阅读说明：本技术 用于合成中孔沸石的有机硅烷模板和方法 (Organosilane templates and methods for synthesizing mesoporous zeolites ) 是由 萨拉·利阿·科巴斯利娅 杰里米·托马斯·奥布赖恩 于 2019-08-07 设计创作，主要内容包括：提供了形成具有可调孔隙宽度的中孔沸石的方法。在一些实施方案中,所述方法包括将含硅材料、含铝材料和至少一种季胺混合以产生沸石前体溶液。在高于125℃的预结晶温度和自生压力下使所述沸石前体溶液预结晶以形成预结晶沸石前体溶液并且与有机硅烷中孔模板组合以产生沸石前体凝胶。在先前没有离散功能化步骤的情况下使所述沸石前体凝胶结晶以产生结晶沸石中间体,并且煅烧所述结晶沸石中间体以产生所述中孔沸石。还提供了根据的有机硅烷中孔模板,其中R是脂肪族、芳香族或含杂原子基团。(A method of forming a mesoporous zeolite with adjustable pore width is provided. In some embodiments, the method comprises mixing a silicon-containing material, an aluminum-containing material, and at least one quaternary amine to produce a zeolite precursor solution. Pre-crystallizing the zeolite precursor solution at a pre-crystallization temperature above 125 ℃ and an autogenous pressure to form a pre-crystallized zeolite precursor solution and combining with an organosilane mesoporous template to produce a zeolite precursor gel. Crystallizing the zeolite precursor gel without a prior discrete functionalization step to produce a crystalline zeolite intermediate, and calcining the crystalline zeolite intermediate to produce the mesoporous zeolite. Also provided is an organosilane mesoporous template according to wherein R is an aliphatic, aromatic or heteroatom-containing group.)

1. A method of forming a mesoporous zeolite with tunable physical properties, the method comprising:

mixing a silicon-containing material, an aluminum-containing material, and at least one quaternary amine to produce a zeolite precursor solution;

pre-crystallizing the zeolite precursor solution at a pre-crystallization temperature above 125 ℃ and an autogenous pressure to form a pre-crystallized zeolite precursor solution, the pre-crystallized zeolite precursor solution exhibiting formation of an amorphous phase in a quasi-steady state in which the solid and solution phases are close to equilibrium and silicate and aluminosilicate anion distributions are established;

combining an organosilane mesoporous template with the pre-crystallized zeolite precursor solution to produce a zeolite precursor gel;

crystallizing the zeolite precursor gel to produce a crystalline zeolite intermediate; and

calcining the crystalline zeolite intermediate to produce the intermediate pore size zeolite,

wherein the process does not include a discrete functionalization step of the zeolite precursor gel prior to crystallizing the zeolite precursor gel.

2. The method of claim 1, wherein the organosilane mesoporous template comprises a mesoporous silica according toWherein R is aliphatic, aromatic or heteroatom containing group.

3. The method of claim 2, wherein R is H, R is Ph, or R is CH ═ CHPh.

4. The method of any of claims 1 to 3, wherein the silicon-containing material comprises SiO₂Sodium silicate, tetramethylsiloxane, tetraethylsiloxane, a silicon salt, a silicon alkoxide, or combinations thereof.

5. The method of any one of claims 1 to 4, wherein the aluminum-containing material comprises aluminum nitrate, aluminum sulfate, aluminum alkoxides, other aluminum salts, or combinations thereof.

6. The process of any one of claims 1 to 5 wherein the medium pore zeolite comprises beta zeolite.

7. The method of any one of claims 1 to 6, wherein the quaternary amine comprises tetraethylammonium hydroxide.

8. The method of any one of claims 1 to 7, wherein the organosilane mesoporous template has a total loading in the range of 0.5 mol% to 25 mol% with respect to the silicon-containing material.

9. The process of any one of claims 1 to 8, wherein the crystallization is accomplished at a crystallization temperature above 140 ℃.

10. An organosilane mesoporous template comprising a compound according toWherein R is aliphatic, aromatic, or a heteroatom containing group.

11. A mesoporous template in an organosilane according to claim 10 wherein R is H, R is a phenyl (Ph) group, or R is CH ═ CHPh.

12. A method of forming a mesoporous template in an organosilane comprising a mesoporous template according toWherein R is aliphatic, aromatic, or a heteroatom-containing group, comprising:

combining 1 equivalent of an aniline derivative with 1 to 1.5 equivalents of 3-glycidoxypropyltrimethoxysilane in the presence of ethanol to form a reaction mixture; and

stirring and heating the reaction mixture;

wherein said aniline derivative comprisesThe structure of (1).

13. The process of claim 12, wherein the stirring and heating of the reaction mixture is accomplished in a schlenk flask by stirring the reaction mixture under reflux for 4 to 24 hours.

14. The method of claim 12, wherein said stirring and heating of said reaction mixture is accomplished in a sealed container by stirring said reaction mixture at 130 to 220 ℃ for 5 to 90 minutes.

15. The method of any one of claims 12-14, wherein R is H, R is phenyl (Ph), or R is CH ═ CHPh.

Technical Field

The present disclosure relates generally to mesoporous zeolites and methods of making mesoporous zeolites. In particular, the present disclosure relates to mesoporous zeolites and methods of making mesoporous zeolites having tunable physical properties.

Background

Zeolites are aluminosilicate minerals that can be used in a variety of applications including oil refining, adsorption and separation processes, as size-selective heterogeneous catalysts, as shape-selective heterogeneous catalysts, as encapsulants, as slow release agents, and for ion exchange. However, the physical properties of zeolites, including the mesopore size, pore volume, and surface area of most zeolites, may limit the use of zeolites in many applications.

In petroleum processes, upgrading or "cracking" of hydrocarbons is often used to refine crude oil and other high molecular weight hydrocarbons into much more valuable smaller "light" hydrocarbons, such as gasoline and olefin gases. One of the most common upgrading techniques is catalytic cracking, in which hydrocarbons are upgraded using a catalyst (most commonly a conventional zeolite catalyst). However, the most effective or desirable pore width distribution centers of zeolites for catalytic cracking may be different for different hydrocarbon feeds or desired products. In particular, it is believed that the mechanism of zeolite catalysis is affected by pore shape and size. Thus, zeolite catalysts are selected for optimal upgrading of hydrocarbons in view of the mesopore size, pore volume and surface area.

