and a porous membrane deposited on at least 30% of the combined surface area of the pores of the macroporous matrix, the porous membrane having a thickness of 50 nanometers to 500 micrometers, and a second porosity of 0.5 nanometers to 2 micrometers.

In some embodiments, the filtration membrane comprises a hierarchical porous material comprising: a three-dimensional macroporous matrix having a first porosity of 10 microns to 1 cm, and comprising a network of interconnected pores extending through the thickness; and a porous membrane deposited on at least 30% of the combined surface area of the pores of the macroporous matrix, the porous membrane having a thickness of 50 nanometers to 500 micrometers, and a second porosity of 0.5 nanometers to 2 micrometers.

6.1. Preparation of macro-level porous hybrid material

The mixture for co-assembling CTPC may combine template materials (e.g., colloidal particles), matrix precursors, and additional components described in some embodiments below, according to the methods described herein.

Successful application of CTPC to a macro-porous monolith according to the methods described in some embodiments herein may be facilitated by one or more of the following: (1) surface activation of the porous substrate monolith (e.g., by exposing the porous substrate monolith to elevated temperatures and/or an etchant and/or plasma); (2) carrying out surface modification by using a bonding agent; and (3) adding a surfactant and/or dispersant and/or a liquid miscible with the copolymeric mixture effective to reduce the surface tension of the mixture and/or enhance its stability to specific ingredients and/or deposition conditions, and to form CTPC with improved uniformity.

In some embodiments, the methods described herein include forming a coating by co-assembling in solution, evaporating the solvent, and/or passing the co-assembled mixture through a substrate.

In some embodiments, the methods described herein include pretreatment with etchants such as acids, bases, and oxidizing agents (e.g., hydrogen peroxide, ozone, plasma).

In some embodiments, the methods described herein include forming a coating by co-assembly in solution and assisted with electrodeposition and/or magnetic deposition.

In some embodiments, the substrate modified with CTPC is immersed in the co-assembly mixture.

In some embodiments, the co-assembly mixture is deposited by spraying.

In some embodiments, the hierarchical porous structure is obtained after removal of the template particles. The treatment methods may include calcination, dissolution, etching, evaporation, sublimation, phase separation, and combinations thereof.

In some embodiments, the porosity of the hierarchical porous material prepared according to the methods described herein may be said to have a hierarchical porosity that transitions from millimeter scale through macropores to mesopores and/or micropores. In some such embodiments, a hierarchical porous material or structure includes a layer or region having a first porosity corresponding to a first type of template material (e.g., size and/or shape), and a layer or region having a second porosity corresponding to a second type of template material (e.g., size and/or shape). In some embodiments, the first and second porosities may differ in size (e.g., pore size) and/or shape. In some embodiments, the hierarchical porous material may also include one or more additional layers or regions having additional porosity values (e.g., a third porosity, a fourth porosity, etc.), which may also differ in size and/or shape from the first and second porosities. In some embodiments, different porosities (e.g., a first porosity, a second porosity, a third porosity, a fourth porosity, etc.) may be present in the same layer or region of the hierarchical porous material. In some embodiments, a layer or region of the hierarchical porous material has a respective porosity that increases along a direction of growth of the hierarchical porous material. In some embodiments, a layer or region of the hierarchical porous material has a porosity that decreases along a growth direction of the hierarchical porous material and/or a porosity that is intermixed along the growth direction. In some embodiments, the hierarchical porous material layer deposited on the substrate having macropores may have two or more of macropores, mesopores, and micropores at the same time.

6.2. Monolithic material

In some embodiments, the porous monolith comprises or is defined within a material having macropores (e.g., "honeycomb" structures, meshes, foams, textiles, and paper), and the coatings described herein are applied such that they cover at least 30% of the walls of the macro-porous material.

In some embodiments, the monolith may be made of ceramic materials such as cordierite, mullite, zeolites, and natural or synthetic clays.

In some embodiments, the monolith can be made from metal salts or metal oxides, such as silica, alumina, iron oxides, zinc oxides, tin oxides, alumina silicates, aluminum titanates, beryllium oxides, noble metal oxides, platinum group metal oxides, titania, zirconia, hafnia, molybdenum oxides, tungsten oxides, rhenium oxides, tantalum oxides, niobium oxides, vanadium oxides, chromium oxides, scandium oxides, yttrium oxides, lanthanum oxides, ceria, thorium oxides, uranium oxides, other rare earth oxides, and combinations thereof.

In some embodiments, the monolith can be made of one or more metals and/or metal alloys, such as stainless steel, ferritic steel (e.g., iron-chromium alloys), austenitic steel (chromium-nickel alloys), copper, nickel, brass, gold, silver, titanium, tungsten, aluminum, palladium, platinum, and combinations thereof.

In some embodiments, the bulk material may be made of a semiconductor, such as silicon carbide, silicon, germanium, tin, silicon doped with a group III or group V element, germanium doped with a group III or group V element, tin doped with a group III or group V element, transition metal oxides, and combinations thereof.

In some embodiments, the monolith can be made of a polymer, such as polyurethane, polystyrene, poly (methyl methacrylate), polyacrylate, polyalkylacrylate, substituted polyalkylacrylate, polystyrene, poly (divinylbenzene), polyvinylpyrrolidone, poly (vinyl alcohol), polyacrylamide, poly (ethylene oxide), polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, other halogenated polymers, hydrogels, organogels, and combinations thereof. Other polymers of different structures may also be applied, such as random and block copolymers, branched, star and dendritic polymers and supramolecular polymers.