Previous attempts have been made to provide zeolites of mesoporosity having different pore width distribution centers by functionalizing the growing seeds using a single organosilane template. The mesopore size is determined by the template structure and thus a single pore width distribution center is created per organosilane template. However, the specific pore width distribution centers are limited to those corresponding to each organosilane template, and many cannot be obtained due to the lack of corresponding organosilane templates currently available.

Disclosure of Invention

Thus, there is a need for new organosilane mesoporous templates and methods to produce mesoporous zeolite catalysts with tunable physical properties. As such, the present disclosure expands the range of mesopore sizes that can be achieved by incorporating specially synthesized organosilane mesopore templates according to the present disclosure. In addition, the method according to the present disclosure does not include a discrete functionalization step during the formation of the mesoporous zeolite, thereby providing a streamlined zeolite synthesis process.

In accordance with an embodiment of the present disclosure, a method of forming a mesoporous zeolite with adjustable pore width is provided. The method includes mixing a silicon-containing material, an aluminum-containing material, and at least one quaternary amine to produce a zeolite precursor solution. The method further includes pre-crystallizing the zeolite precursor solution at a pre-crystallization temperature above 125 ℃ and an autogenous pressure to form a pre-crystallized zeolite precursor solution, the pre-crystallized zeolite precursor solution exhibiting formation of an amorphous phase in a pseudo-steady state in which the solid and solution phases are near equilibrium and silicate and aluminosilicate anion distributions are established. Further, the method includes combining an organosilane mesoporous template with a pre-crystallized zeolite precursor solution to produce a zeolite precursor gel, and crystallizing the zeolite precursor gel to produce a crystalline zeolite intermediate. Finally, the method includes calcining the crystalline zeolite intermediate to produce a mesoporous zeolite. Furthermore, the method does not include a discrete functionalization step of the zeolite precursor gel prior to crystallizing the zeolite precursor gel.

According to an embodiment of the present disclosure, an organosilane mesoporous template is provided. The mesoporous template in the organosilane includes structures according to wherein R is aliphatic, aromatic or a heteroatom containing group.

According to an embodiment of the present disclosure, there is provided a method of forming a mesoporous template in an organosilane, the template comprising a structure according to, wherein R isAliphatic, aromatic or heteroatom containing groups. The method comprises combining 1 equivalent of an aniline derivative with 1 to 1.5 equivalents of 3-glycidoxypropyltrimethoxysilane in the presence of ethanol to form a reaction mixture, and stirring and heating the reaction mixture. In addition, the aniline derivatives includeThe structure of (1).

Additional features and advantages of the technology disclosed in this disclosure will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the technology as described in this disclosure, including the detailed description which follows, the claims, as well as the appended drawings.

Drawings

The following detailed description of specific embodiments of the present disclosure can be best understood when read in conjunction with the following drawings.

Fig. 1A is an X-ray diffraction spectrum of the present porous and mesoporous zeolites formed in accordance with one or more embodiments shown and described herein.

Fig. 1B is an X-ray diffraction spectrum of a comparative mesoporous zeolite and a mesoporous zeolite formed according to one or more embodiments shown and described herein.

Fig. 2 is a graph comparing the pore width distribution centers of mesoporous zeolites and mesoporous zeolites formed according to one or more embodiments shown and described herein.

Fig. 3 is a graph of the center of the pore width distribution of a mesoporous zeolite formed at different organosilane template loadings according to one or more embodiments shown and described herein.

Figure 4 is a magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopic analysis spectrum of a comparative mesoporous zeolite, uncalcined mesoporous zeolite, and mesoporous zeolite formed according to one or more embodiments shown and described herein.

Fig. 5 is a Fourier transform infrared spectroscopy (FTIR) spectrum of an organosilane mesoporous template, a comparative mesoporous zeolite, zeolite seeds, and an uncalcined mesoporous zeolite formed according to one or more embodiments shown and described herein.

Figure 6 is a fourier transform infrared spectroscopy (FTIR) spectrum of an organosilane mesoporous template, comparative mesoporous zeolite, and uncalcined mesoporous zeolite formed according to one or more embodiments shown and described herein.

Fig. 7A is an adsorption profile of a comparative mesoporous zeolite formed with discrete functionalization steps and a mesoporous zeolite formed without discrete functionalization steps according to one or more embodiments shown and described herein.

Fig. 7B is an adsorption profile of a comparative mesoporous zeolite formed with discrete functionalization steps and a mesoporous zeolite formed without discrete functionalization steps according to one or more embodiments shown and described herein.

Figure 7C is an adsorption profile of a comparative mesoporous zeolite formed with discrete functionalization steps and a mesoporous zeolite formed without discrete functionalization steps according to one or more embodiments shown and described herein.

Figure 7D is an adsorption profile of a comparative mesoporous zeolite formed with discrete functionalization steps and a mesoporous zeolite formed without discrete functionalization steps according to one or more embodiments shown and described herein.

Fig. 8A is a Temperature Programmed Desorption (TPD) signal return plot of a comparative mesoporous zeolite formed with and without discrete functionalization steps according to one or more embodiments shown and described herein.

Figure 8B is a Temperature Programmed Desorption (TPD) signal return plot of a comparative mesoporous zeolite formed with and without the discrete functionalization steps according to one or more embodiments shown and described herein.

Figure 8C is a Temperature Programmed Desorption (TPD) signal return plot of a comparative mesoporous zeolite formed with and without the discrete functionalization steps according to one or more embodiments shown and described herein.

Figure 8D is a Temperature Programmed Desorption (TPD) signal return plot of a comparative mesoporous zeolite formed with and without the discrete functionalization steps according to one or more embodiments shown and described herein.

Reference will now be made in more detail to various embodiments.

Detailed Description

The present disclosure relates to various embodiments of methods of forming mesoporous zeolites having tunable physical properties. "zeolitic material" or "zeolite" refers to an inorganic material having regular crystalline internal cavities and molecular size channels. The porous structure of zeolites can provide a large surface area and desirable size and shape selectivity, which may be advantageous for catalysis. The mesoporous zeolites described may include aluminosilicates, titanosilicates, or pure silicates. As used throughout this disclosure, "mesoporous" or "mesoporous" refers to pores in a structure having a diameter greater than 2 nanometers (nm) and less than or equal to 50 nm. Similarly, to the extent used throughout this disclosure, "microporous" or "microporous" refers to pores in a structure having a diameter of less than or equal to 2nm and greater than or equal to 0.1 nm.