In some embodiments, the monolith may be made of one or more natural materials, such as cellulose, natural rubber (e.g., latex), wool, cotton, silk, linen, hemp, flax fibers, and feather fibers.

In some embodiments, the monolithic material may be made of a combination of any of the above materials. For example, cermets formed from a combination of metals (e.g., nickel, molybdenum, cobalt, titanium, and tungsten) and their oxides, borides, and carbides may be used to form the monolith.

6.3. Template material

In some embodiments, the colloids discussed in section iii.6 are defined as dispersed particles or macromolecules of any shape or form (e.g., spherical or fibrous) suspended in another substance, and may also be referred to as colloidal dispersions. As used herein, the dispersed substance or particles may alternatively be referred to as "colloids" or "colloidal particles" or "NP-decorated template material". Many different types of colloidal particles can be used to practice the methods described herein. The gel may be made of various materials or mixtures of materials. In some embodiments, to be used as a sacrificial template material, at least a portion of the colloidal material should be flammable, soluble, sublimable, or meltable during formation of the CTPC. The colloidal particle size (particle size) can be in the microporous (2nm), mesoporous (2-50nm) and/or macroporous (>50nm) grades.

In some embodiments, the dispersing substance or particle comprises a polymer colloid, a biopolymer colloid, an organometallic compound, a supramolecular self-assembled colloid, or a combination thereof.

In some embodiments, the material comprises a polymeric fiber, a biopolymer fiber, a fiber containing an organometallic composition, a supramolecular self-assembled fiber, or a combination thereof.

In some embodiments, the material is a polymer and includes one or more of: poly (methyl methacrylate), polyacrylate, polyalkylacrylate, substituted polyalkylacrylate, polystyrene, poly (divinylbenzene), polyvinylpyrrolidone, poly (vinyl alcohol), polyacrylamide, poly (ethylene oxide), polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, other halogenated polymers, hydrogels, organogels, or combinations thereof. Other polymers of different structures may also be used, such as random and block copolymers, branched, star and dendritic polymers and supramolecular polymers.

In some embodiments, the material is of natural origin (biopolymer colloids), such as protein or polysaccharide based materials, silk fibroin, chitin, shellac, cellulose, chitosan, alginate, gelatin, or mixtures thereof.

In some embodiments, the material comprises one or more organometallic compounds, such as a metal organic framework, an inorganic polymer (e.g., siloxane), an organometallic complex, or a combination thereof.

In some embodiments, the size (e.g., diameter) of the template particles may be from about 1nm to tens or hundreds of microns. Some exemplary dimensions include about 1-1000nm to provide specific optical properties that are less susceptible to gravitational forces and/or improved assembly properties. Some exemplary dimensions include 200 and 50000nm to obtain porosity for specific mass transfer characteristics and/or filtration and/or catalytic applications. Depending on the application, various types of sacrificial particles may be applied.

In some embodiments, the template particles comprise colloidal dispersions of spherical, elongated, concave, amorphous, or polyhedral particles made of polymers, metals, metal oxides, supramolecular aggregates, crystals or salts of organic, inorganic, and organometallic compounds.

6.4. Base material

In some embodiments described herein, a "matrix precursor material" may be converted to a "matrix material" by one or more of the manufacturing process steps described herein, such as high temperature calcination, drying (e.g., for polymer foams), light-induced polymerization, thermal polymerization, free radical polymerization, supramolecular polymerization, other curing methods, and combinations thereof.

In some embodiments, the matrix material may be made of various materials or mixtures of materials. The choice of the matrix material may depend on its intended use and its ability of the precursor to meet the processing conditions for CTPC (e.g., its ability to form a stable mixture with other components, exhibit specific self-assembly or polymerization kinetics, and/or withstand calcination or other template removal conditions). For example, the matrix material may have catalytic activity, a stimulus response, be chemically stable, be degradable, and/or exhibit specific thermal and mechanical properties.

In some embodiments, the material comprises one or more metals, such as gold, palladium, platinum, silver, copper, rhodium, ruthenium, rhenium, titanium, osmium, iridium, iron, cobalt, or nickel, or combinations thereof.

In some embodiments, the material comprises a semiconductor, such as silicon, germanium, tin, silicon doped with a group III or group V element, germanium doped with a group III or group V element, tin doped with a group III or group V element, or combinations thereof. In some embodiments, the material comprises a conductive material.

In some embodiments, the material comprises one or more oxides, such as silica, alumina, beryllia, noble metal oxides, platinum group metal oxides, titania, tin oxides, zirconia, hafnia, molybdenum oxides, tungsten oxides, rhenium oxides, vanadium oxides, tantalum oxides, niobium oxides, chromium oxides, scandium oxides, yttrium oxides, lanthanum oxides, ceria, thorium oxides, uranium oxides, other rare earth oxides, or combinations thereof.

In some embodiments, the material comprises one or more metal sulfides, metal chalcogenides, metal nitrides, metal pnictides, or combinations thereof.

In some embodiments, the matrix may include one or more organic materials, such as polymers, natural materials, and mixtures thereof.