Embodiments of the present disclosure relate to methods for producing mesoporous zeolites having tunable physical properties. The method includes mixing a silicon-containing material, an aluminum-containing material, and a quaternary amine to form a zeolite precursor solution. The zeolite precursor solution is then pre-crystallized at a pre-crystallization temperature greater than 125 ℃ and an autogenous pressure to produce a pre-crystallized zeolite precursor solution. Subsequently, the pre-crystallized zeolite precursor solution is combined with an organosilane mesoporous template to form a zeolite precursor gel. The precursor gel may then be crystallized to produce a crystalline zeolite intermediate. The crystalline zeolite intermediate may be centrifuged, washed and dried, and finally two or more different organosilane mesoporous templates may be removed by a calcination step to produce a mesoporous zeolite. Without being bound by theory, it is believed that removal of the mesoporous template from the organosilane forms at least a portion of the mesopores of the mesoporous zeolite, wherein mesopores are present in the interstices or voids once occupied by the mesoporous template from the organosilane.

Without being bound by any particular theory, mesoporous zeolites can be synthesized using templates such as organosilane mesoporous templates. Mesoporosity can be introduced into zeolites by destructive or constructive means. Destructive methods include dealumination and desilication, which leach atoms from commercially available materials. However, destructive methods lack control over pore generation size and frequency, may result in amorphization, and have limited flexibility in Si/Al ratio. A constructive process involves the synthesis of zeolites by crystallization of the minerals around a template structure, which burns out during the calcination step, leaving pores and channels and being the focus of the present disclosure.

The present disclosure relates to the use of organosilane mesoporous templates to synthesize mesoporous zeolites with tunable physical properties. In particular, the surface area, pore size, and pore volume of the mesoporous zeolite formed may be adjusted or tuned based on the size and structure of the mesoporous template of the organosilane utilized in forming the mesoporous zeolite. The methods of the present disclosure and the disclosed custom-designed organosilane templates provide the ability to form mesoporous zeolites having pore sizes that are different from those formed using commercially available organosilane templates.

The mesoporous template in the organosilane may comprise a general structure according to chemical structure 1, wherein R is an aliphatic, aromatic, or heteroatom-containing group.

In one or more embodiments, the organosilane mesoporous template is synthesized by combining an aniline derivative comprising the selected R group of chemical structure 1 with 3-glycidoxypropyltrimethoxysilane in the presence of ethanol to form a reaction mixture. Specifically, the mesoporous template in the organosilane can be synthesized by combining 1 equivalent of aniline derivative with 1 to 1.5 equivalents of 3-glycidoxypropyltrimethoxysilane in the presence of ethanol. The synthesis reaction was completed according to reaction 1 provided later. In one or more embodiments, the synthesis can be accomplished in a Schlenk flask (Schlenk flash) while the reaction mixture is stirred at reflux for 4 to 24 hours, 6 to 20 hours, 12 to 18 hours, or about 16 hours. In some embodiments, the temperature may be maintained at about 110 ℃ when the system is sealed, which is above reflux. In one or more other embodiments, the synthesis can be accomplished in a sealed container, e.g., a sealed microwave vial, while the reaction mixture is stirred at a temperature of 120 to 180 ℃, 130 to 170 ℃, or about 150 ℃ for 10 to 90 minutes, 15 to 60 minutes, or 20 to 45 minutes. The resulting organosilane mesoporous template synthesized according to either method can then be purified using silica gel column chromatography. Without wishing to be bound by theory, it is believed that heating at too high a temperature or for too long a time may cause the sample to decompose.

As indicated previously, the R groups in chemical structure 1 can be aliphatic, aromatic, or heteroatom containing groups. In one or more embodiments, the R group in chemical structure 1 can be an aliphatic group. Exemplary aliphatic groups include a single hydrogen atom (H), methyl, ethyl, propyl, and cyclic alkanes. In one or more embodiments, the R group in chemical structure 1 can be an aromatic group. Exemplary aromatic groups include phenyl (Ph) (C)₆H₅) Styryl, substituted phenyl and substituted styryl. In one or more embodiments, the R group in chemical structure 1 can be a heteroatom-containing group. Exemplary heteroatom-containing groups include cyclic compounds containing one or more silicon, nitrogen, or oxygen atoms.

Without being bound by any theory, the use of a mesoporous template in an organosilane according to chemical structure 1 may help alleviate potential problems typically associated with template-driven zeolite synthesis. The use of a template may improve control over the size and shape of mesopores formed during zeolite synthesis compared to destructive mesopore formation methods; conventionally, however, there are several disadvantages with existing templating procedures. One of the problems is that the mesopore size can only be changed by changing the structure of the organosilane mesopore template and is thus limited by the availability of different and unique organosilane mesopore templates. Since the pore widths are limited to those of the corresponding organosilane templates that have a correlation with the desired static center of the particular pore width distribution, it may not be possible to produce a mesoporous zeolite having the desired center of the pore width distribution from a previously available organosilane mesoporous template. The generation of a newly custom designed and synthesized organosilane mesotemplate according to chemical structure 1 provides more choice of pore width than previously available organosilane mesotemplates.

In some embodiments, the silicon-containing material, the aluminum-containing material, or both, may be combined with a quaternary amine to form a zeolite precursor solution. Quaternary amines can be used as Structure Directing Agents (SDA) for making zeolite microstructures. The quaternary amines are depicted generically in chemical structure 2. The quaternary ammonium cations act as crystalline centers for the formation of zeolite subunits, thereby forming a regular microporous system in the zeolite structure.

As used throughout this disclosure, a circled plus sign ("+") shows a positive center of cation charge. The R groups (including R1, R2, R3, R4) represent chemical moieties. One or more of the individual R groups may be structurally the same or may be structurally different from each other.