In some embodiments, the material is a polymeric material and includes one or more of: polyurethanes, poly (methyl methacrylate), polyacrylates, polyalkylacrylates, substituted polyalkylacrylates, polystyrenes, poly (divinylbenzene), polyvinylpyrrolidone, poly (vinyl alcohol), polyacrylamide, poly (ethylene oxide), polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, other halogenated polymers, hydrogels, organogels, and combinations thereof. Other polymers of different structures may also be applied, such as random and block copolymers, branched, star and dendritic polymers and supramolecular polymers.

In some embodiments, the material is of natural origin and includes, for example, a protein or polysaccharide based material, silk fibroin, chitin, shellac, cellulose, chitosan, alginate, gelatin, or mixtures thereof.

In some embodiments, the matrix precursor material is in the form of a sol-gel precursor, a nanoparticle precursor, or a combination thereof.

In some embodiments, the sol-gel matrix precursor material is silica, alumina, titania, and/or zirconia sol-gel.

In some embodiments, the nanoparticle precursor comprises a single nanoparticle of the above-described matrix materials or mixtures thereof.

6.5. Catalytic applications

In some embodiments, the methods described herein facilitate the formation of structures capable of catalyzing one or more reactions, such as oxidation, hydrogenation, dehydrogenation, hydration, dehydration, isomerization, oxidative coupling, dehydrocoupling, hydrosilylation, amination, hydroamination, C-H activation, intercalation, decomposition, redox, or polymerization/depolymerization reactions.

In some embodiments, the methods described herein facilitate the preparation of structures that form or otherwise exhibit selective catalytic activity for a particular product when different functional groups are present in the same matrix molecule.

In some embodiments, the methods described herein facilitate the preparation of structures that are catalytically active towards the formation of methanol and ammonia.

In some embodiments, the methods described herein facilitate the introduction of multiple catalytic functions in the same structure, such that activation of a cascade or multi-step catalytic reaction can be achieved.

In some embodiments, the methods described herein facilitate the preparation of structures for catalyzing the chemical conversion of mono-and polyunsaturated carbon-carbon and carbon-heteroatom functional groups (including di-, tri-, and aromatic bonds) and saturated hydrocarbons of different backbone structures (linear, branched, and cyclic).

Fig. 38 views a-C are a series of schematic views of a hierarchical porous material 3800 according to some embodiments. As shown in fig. 38 view a, the hierarchical porous material 3800 can include a first set of porous monoliths having dimensions on the centimeter (cm) scale and defined therein as being of the macro-porous scale (e.g., having a minimum dimension, such as a diameter, on the order of sub-millimeters to several millimeters (mm)). The walls of the monolith can include a second set of pores of a macropore level defined therein, which can have the same or different minimum size (e.g., diameter) as the first set of pores (e.g., the pores of the second set of pores can have a minimum size of >50nm) (see fig. 38, view B). The second set of porous walls may include a third set of pores defined therein, such as mesopores (2-50nm) and/or micropores (<2nm) (see fig. 38 view C). As discussed above, the porosity of the hierarchical porous material 3800 can thus be said to have a hierarchical porosity that transitions from millimeter-scale pores through macropores to mesopores and/or micropores.

Fig. 39 depicts a method of making a hierarchical porous catalytic material structure according to some embodiments, wherein a colloidal co-assembly method is applied, for example, by applying a catalytic porous material coating (e.g., inverse proteolitic membrane) described in some embodiments as a coating on a macroscopic porous substrate (e.g., cordierite, polyurethane or other polymer foams, carbon-based porous substrates, and metal substrates). More specifically, fig. 39 describes a method of preparing hierarchical porous structures using a macro-porous matrix 3902 using a co-assembly method, according to some embodiments. The substrate 3902 with large pores (D >1 μm) is pretreated by applying adhesion promoters and/or surface activation methods. Although macropores with a diameter D >11 μm are depicted in FIG. 39, other pore sizes of matrix 3902 are also contemplated (e.g., D >10 μm, etc.). The co-assembly method (step i) was then applied to modify the matrix with CTPC 3904 containing the template and matrix precursor materials. Subsequently, the colloid is removed (step ii), forming a porous membrane 3906 (having macropores, mesopores, and micropores) on the macro-porous substrate. In some embodiments, after the CTPC formation process is complete, the macroporous membrane 3906 can have an average pore size of about 50nm to 2000nm, and its matrix can include micropores and mesopores (from sub-nanometers to 50 microns). The co-assembly process allows for fine control of the composition and porosity of the formed CTPC. In particular, various precursor materials and functional components can be used to control the composition of the formed matrix, while various template components can be used to control the final porosity at the macro-, meso-, and micro-pore scale.

FIG. 40 shows an exemplary catalytic level porous material obtained by coating a cordierite substrate with the catalytic porous template material described herein. View A is a macroscopic sample of cordierite, and view B is a macroscopic sample comprising Pt/SiO₂、Pd/SiO₂And Pt/Al₂O₃Serial SEM images of the coated samples. The top row of view B includes a large field view and the bottom row is a high magnification SEM image. Individual Pd NPs embedded in the silica matrix are indicated by arrows in the inset of the corresponding SEM images.

FIG. 41 depicts the use of catalytic polypeptides according to some embodiments described hereinAn exemplary catalytic-grade cellular material obtained by coating a polyurethane matrix with a cellular template material. View A shows a partial coating with Au/SiO according to some embodiments₂A macroscopic sample of polyurethane foam of (1). The coated side on the right clearly shows a lighter color due to the coating. View B gives a large field view and high magnification SEM image of the coated portion of the sample, showing a uniform conformal coating of catalytic material over the macropores.