In chemical structure 2, R1, R2, R3, and R4 may include a hydrogen atom or a hydrocarbon, such as a hydrocarbon chain. As used throughout this disclosure, "hydrocarbon" refers to a chemical or chemical moiety that contains only hydrogen and carbon atoms. In some other embodiments, R1, R2, R3, and R4 may contain one or more heteroatoms, such as oxygen, sulfur, nitrogen, or phosphorus. For example, the hydrocarbon chain may be branched or unbranched, and may include an alkane chain, an alkene chain, or an alkyne chain, including cyclic or aromatic moieties. In some embodiments, one or more of R1, R2, R3, or R4 may represent a hydrogen atom. As used throughout this disclosure, heteroatoms are non-carbon and non-hydrogen atoms. In embodiments, the quaternary amine may be present in a cyclic moiety, such as a five atom ring, a six atom ring, or a ring containing different numbers of atoms. For example, in chemical structure 2, the R1 and R2 components can be part of the same cyclic moiety.

In one or more embodiments, two cationic moieties can form an ionic bond with an anion. Various anionic chemicals are contemplated, including Cl^-、Br^-、F^-、I^-、OH^-、1/2SO₄ ^2-、1/3PO₄ ^3-、1/2S^2-、AlO₂ ^-. In some embodiments, anions having a negative charge greater than 1-, such as 2-, 3-, or 4-, may be utilized, and in those embodiments, a single anion may pair with multiple cations of the structure directing agent. As used throughout this disclosure, the fractions listed before the anionic composition mean that the anion is paired with more than one cation, and may, for example, be paired with a number of cations equal to the negative charge of the anion.

In one or more embodiments, the two cations of the monomer can be separated from each other by a hydrocarbon chain. The hydrocarbon chain may be branched or unbranched, and may include an alkane chain, an alkene chain, or an alkyne chain, including cyclic or aromatic moieties. In one embodiment, the length of the hydrocarbon chain (measured in carbon number connecting the two cations directly in the chain) may be an alkane chain of 1 to 10,000 carbon atoms, for example 1 to 20 carbon atoms.

In some embodiments, the quaternary amine may comprise a tetraalkylammonium hydroxide, such as tetraethylammonium hydroxide (TEAOH). In other embodiments, the quaternary amine may include propyltrimethylammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammonium hydroxide, octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, or combinations of these.

In one or more embodiments, the silicon-containing material comprises silicon dioxide (SiO)₂) Sodium silicate, tetramethylsiloxane, tetraethylsiloxane, silicate, silicon alkoxide or mixtures thereofAnd (4) combining.

In one or more embodiments, the aluminum-containing material comprises aluminum oxide (Al)₂O₃) Aluminum nitrate, aluminum sulfate, aluminum alkoxides, other aluminum salts, or combinations thereof.

As previously indicated, the zeolite precursor solution is pre-crystallized to produce a pre-crystallized zeolite precursor solution. Pre-crystallization means the formation of an amorphous phase in a quasi-steady state where the solid and solution phases approach equilibrium and silicate and aluminosilicate anion distributions are established. In one or more embodiments, the zeolite precursor solution is pre-crystallized in a stainless steel autoclave lined with Polytetrafluoroethylene (PTFE), commonly known as teflon, at 135 ℃ and autogenous pressure for 48 hours. In various embodiments, the pre-crystallization is accomplished at a pre-crystallization temperature above 105 ℃, above 115 ℃, above or above 125 ℃, including in the range of 115 ℃ to 145 ℃, 125 ℃ to 135 ℃, and 135 ℃ to 145 ℃. Further, in various embodiments, the zeolite precursor solution is maintained in a PTFE lined stainless steel autoclave at a pre-crystallization temperature and autogenous pressure for 24 hours, 30 hours, 36 hours, 42 hours, 54 hours, 60 hours, or 72 hours, including 24 hours to 72 hours, 30 hours to 48 hours, 36 hours to 54 hours, and 42 hours to 72 hours.

In embodiments, the pre-crystallized zeolite precursor solution may be combined with an organosilane mesoporous template to form a zeolite precursor gel. In one or more embodiments, a quaternary amine may be additionally added to the pre-crystallized zeolite precursor solution to create a zeolite precursor gel. The quaternary amine may be the same as the quaternary amine utilized in the initial combination of the silicon-containing material, the aluminum-containing material, or both with the quaternary amine to form the zeolite precursor solution. In one or more particular embodiments, the quaternary amine is TEAOH.

The loading of the organosilane mesoporous template determines the total pore volume of the final mesoporous zeolite. An increase in the loading of the mesoporous template in the organosilane corresponds to an increase in the total pore volume of the mesoporous zeolite. In various embodiments, the total loading of the mesoporous template in the organosilane can be 0.5 mol%, 1 mol%, 2.5 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, or 25 mol%, including all ranges subsumed therein, in mole percent (mol%) with respect to the loading of the silicon-containing material.

The precursor gel may then be crystallized to produce a crystalline zeolite intermediate. In one or more embodiments, the precursor gel is crystallized in a PTFE lined stainless steel autoclave at 170 ℃ and autogenous pressure for 7 days. In various embodiments, crystallization is accomplished at a crystallization temperature above 140 ℃, above 150 ℃, above or above 160 ℃, including in the range of 140 ℃ to 170 ℃, 150 ℃ to 160 ℃, and 150 ℃ to 170 ℃. Further, in various embodiments, the zeolite precursor solution is maintained in a PTFE lined stainless steel autoclave at the crystallization temperature and autogenous pressure for 3 days, 5 days, 10 days, or 12 days, including 3 days to 12 days, 5 days to 7 days, 7 days to 12 days, and 3 days to 10 days.

In some embodiments, the crystalline zeolite intermediate may be calcined. The calcination may take place in the presence of air at a temperature above 500 ℃, above 550 ℃, above 600 ℃ or even above 750 ℃. The calcination step may remove the two or more different organosilane mesoporous templates and structure directing agents, for example, by burning them out. The elevated temperature at which the crystalline zeolite intermediate is calcined can be maintained for 3 hours, 5 hours, 6 hours, or 8 hours, including 3 hours to 8 hours, 5 hours to 8 hours, and 6 hours to 8 hours. After calcination, the organosilane mesoporous template can be removed to form mesopore size voids in the resulting mesoporous zeolite. It is contemplated that various heater units are suitable, including ovens and autoclaves, or using any other technique known in the industry.