Fig. 42 depicts an exemplary catalytic porous material obtained by coating an electrically conductive substrate with a catalytic porous template material according to some embodiments described herein. Examples include coatings on metal (FeCrAl) substrates, indium tin oxide coatings on polyethylene terephthalate (PET) substrates, and carbon paper, showing a uniform conformal coating of catalytic material over the macropores.

FIGS. 43 and 44 are graphs utilizing 1 w% Pt/Al according to the method shown in FIG. 39, according to some embodiments₂O₃Catalytic Material modified cordierite matrix (length 3 ", diameter 1") completely oxidized methanol to CO₂And examples of Experimental results for Water samples were tested at different reactant flow rates 50m L/min (FIG. 43) and 400m L/min (FIG. 44.) catalyst activity was measured using a conventional fixed bed reactor cordierite samples were loaded into a quartz reaction tube and pretreated at a He flow rate of 25ml/min at 150 ℃ for 30min to remove any water and air, then cooled to-25 ℃₂At a rate of 10 ℃/min, the reactor temperature was raised back to 150 ℃, 10 ℃ per liter, the reaction conditions were kept constant for 1 hour to allow the catalyst to reach a stable conversion, at a low flow rate of 50m L/min, methanol to CO at room temperature₂(FIG. 43), while at a high flow rate of 400m L/min, methanol was completely combusted at 60 deg.C (FIG. 44). Low light-off temperatures even at high flow rates make these systems very useful in practical catalytic applications where a macroporous matrix was used and high flow rates were used.

FIG. 45 is a graph showing the utilization of 1 w% Pt/Al according to the method shown in FIG. 39, as applied in accordance with some embodiments herein₂O₃Catalytic Material modified cordierite matrix (length 3 ", diameter 1") completely oxidized Isopropanol (IPA) to CO₂Cordierite samples were loaded into a quartz reaction tube and pretreated by heating at 150 ℃ for 30min at a He flow rate of 25ml/min to remove any water and air, then cooled to-25 ℃ at 50m L/min containing 3 mol% IPA and 22 mol% O₂The reactor temperature was raised back to 350 ℃ at a rate of 10 ℃/min under He flow. The reaction conditions were kept constant for 1 hour for every 10 ℃ rise to allow the catalyst to reach a stable conversion. Complete conversion of IPA to CO₂Occurs at-180 deg.C (FIG. 45).

7. Discussion and prospect

Catalysis involves complex interactions of physical and chemical processes, and in practice, designing catalytic materials capable of optimizing multiple parameters simultaneously remains a challenge. As described in some embodiments herein, the application of metal-containing colloids to construct porous lattices and organize catalysts within them can provide an efficient material strategy that combines state-of-the-art techniques in nanoparticle synthesis, mesoscale self-assembly, bulk material synthesis, and post-synthesis conversion into a single platform that creates new cooperativity and opens up synthetic freedom across hierarchical scales (see fig. 35). In some embodiments, the nano-sized catalytic particles may be a number of single metal or multi-metal mixed structures or core-shell structures, the overall size of which is uniformly controlled, or may be composed of transition metal compounds having controlled crystallinity. According to some embodiments, at a microscopic scale, the sacrificial colloid can direct the positioning of the metal NPs within a single pore, enabling multiple options of uniform distribution, positioning at the pore surface, and structure, e.g., different catalysts in different pores, possibly catalysts corresponding to a particular pore size, or controlling the ratio of two or more catalysts in the same pore. Transition metal dopants having catalytic and other properties may be selectively positioned at pore interfaces or controllably distributed between the interfaces and the bulk matrix, according to some embodiments. According to some embodiments, lattice characteristics such as degree of disorder, connectivity, pore size, and shape can be fine-tuned separately on the scale of the overall structure, and a variety of bulk matrix materials and tailored composites can be applied to create combinatorial libraries of matrix and catalyst compositions. According to some embodiments, the macroscopic gradient of surface properties and reactivity can be further engineered by patterning surface chemistry, NP size, and NP composition. Finally, according to some embodiments, all of these chemical and structural choices can be applied in a variety of macroscopic forms, including thin films and dispersible SHARDS or photonic spheres.

These hierarchical features then specify the functional properties of the catalytic material, including mass transfer, heat and fluid diffusion, affinity for various reactants and products, ability to undergo redox conversion, and electronic and photonic behavior, as desired for some embodiments. For example, in some embodiments, the strategy allows for quasi-compartmentalization and spatio-temporal control of multi-step reactions. In some embodiments, the ability to place different catalysts at close distances within the pores or separate within different pores makes it possible to construct catalytic systems that take into account variations in the different intermediates in their lifetimes, diffusion rates, and compatibility with different catalysts. According to some embodiments, additional surface modification of the pores and patterned modification of the embedded catalyst can result in wettability and reactivity gradients throughout the structure that, along with tailored connectivity and pore and neck dimensions, will further direct fluid flow and optimize reaction efficiency and selectivity.

The ability to quasi-compartmental and spatio-temporal control, the ability to systematically vary multiple features, individually or in combination, and tunable photonic properties, collectively or individually, creates a powerful system for designing multiple catalytic reactions. Additionally, in some embodiments, inverse opals can be used in some embodiments as colorimetric sensors with high spatial resolution. Thus, in some embodiments, the designed catalytic material may also be used as a self-reporting system that monitors the evolution of chemical and thermal profiles over space and time as a function of different NP, pore, connectivity and matrix properties. This may allow various factors to be systematically varied and analyzed in a single system, providing a comprehensive basic understanding and toolkit for building design systems for multiple reactions.

In addition to optimizing the reaction, it is important in some embodiments that the hierarchical degrees of freedom simultaneously provide a unique set of comprehensive or exemplary means for addressing many of the practical issues involved in using these materials to address the pressing global challenge. Catalysis is almost central to support various aspects of population growth and increasingly severe energy applications and air pollution crisis in developed and developing countries: the quality of the reaction determines the efficiency and carbon emissions of power generation, fuel collection and extraction, steel production, transportation and communications infrastructure, and food, clothing and pharmaceutical production, and plays an important role in the decomposition of pollutants before and after they enter the air. Optimizing catalysis can halve energy consumption in the united states and is critical to meeting regulatory requirements and maintaining public health, but there is still a significant distance between dramatic research progress and the development of a wide range of robust and viable systems. The main obstacles are stability, cost, scalability and adaptability, each representing a complex multi-scale problem, and just as the strategy described in the embodiments herein faces.

According to some embodiments, the lifetime of the catalytic material is extended as much as possible by controlling the embedding, distribution, size and composition of the nanoparticles and the mechanical and thermal properties of the structure and matrix material. As discussed in some embodiments, a unique, particularly useful feature of NP-decorative particle co-assembly is the implantation or embedding of the NP moiety within the pore walls. This locking of the NP sites fixed to the wall and their uniform distribution make them stable against mechanical damage and thermally induced migration and fusion. In some embodiments, uniform control of NP size is important to ensure that all NPs have a sufficiently large embedded surface area, as small NPs may migrate or be translocated due to flow under reaction conditions. In some embodiments, the multi-metallic component may further stabilize the NPs against leaching, oxidation, and evaporation. On a larger scale, in some embodiments, the co-assembly process may prevent cracks that make the material susceptible to mechanical stress and heat concentration, and in some embodiments, a controlled degree of disorder may be introduced into the pore lattice to increase mechanical toughness. According to some embodiments, these design features may be complementary to a matrix material or combination thereof having the desired mechanical or thermal properties under the particular equipment and reaction conditions.

The control described in the embodiments herein may also minimize the cost and material requirements of production. Directly aligning the NPs to the pore walls and uniformly maximizing their exposed surface area can greatly reduce the need for expensive and precious metals by making substantially every NP available for catalysis rather than embedding in the bulk matrix. In addition, the control of the pore connectivity provided by the co-assembly system can avoid dead and tortuous paths that may become blocked from contacting the NP. The ability to align different metals to different pores by locating them on different NP-decorated particles further reduces the metal requirements by allowing each NP to be not only accessible but also precisely positioned for optimal use in the reaction sequence. At the same time, maximizing the exposed surface area and connectivity of the pores can reduce the amount of bulk matrix material needed, and adjusting the surface chemistry and roughness can supplement these methods by further increasing the effective specific surface area and exposure to the reactants.

In some embodiments, the ability to introduce gradients in the wettability and reactivity of the wells makes it possible to integrate a variety of catalytic processes into microfluidic and lab-on-a-chip systems. The method is also versatile in that it can be extended to matrix materials other than metal oxides in some embodiments. According to some embodiments, biocompatible and biodegradable materials such as silk may allow the formation of implantable devices capable of performing catalytic functions, possibly in combination with degradation in response to specific triggers, while stimulus-responsive matrix materials such as hydrogels may adapt their geometry or chemical properties in response to specific chemicals or changes in temperature, pH or light, thereby enabling the catalytic system to adapt to changing environments or to be self-regulating.

Finally, the diversity of co-assembly methods (e.g., raspberry co-assembly) discussed in the embodiments herein facilitates custom integration of optimized catalytic materials into a large number of existing systems. The multi-scale properties of the material are formed by a simple evaporative self-assembly process, which in some embodiments can be scaled up to large-scale industrial applications from small model systems, and in some embodiments can be implemented on a variety of flat or curved surfaces, or mass produced in a dispersible form having controlled shape and size. As discussed, the hierarchical degrees of freedom enable materials to be adapted for important responses to many aspects of current energy, environmental and health challenges, several embodiments that may be mentioned are as follows: catalytic and photocatalytic decomposition of environmental pollutants such as CO, soot, NOx and volatile organic compounds, production of raw materials and fine chemicals, solar energy utilization and energy storage. According to some embodiments, these catalysts have excellent performance in a series of simulated industrially important chemical reactions (such as oxidation of alcohols and carbon monoxide), which makes us reasonable to believe that the strategy described herein provides a broad platform for the development of multifunctional catalytic materials, opening the idea that not only can be integrated into existing systems, but new ways and sites can be envisaged to introduce complex catalytic reactions into functional materials inside buildings, air and water treatment facilities, energy collection and storage systems, medical devices, textiles, etc.

The embodiments described herein (including those discussed above) can be implemented alone or in combination to produce benefits tailored to specific uses.