In embodiments, the mesoporous zeolites made according to the present disclosure are characterized as exhibiting a Y or faujasite framework, an MFI (mordenite framework inverted) framework, or a BEA (beta polymorphs a and B) framework. For example, the described mesoporous zeolites can be characterized as ZSM-5 (i.e., having an aluminosilicate MFI framework type), TS-1 (i.e., having a titanosilicate MFI framework type), or silicalite-I (i.e., having a pure silicate MFI framework type) zeolites. In other embodiments, the mesoporous zeolites described may be characterized as beta (i.e., having an aluminosilicate BEA framework type) or faujasite (having a Y framework type). In some particular embodiments, the mesoporous zeolite produced by the methods of the present disclosure may be a beta framework zeolite.

Without being bound by any particular theory, the material composition of the resulting mesoporous zeolite, which may be an aluminosilicate, titanosilicate, or pure silicate zeolite, may be determined by the at least one siliceous material, alumino-containing material, or both. In some embodiments, the mesoporous zeolite of the present disclosure may be an aluminosilicate mesoporous zeolite having a Si/Al molar ratio greater than or equal to 5, greater than or equal to 10, greater than or equal to 30, or greater than or equal to 50. In some embodiments, the mesoporous zeolites of the present disclosure may be aluminosilicate mesoporous zeolites having a Si/Al molar ratio greater than or equal to 5 and less than 100, greater than or equal to 10 and less than 100, greater than or equal to 25 and less than 100, greater than or equal to 30 and less than 100, greater than or equal to 20 and less than 80, greater than or equal to 40 and less than 80, greater than or equal to 25 and less than 75, or even greater than or equal to 35 and less than 95. In other embodiments, the mesoporous zeolites of the present disclosure may be pure silicate zeolites and may have negligible or no amount of aluminum, with Si/Al molar ratios theoretically approaching infinity. As used herein, "pure silicate" refers to a material that contains at least about 99.9 weight percent (wt.%) silicon and oxygen atoms. Pure silica mesoporous zeolites can be formed by utilizing only siliceous materials and not aluminum.

The mesoporous zeolites of the present disclosure may comprise mesopores and micropores. The mesoporous zeolite may have a surface area and pore volume greater than conventionally produced zeolites. In the present disclosure, "conventional zeolite" or "conventionally produced zeolite" refers to a zeolite that contains substantially no mesopores (e.g., less than 0.5% of the zeolite pore volume is characterized as mesopores). Without being bound by any particular theory, it is believed that the quaternary amines utilized by the present disclosure may help form micropores, which may result from void formation during calcination of the organosilane mesoporous template.

The mesoporous zeolites described in this disclosure may have enhanced catalytic activity. Adjusting the center of the pore width distribution of mesopores by using the organosilane mesopore template according to chemical structure 1 allows to select mesopore sizes optimized for a specific catalytic reaction. In particular, the adjusted mesopore size can allow for higher catalytic functionality, as more catalytically active sites are available for contact with reactants in the catalytic reaction. Similarly, mesopores can allow better access to the microporous catalytic sites on the mesoporous zeolite.

The mesoporous zeolites described may be shaped into particles having a generally spherical shape or an irregular spherical shape (i.e., non-spherical). In embodiments, the particles have a "particle size" measured as the maximum distance between two points located on a single zeolite particle. For example, the size of a spherical particle will be its diameter. In other shapes, particle size is measured as the distance between the two farthest points of the same particle, where the points may be located on the outer surface of the particle. The particle size of the particles may be 25nm to 500nm, 50nm to 400nm, 100nm to 300nm, or less than 900nm, less than 800nm, less than 700nm, less than 600nm, less than 500nm, less than 400nm, less than 300nm, or less than 250 nm. Particle size can be determined by inspection under TEM or SEM microscopy.

Using physical adsorption, the surface area, pore size and pore volume can be calculated. Physical adsorption measures the amount of gas absorbed to calculate surface area, pore size and pore volume. The output from the physisorption isotherm is in the form of a graph representing cumulative pore volume versus pore size. The first derivative of this figure provides the differential pore volume (dv (d)) and pore size distribution.

The binding energy of the mesoporous zeolite can be calculated using Temperature Programmed Desorption (TPD), also known as Thermal Desorption Spectroscopy (TDS). TPD works on the principle that when molecules or atoms come into contact with a surface, they adsorb to the surface, minimizing their energy by forming bonds with the surface. The binding energy varies with the combination of the adsorbate and the surface. If the surface is heated, the energy transferred to the adsorbed species will cause the species to desorb. The temperature at which this occurs is called the desorption temperature and provides information about the binding energy.

Examples

Using the methods of the present disclosure, mesoporous zeolites were produced to illustrate the properties previously described. Four exemplary methods were performed according to the present disclosure, wherein the methods did not include a discrete functionalization step of the zeolite precursor gel prior to crystallizing the zeolite precursor gel. Four additional exemplary methods were performed, wherein the methods included a discrete functionalization step of the zeolite precursor gel prior to crystallizing the zeolite precursor gel. Additional exemplary methods were accomplished with varying the total loading of the mesoporous template in the organosilane and in the absence of the mesoporous template in the organosilane.

Exemplary preparation scheme 1 (No functionalization step)

Each exemplary zeolite is zeolite beta prepared with the following molar composition: 1Al₂O₃:60SiO₂:31TEAOH:1000H₂And O. An initial formulation was prepared by combining fumed silica (2.955g), aluminum powder (0.044g), tetraethylammonium hydroxide (TEAOH) (10.693 g-35% aqueous solution), and distilled water (7.742 g). Lined with Polytetrafluoroethylene (PTFE) (commonly known as Teflon @)^TM) The initial formulation mixture was pre-crystallized at 135 c and autogenous pressure for 48 hours in a stainless steel autoclave. The resulting gel was mixed with additional TEAOH aqueous solution (27.86 g-13% aqueous solution) and each organosilane mesoporous template at the loading provided for each example. The gel with the additional aqueous TEAOH solution was then crystallized in a PTFE lined stainless steel autoclave at 170 ℃ and autogenous pressure for 7 days. The mole% (mol%) of each loading is based on the silicon content of the gel. The resulting zeolite product was then separated by centrifugation, washed several times with water, dried, and then calcined at 550 ℃ for 6 hours.

An initial set of inventive examples was prepared using template 1, template 2, template 3, and template 4 according to exemplary preparation scheme 1 provided previously. Template 1 is an organosilane template having the chemical structure illustrated below.

Template 2 is an organosilane template having the chemical structure illustrated below.

Template 3 is an organosilane template having the chemical structure illustrated below.

Template 4 is a commercially available organosilane template, phenylaminopropyltrimethoxysilane (PHAPTMS), having the chemical structure illustrated below.

Inventive examples 1-5 mol% template 1

Inventive example 1 was prepared according to the exemplary preparation scheme 1 provided above with the addition of an organosilane mesoporous template comprising a loading of 5 mol% template 1.

Inventive example 2-5 mol% template 2

Inventive example 2 was prepared according to the exemplary preparation scheme 1 provided above with the addition of an organosilane mesoporous template comprising a loading of 5 mol% template 2.

Inventive example 3-5 mol% template 3

Inventive example 3 was prepared according to the exemplary preparation scheme 1 provided above with the addition of an organosilane mesoporous template comprising a loading of 5 mol% template 3.

Inventive example 4-5 mol% template 4

Inventive example 4 was prepared according to the exemplary preparation scheme 1 provided above with the addition of an organosilane mesoporous template comprising a loading of 5 mol% template 4.

Exemplary preparation scheme 2 (with functionalization step)

Each exemplary zeolite is zeolite beta prepared with the following molar composition: 1Al₂O₃:60SiO₂:31TEAOH:1000H₂And O. An initial formulation was prepared by combining fumed silica (2.955g), aluminum powder (0.044g), tetraethylammonium hydroxide (TEAOH) (10.693 g-35% aqueous solution), and distilled water (7.742 g). Lined with Polytetrafluoroethylene (PTFE) (commonly known as Teflon @)^TM) The initial formulation mixture was pre-crystallized at 135 c and autogenous pressure for 48 hours in a stainless steel autoclave. The resulting gel was mixed with additional TEAOH aqueous solution (27.86 g-13% aqueous solution) and each organosilane mesoporous template at the loading provided for each example. The gel with the additional TEAOH aqueous solution was then stirred at ambient pressure and 90 ℃ for 6 hours, followed by crystallization in a PTFE-lined stainless steel autoclave at 170 ℃ and autogenous pressure for 7 days. The mole% (mol%) of each loading is based on the silicon content of the gel. The resulting zeolite product was then separated by centrifugation, washed several times with water, dried, and then calcined at 550 ℃ for 6 hours.

An initial set of comparative examples was prepared using template 1, template 2, template 3, and template 4 according to the exemplary preparation scheme 2 provided previously.

Comparative examples 5-5 mol% template 1

Comparative example 5 was prepared according to the exemplary preparation scheme 2 provided above with the addition of an organosilane mesoporous template comprising a loading of 5 mol% template 1.

Comparative example 6-5 mol% template 2

Comparative example 6 was prepared according to the exemplary preparation scheme 2 provided above with the addition of an organosilane mesoporous template comprising a loading of 5 mol% template 2.

Comparative example 7-5 mol% template 3

Comparative example 7 was prepared according to the exemplary preparation scheme 2 provided above with the addition of an organosilane mesoporous template comprising a loading of 5 mol% template 3.

Comparative example 8-5 mol% template 4

Comparative example 8 was prepared according to the exemplary preparation scheme 2 provided above with the addition of an organosilane mesoporous template comprising a loading of 5 mol% template 4.

Another set of examples of the invention was prepared by varying the loading of the mesoporous template in the organosilane in the preparation scheme. Inventive examples were prepared using template 2 with loadings of 2.5 mol% and 10 mol% and template 3 with loadings of 2.5 mol% and 10 mol%. In conjunction with inventive examples 2 and 3, loadings of 2.5 mol%, 5 mol%, and 10 mol% were provided for each of template 2 and template 3.

Inventive example 9-10 mol% template 2

Inventive example 9 was prepared according to the exemplary preparation scheme 1 provided above with the addition of an organosilane mesoporous template comprising a loading of 10 mol% template 2.

Inventive example 10-2.5 mol% template 2

Inventive example 10 was prepared according to the exemplary preparation scheme 1 provided above with the addition of an organosilane mesoporous template comprising a loading of 2.5 mol% template 2.

Inventive example 11-10 mol% template 3

Inventive example 11 was prepared according to the exemplary preparation scheme 1 provided above with the addition of an organosilane mesoporous template comprising a loading of 10 mol% template 3.

Inventive example 12-2.5 mol% template 3

Inventive example 12 was prepared according to the exemplary preparation scheme 1 provided above with the addition of an organosilane mesoporous template comprising a loading of 2.5 mol% template 3.

Comparative example 13 No template

The final comparative example, comparative example 13, was prepared according to the exemplary preparation scheme 1 provided above, but without the addition of an organosilane mesoporous template.

Referring to fig. 1A and 1B, characteristic zeolite beta peaks can be observed in the X-ray diffraction spectra. In fig. 1A, the X-ray diffraction spectra of each of inventive examples 1, 2, 3 and 4 and comparative example 13 show peaks at about 7 ° and about 22 ° 2 θ and a plurality of lower intensity peaks at various other angles, which are characteristic of zeolite β. This demonstrates that the procedure of exemplary preparation scheme 1 produces zeolite beta. Similarly, in fig. 1B, the X-ray diffraction spectrum of each of comparative examples 5, 6, 7, and 13 shows peaks identical to the features of zeolite β at about 7 ° and about 22 ° 2 θ. This demonstrates that the procedure of exemplary preparation scheme 1 produces zeolite beta regardless of the inclusion of a functionalization step.