Exemplary use

The demand for indoor air purification in homes, industries and offices is increasing. Current methods mainly involve ventilation and filtration. Ventilation is often difficult or impossible for a variety of reasons derived from building design and, if possible, is energy inefficient due to energy losses resulting from the exchange of hot or cold indoor air with outdoor air. Filtration also requires energy consumption, which is generally effective in removing particulate matter from air. Toxic Volatile Organic Compounds (VOCs) are responsible for a variety of health problems, from asthma and lung disease to systemic hematological, neurological and oncological diseases, and these VOCs are best removed by chemical decomposition to convert them to non-toxic gases in clean air, such as nitrogen, carbon dioxide and water vapor.

The concept disclosed in the embodiments herein is extended by an earlier patent application entitled "High Surface Area functional on material COated Structures" (application No.14/900,567) to catalytically decompose VOCs at ambient or slightly elevated temperatures, provided that porous catalytically active material is deposited as a coating (including paint) on indoor air heaters, air conditioning units, fans, hair dryers of hair salons (which typically share space with nail shops and therefore always have a large amount of VOC emitted into the indoor air), surfaces of other air recirculation equipment such as air purifiers, humidifiers or dehumidifiers, surfaces of indoor electrical/lighting equipment, even walls or ceilings or furniture surfaces (fig. 36). One aspect of the present invention is that the catalytically active material can be designed to be very highly active, allowing it to operate and decompose VOCs efficiently at room temperature and/or under very mild heating conditions, provided that the heating is inherent in the equipment in question (e.g., AC units, recirculating air heaters, warm surfaces of lighting equipment, etc.). Importantly, even operating at room temperature, produces a significantly measurable and beneficial air purification effect to allow the catalytic coating of the present invention to be applied to other indoor surfaces, including walls and ceilings. In some embodiments, very small heating elements are integrated into the air circulation device, dedicated to heating a small area near where the functional catalytic coating is located.

FIG. 37 depicts additional embodiments of the use of the catalytic materials disclosed herein, in accordance with some embodiments. For example, in some embodiments, the catalytic material may be used in, for example, ducts within an HVAC system to filter contaminated input air flowing therethrough. In some embodiments, the catalytic material is applied as a coating to a surface of, for example, an HVAC system to filter contaminated air. In some embodiments, the catalytic coating may be applied to a duct that inputs air from the outside to filter external contaminants, or to a duct that inputs air from the inside to filter contaminants. In some embodiments, the coating may be applied directly to a ventilation surface or an interior surface of an HVAC system.

FIGS. 14-19 show Pt/A prepared using the method described in view A of FIG. 25l₂O₃And Pd/Al₂O₃Ignition profile for complete combustion of methanol with catalytic material. In fig. 14 and 16, the measured light-off temperature for a commercial catalyst (containing 1 w% Pt) was 90 ℃ (open circles), while our catalyst (black squares) was targeted at Al at the same NP loading₂O₃And TiO₂Both supports achieved room temperature operation. When the Pt NP loading was reduced to 0.5% (figure 17 circles) and 0.05% (figure 18 triangles), our catalyst still maintained a lower light off temperature than the commercial catalyst. As shown in FIGS. 15 and 19, for Pd/Al₂O₃Similar catalytic activity was observed for the system.

In some embodiments, the coating is a hierarchical porous matrix, typically composed of a suitably selected oxide material (e.g., silica, alumina, other related oxides) and particles embedded therein, including known catalytically active metals (Pt, Pd, Rh, Ru, Os, Ir, Au, Ag, less noble metals such as Cu, CO, Ni, Fe, MO, Ti-this list is exemplary, and certainly not limiting) and/or compounds thereof (including mono-, di-or multi-metal containing mixtures or alloys thereof). Additionally, in some embodiments, VOC decomposition may be achieved by designing the coating to be a photochemically active support such as titanium dioxide, which may further enhance the catalytic activity of the coating.

In addition, those skilled in the art will certainly appreciate that a variety of existing catalytic materials may be used for the purposes of the present invention-either alone or in combination with the hierarchical porous catalytic materials described in the above-mentioned application "High Surface Area functiononal MateriAl coated structures" (application No.14/900,567). Any of the catalytic materials and concepts discussed above may also be applied to such uses, alone or in combination.

In some embodiments, an essential requirement of various methods of applying such coatings/paints is that they be deposited as a topcoat or coating, which is directly exposed to the air to be purified. In some embodiments, the functional elements may be uniformly dispersed within the coating or introduced only as portions or segments, such as stripes, other periodic or random regions, depending on technical, manufacturing, and other constraints. In addition, the combination of structural color with catalytic function can be used in decorative arts and crafts such as graphic arts, wallpaper, posters, tiles, floors, etc. to create objects that are both aesthetic and practical.

Exemplary materials

Disclosed below are exemplary materials that can be used in any of the embodiments discussed above.

Base body

In some embodiments, the matrix material may be made of various materials or mixtures of materials. The choice of the matrix material depends on its intended use and its ability of the precursor to meet the templating conditions (e.g., its ability to form a stable mixture with other components, exhibit specific self-assembly or polymerization kinetics, and/or withstand calcination or other template removal conditions). For example, the matrix material may be catalytically active, stimuli-responsive, chemically stable, degradable, and/or exhibit specific thermal and mechanical properties.