Referring to fig. 2, the pore width distributions of inventive examples 1 to 4 and comparative example 13 show that the centers of the pore width distributions are shifted as the type of the mesoporous template in the organosilane is changed. In particular, varying the template type allows the resulting pore size distribution of the final zeolite crystals to be adjusted. The pore size distribution thus obtained depends on the size and shape of the pore template in the organosilane. Inventive example 1 (template 1) is indicated as having about 32 angstromsThe pore width distribution center. Inventive example 2 (template 2) is indicated as having an approximateThe pore width distribution center. Inventive example 3 (template 3) is indicated as having an approximateThe pore width distribution center. Inventive example 4 (template 4) is indicated as having an approximateThe pore width distribution center. As expected, comparative example 13 (without template) does not have a distinct peak representing the center of the pore width distribution. It can be appreciated from a review of FIG. 2 that the pore template in the organosilane used for zeolite synthesis can be modified and more specifically modified withThe size and shape of the pore template in the organosilane is used to adjust the center of the pore width distribution. Without wishing to be bound by theory, it is noted that the R groups of each of templates 1, 2, and 3 are progressively larger for each of templates 1, 2, and 3, respectively, and a corresponding increase in pore width is observed.

For the purposes of this disclosure, the term "pore width distribution center" refers to the value of the pore width of the pores of the most ubiquitous mesoporous zeolites. Referring to fig. 2, it can be observed that the frequency of occurrence of individual pore widths in medium pore zeolites follows an incomplete Gaussian function (imperfect Gaussian function). The pore width distribution center corresponds to a particular pore width with the maximum frequency of occurrence represented by the peaks of the individual pore widths plotted.

The total pore volume within the mesoporous zeolite formed can also be adjusted by varying the loading of the organosilane mesoporous template during zeolite formation. Referring to fig. 3, the pore width distributions of inventive example 2(5 mol% template 2), inventive example 9(10 mol% template 2) and inventive example 10(2.5 mol% template 2) demonstrate a shift in total pore volume as the loading of the mesoporous template in the organosilane is varied. Specifically, increasing the loading of the mesoporous template in the organosilane from 2.5 mol% to 5 mol% and then to 10 mol% resulted in a corresponding increase in pore volume, while the center of the pore width distribution remained consistent, approximately

During the formation of the mesoporous zeolite, the organosilane mesoporous template is covalently attached to the zeolite seeds formed in the pre-crystallization step. Using solid state²⁹Si magic angle rotating nuclear magnetic resonance (MAS-NMR) spectroscopic analysis confirmed that the organosilane mesoporous template was attached to the uncalcined zeolite crystals. The uncalcined zeolite crystals represent the mesoporous zeolite prior to the calcination step being carried out at 550 c for 6 hours, so that the organosilane mesoporous template is still present in the sample. Magic Angle rotation is a technique used in nuclear magnetic resonance testing in which a sample is brought to a magic Angle θ relative to the direction of a magnetic field_m(about 54.74 °, where cos is²θ_m1/3) rotation so as to be generally relatively largeThe wide lines are narrowed, thereby increasing the resolution for better identification and analysis of the spectrum. The MAS-NMR of the invention was accomplished by rotating the sample at a frequency of 100MHz under 500MHz NMR. Referring to FIG. 4, MAS-NMR spectra of inventive example 4 (inventive example 4-calcined), inventive example 4 without calcination step (inventive example 4-uncalcined), and commercial beta zeolite. Commercial beta zeolites include 931HOA from Tosoh Corporation, Tokyo Japan. In inventive example 4-no calcination a signal of about-70 ppm indicates that the silicon atom is attached to a carbon atom from the mesoporous template in the organosilane, with the exception of the three other silicon atoms attached by oxygen bridges. This peak disappeared in the spectrum of the calcined sample (inventive example 4), confirming the removal of the template after calcination. It was also noted that this peak was not present in the commercially available zeolite beta samples. The NMR parameters used for the test are based on chem. mater.200921, 641-654, such parameters being incorporated herein by reference.

The attachment of the template to the zeolite seeds was also verified by fourier transform infrared spectroscopy (FTIR). At 1500cm^-1And 1600cm^-1The ambient FTIR signals correspond to N-H stretching and C ═ C aromatic stretching in the template, respectively. Referring to fig. 5, these same signals can be observed for FTIR spectra of the unincorporated template 4(PHAPTMS) and the uncalcined inventive example 4 as well as the control zeolite and the initially formed zeolite seeds. Specifically, 1500cm for template 4 samples^-1And 1600cm^-1Larger peaks are seen around, whereas smaller peaks are seen for the uncalcined inventive example 4 sample and no peaks are seen for the control zeolite. A control zeolite was prepared according to comparative example 13. Similarly, referring to fig. 6, the same signal can be observed for FTIR spectra of the unincorporated template 3 and inventive examples 3 and 11-12 and the control zeolite. In particular, the sample was at 1500cm for the unincorporated template 3^-1And 1600cm^-1Larger peaks are seen around, while smaller peaks are seen for the uncalcined samples of examples 3 and 11-12 of the invention. Furthermore, no corresponding peaks were visible for the control zeolite. The control zeolite is again comparative example 13.

Verifies the connection and the mesopores to the template in the absence of a functionalization stepAnd (5) verification of formation. Referring to FIG. 5, it is noted in FIG. 5 that the unincorporated template 4 and the uncalcined inventive example 4 are at 1500cm^-1And 1600cm^-1The surrounding showed peaks, but the control zeolite and zeolite seeds showed no peaks. The FTIR spectra of figure 5 graphically show that template attachment and mesopore formation are possible in the absence of a functionalization step, since there is no functionalization for the zeolite seed sample, but inventive example 4 thus formed still shows functionalization even in the absence of a discrete functionalization step.

The properties of inventive examples 1-4, comparative examples 5-8 and comparative example 13 are listed in table 1. As demonstrated by the physisorption and temperature programmed desorption data listed in table 1, omitting the discrete functionalization step does not adversely affect the physical properties of the resulting mesoporous zeolite.

For physisorption analysis, argon physisorption measurements were performed at 87K (-186.7 ℃). Before the measurement, the sample was degassed at 350 ℃ overnight. Adsorption isotherms as a function of relative pressure (p/p) were collected for p/p ° from 0.000035 to 0.99, and desorption isotherms were collected for p/p ° from 0.99 to 0.15. It will be appreciated that with respect to p/p °, p is the equilibrium pressure and p ° is the saturated vapor pressure at the adsorption temperature.