In some embodiments, the matrix material comprises at least one of: oxides, metals, semiconductors, metal sulfides, metal chalcogenides, metal nitrides, metal pnictides, organometallic compounds, organic materials, natural materials, polymers, and combinations thereof. In some embodiments, the matrix precursor material comprises a sol-gel precursor. In some embodiments, the matrix material is formed from precursor materials including, but not limited to, nanoparticle precursors, such as metal oxide nanoparticles.

According to some embodiments, the matrix comprises at least one metal oxide. Examples of metal oxides include, but are not limited to, silica, alumina, iron oxides, zinc oxides, tin oxides, alumina silicates, aluminum titanates, beryllium oxide, noble metal oxides, platinum group metal oxides, titania, zirconia, hafnia, cobalt oxides, manganese oxides, molybdenum oxides, tungsten oxides, rhenium oxides, tantalum oxides, niobium oxides, vanadium oxides, chromium oxides, scandium oxides, yttrium oxides, lanthanum oxides, ceria, thorium oxides, uranium oxides, and rare earth oxides.

In other embodiments, the matrix material comprises a semiconductor including at least one of: silicon carbide, silicon, germanium, tin, silicon doped with a group III element, silicon doped with a group V element, germanium doped with a group III element, germanium doped with a group V element, tin doped with a group III element, tin doped with a group V element, and transition metal oxides.

In some embodiments, the matrix material may be a ceramic, such as cordierite, and/or include at least one of: mullite, zeolite, natural clay, and synthetic clay.

In other embodiments, the matrix material comprises at least one of a metal and a metal alloy. Examples of metals include, but are not limited to, gold, palladium, platinum, silver, copper, rhodium, ruthenium, rhenium, titanium, osmium, iridium, iron, cobalt, or nickel, or combinations thereof. Examples of metal alloys include, but are not limited to, stainless steel, ferritic steel (e.g., iron-chromium alloys), austenitic steel (chromium-nickel alloys), copper, nickel, brass, gold, silver, titanium, tungsten, aluminum, palladium, and platinum.

In other embodiments, the matrix material comprises an oxidizing agent. In other embodiments, the matrix material comprises a reducing agent.

In some embodiments, the matrix material further comprises a complex salt with at least one of: alkali metal, alkaline earth metal, group (III) metal, and transition metal salts. In some embodiments, the matrix material is selected from the group consisting of silica, titania, zirconia, ceria, vanadia, group II oxides, group III oxides, rare earth oxides, iron oxides, mixed oxides, nanoparticles, inorganic sol-gel derived oxides, alumina, iron oxides, metals, polymers, and combinations thereof.

In some embodiments, the material comprises one or more metal sulfides, metal chalcogenides, metal nitrides, metal pnictides, or combinations thereof.

In some embodiments, the matrix may include one or more organic materials, such as polymers, natural materials, and mixtures thereof.

In some embodiments, the material is a polymer, and includes one or more of: polyurethanes, poly (methyl methacrylate), polyacrylates, polyalkylacrylates, substituted polyalkylacrylates, polystyrenes, poly (divinylbenzene), polyvinylpyrrolidone, poly (vinyl alcohol), polyacrylamide, poly (ethylene oxide), polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, other halogenated polymers, hydrogels, organogels, and combinations thereof. Other polymers of different structures may also be applied, such as random and block copolymers, branched, star and dendritic polymers and supramolecular polymers.

In some embodiments, the matrix precursor material is in the form of a sol-gel precursor, a nanoparticle precursor, or a combination thereof.

In some embodiments, the sol-gel matrix precursor material is silica, alumina, titania, vanadia, ceria, and/or zirconia sol-gel.

In some embodiments, the nanoparticle precursor comprises individual nanoparticles of the above-described matrix materials or mixtures thereof.

Template component

In some embodiments, the template component comprises at least one of: polymers, random copolymers, biopolymers, organometallic compounds, supramolecular polymers, and combinations thereof.

In other embodiments, the template component comprises a polymer, such as a polyurethane, and/or comprises at least one of: polystyrene, poly (methyl methacrylate), polyacrylates, polyalkylacrylates, substituted polyalkylacrylates, polystyrene, poly (divinylbenzene), polyvinylpyrrolidone, poly (vinyl alcohol), polyacrylamide, poly (ethylene oxide), polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, other halogenated polymers, hydrogels, organogels, chitin, chitosan, random and block copolymers, branched, star and dendritic polymers, and supramolecular polymers.

In some embodiments, the template set is a biologically derived material, such as an enzyme or protein.

In other embodiments, the templating component includes a natural material, for example, including at least one of: cellulose, natural rubber (such as latex), wool, cotton, silk, flax, hemp, flax fiber and feather fiber

In other embodiments, the template component comprises at least one of: polymeric fibers, biopolymer fibers, fibers containing organometallic compositions, supramolecular self-assembled fibers, and combinations thereof.

In other embodiments, the templating component includes a composite material that combines organic and inorganic components.

In the context of the present application, colloid is defined as dispersed particles or macromolecules suspended in another substance, and may alternatively be referred to as a colloidal dispersion. As used herein, the dispersed substance or particles may alternatively be referred to as "colloids" or "colloidal particles". Many different types of colloidal particles can be used to practice the methods described herein. The gel may be made of various materials or mixtures of materials. To be useful as a sacrificial template material, at least a portion of the colloidal material should be flammable, soluble, sublimable, or meltable during formation of the porous template material disclosed herein. The colloidal particle size (particle size) can be in the microporous (2 nm), mesoporous (2-50nm) and/or macroporous (>50nm) grades.

In some embodiments, the material comprises a polymeric fiber, a biopolymer fiber, a fiber containing an organometallic composition, a supramolecular self-assembled fiber, or a combination thereof.

In some embodiments, the size (e.g., diameter) of the template particles may be from about 1nm to tens or hundreds of microns. Some exemplary dimensions include about 1-1000nm to provide specific optical properties that are less susceptible to gravity and/or improved assembly properties. Some exemplary dimensions include 200 and 50000nm to achieve porosity for particular mass transfer characteristics and/or filtration and/or catalytic applications. Depending on the application, various types of sacrificial particles may be applied.

Catalytic NPs and other catalytic or/and co-catalytic components

In some embodiments, the catalytic NP may include at least one of: metal NPs, metal alloy NPs, bimetals, multi-metal NPs, semiconductor NPs, metal oxide NPs, mixed metal oxide NPs, metal sulfide NPs, solid solutions, and combinations thereof.

In some embodiments, the catalytic nanoparticles comprise a metal, a transition metal, a main group metal, a metal oxide, a mixed metal oxide, an oxide of any one or more metals of groups I, II, III, IV, V, VI, VII, VIII (from the main group or transition series) or, alternatively, groups 1 to 16, a metal oxide, a metal sulfide, a metal pnictide, a metal carbide, a bimetallic salt, a composite metal salt, an organic acid salt, an inorganic acid salt, a composite metal salt, a base, an acid, a metal alloy, a multimetallic substance, an intermetallic compound, a non-stoichiometric phase, an organometallic compound, a coordination compound, One or more platinum group metals, one or more platinum group metal oxides, carbon, iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, iron oxides, cobalt oxides, nickel oxides, ruthenium oxides, rhodium oxides, palladium oxides, osmium oxides, iridium oxides, platinum oxides, copper oxides, silver oxides, gold oxides, titanium oxides, zirconium oxides, hafnium oxides, vanadium oxides, niobium oxides, tantalum oxides, chromium oxides, molybdenum oxides, tungsten oxides, manganese oxides, rhenium oxides, scandium oxides, yttrium oxides, lanthanum oxides, rare earth metal oxides, any of the foregoing in a single crystal polymorph or several polymorphs, any of the foregoing that provides specific crystal planes to the channel, any of the foregoing in an amorphous form, and combinations thereof.

In some embodiments, the NPs may include metals, such as gold, silver, platinum, palladium, ruthenium, rhodium, cobalt, iron, nickel, osmium, iridium, rhenium, copper, chromium, tungsten, molybdenum, vanadium, niobium, tantalum, titanium, zirconium, hafnium, bimetals, metal alloys and the like, metal compounds such as pnictides, hydroxides, binary and complex salts (including heteropolyacids and their derivatives or combinations thereof); semiconductors such as silicon, germanium, and the like (pure substances or doped with group III or group V elements or compounds) and combinations thereof; metal oxide of, including V₂O₅Silica, alumina, noble metal oxides, platinum group metal oxides, titania, zirconia, hafnia, molybdenum oxides, tungsten oxides, rhenium oxides, tantalum oxides, niobium oxides, chromium oxides, scandium, yttrium, lanthanum and rare earth oxides, thorium and uranium oxides, and the like; a metal sulfide or a combination thereof. In some embodiments, the multi-metallic nanoparticles comprise two or more metals selected from gold, silver, platinum, palladium, ruthenium, rhodium, cobalt, iron, nickel, osmium, iridium, rhenium, copper, and chromium.

In some embodiments, the catalytically relevant component comprises a complex salt with: alkali metal, alkaline earth metal, group (III) metal and transition metal salts, such as salts of nickel, copper, cobalt, manganese, magnesium, chromium, iron, platinum, tungsten, zinc or other metals.

In some embodiments, the catalysis-related species deposited at the matrix-pore and/or NP-pore interfaces may include carbon, polycyclic/polycondensed carbon-rich species, acidic species such as heteropolyacids, solid acid or basic species, metal particles, metal oxide particles, or combinations thereof. In some embodiments, the catalytically relevant species deposited at the matrix-pore and/or NP-pore interfaces is derived from an interconnected template component. In some embodiments, the template component is an organometallic and the catalytically relevant species deposited at the matrix-pore and/or NP-pore interfaces are metal or metal oxide particles.

In some embodiments, the template component (i.e., NP-decorated template particles or colloids) may comprise one or more of the following shapes: spherical, elongated, concave, amorphous, polyhedral, fibrous, and platelet-shaped.

In some embodiments, the methods described herein facilitate the formation of highly porous structures with interconnected pores over multiple length scales, as well as the decoration of the pore surfaces with functional components (including, but not limited to, catalytic and co-catalytic components). The functional component can be designed to provide catalytic, photocatalytic, electrocatalytic, photonic, antibacterial, UV-visible light absorption and/or emission and sensing properties, and combinations thereof.

In some embodiments, the functional component may be further modified by one or more growth methods.

After combining the description and embodiments provided herein, those skilled in the art will understand that various modifications and equivalent substitutions can be made in the practice of the invention without departing from the spirit thereof. Accordingly, the present invention is not limited to the embodiments explicitly described above.

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