For TPD analysis, each sample was activated at 600 ℃ under helium, followed by ammonia adsorption at 180 ℃. It is understood that ammonium is the adsorbate. The ammonia absorption was recorded and the acid position indicated. The ammonia adsorbed zeolite was then purged under helium for 4 hours to minimize the extent of ammonia physisorption. Finally, the TPD spectra were recorded by heating the sample from 180 ℃ to 600 ℃ at a rate of 15 ℃/min under a helium stream. The temperature with the peak TPD signal is denoted as T_max。

Table 1: physical adsorption and temperature programmed desorption data

The pore volumes indicated in table 1 were calculated using the Density Functional Theory (DFT) method. The DFT method is a modeling technique that is considered to be one of the most reliable methods of calculating the pore size and volume of porous materials. In addition, the total pore volume of pores in the range of 0 to 40 nanometers (nm) was determined. The upper limit of 40nm excludes pores of such large size that they are no longer considered pores and functionally become cavities in the mesoporous zeolite. The mesopore pore volume is determined by subtracting the micropore volume calculated according to the DFT method from the total pore volume, which is also calculated according to the DFT method. Exemplary characterization of porous materials using the DFT method is detailed in J.Landers, G.Y.Gor, A.V.Neimark, Colloids and Surfaces A: Physicochem.Eng.accessories 437(2013) 3-32.

Referring to fig. 7A-7D, the amount of argon adsorbed as a function of relative pressure is provided for each of inventive examples 1-4 and comparative examples 5-8. FIG. 7A provides a comparison of the adsorption curves of example 1 (template 1, without functionalization step) of the present invention and comparative example 5 (template 1, with functionalization step). FIG. 7B provides a comparison of the adsorption curves of inventive example 2 (template 2, without functionalization step) and comparative example 6 (template 2, with functionalization step). FIG. 7C provides a comparison of the adsorption curves of example 3 (template 3, without functionalization step) of the present invention and comparative example 7 (template 3, with functionalization step). FIG. 7D provides a comparison of the adsorption curves of inventive example 4 (template 4, without functionalization step) and comparative example 8 (template 4, with functionalization step). Note that in each of fig. 7A-7D, the inventive and comparative examples maintained similar adsorption curves, indicating that the impact on adsorption was minimal when either discrete functionalization steps were included or omitted. Each of fig. 7A-7D includes two lines per sample, as the relative pressure first increases and then decreases during the test, resulting in two lines. One line for each sample is the adsorption branch and the other is the desorption branch.

Referring to fig. 8A-8D, TPD signals as a function of desorption temperature are provided for each of inventive examples 1-4 and comparative examples 5-8. Specifically, fig. 8A provides a comparison of TPD signals for inventive example 1 (template 1, no functionalization step) and comparative example 5 (template 1, with functionalization step). Figure 8B provides a comparison of TPD signals for inventive example 2 (template 2, no functionalization step) and comparative example 6 (template 2, with functionalization step). Figure 8C provides a comparison of TPD signals for example 3 of the invention (template 3, without functionalization step) and comparative example 7 (template 3, with functionalization step). Figure 8D provides a comparison of TPD signals for example 4 of the present invention (template 4, without a functionalization step) and comparative example 8 (template 4, with a functionalization step). The peak of each graph indicates the temperature at which ammonia is desorbed. The higher the temperature required for desorption, the stronger the acid sites. The area under each peak indicates how much ammonia is desorbed and thus how many acid sites each zeolite contains. Note that in each of fig. 8A-8D, the present invention embodiment and the comparative embodiment maintain similar TPD signals, indicating that there is little impact on the binding performance when either discrete functionalization steps are included or omitted. Given the minimal differences between each inventive example and its corresponding comparative example, it can be concluded that the removal of the functionalization step has little effect on the acid site intensity or concentration.

The inventive and comparative examples characterized in table 1 demonstrate the ability to produce mesoporous zeolites without discrete functionalization steps while avoiding adverse effects on the physical properties of the resulting mesoporous zeolites. In particular, the BET surface area of the mesoporous zeolite formed with and without the functionalization step is similar, with a slight increase in BET surface area with the functionalization step for some organosilane mesoporous templates (templates 1 and 3) and a slight decrease in BET surface area with the functionalization step for some organosilane mesoporous templates (templates 2 and 4). Similarly, the mesopore volume of the mesoporous zeolite formed with and without the functionalization step is similar, with the mesopore volume increasing slightly with the functionalization step for some organosilane mesopore templates (templates 2 and 3) and decreasing slightly with the functionalization step for some organosilane mesopore templates (templates 1 and 4). It is also noted that the center of the pore width distribution remains substantially the same between the mesoporous zeolites formed with and without the discrete functionalization steps.

It should be appreciated that various aspects of the method of forming a mesoporous zeolite having tunable physical properties are described and can be used in combination with various other aspects.

In a first aspect, a method of forming a mesoporous zeolite having tunable physical properties is provided. The method comprises mixing a silicon-containing material, an aluminum-containing material, and at least one quaternary amine to produce a zeolite precursor solution; pre-crystallizing the zeolite precursor solution at a pre-crystallization temperature above 125 ℃ and an autogenous pressure to form a pre-crystallized zeolite precursor solution, the pre-crystallized zeolite precursor solution exhibiting formation of an amorphous phase in a quasi-steady state in which the solid and solution phases are close to equilibrium and silicate and aluminosilicate anion distributions are established; combining two or more different organosilane mesoporous templates with the pre-crystallized zeolite precursor solution to produce a zeolite precursor gel; crystallizing the zeolite precursor gel to produce a crystalline zeolite intermediate; and calcining the crystalline zeolite intermediate to produce the mesoporous zeolite.

The second aspect may include the first aspect, wherein the crystalline zeolite intermediate is calcined by exposure to a temperature of at least 500 ℃.

A third aspect may include the first or second aspect, wherein the mesoporous template in the organosilane comprises a compound according to, wherein R is aliphatic, aromatic or a heteroatom containing group.

The fourth aspect may include the third aspect, wherein R is H, R is Ph, or R is CH ═ CHPh.

A fifth aspect may include any of the first to fourth aspects, wherein the silicon-containing material comprises SiO₂Sodium silicate, tetramethylsiloxane, tetraethylsiloxane, a silicon salt, a silicon alkoxide, or combinations thereof.

The sixth aspect may include any one of the first to fifth aspects, wherein the aluminum-containing material includes aluminum nitrate, aluminum sulfate, aluminum alkoxide, other aluminum salts, or combinations thereof.

A seventh aspect may include any one of the first to sixth aspects, wherein the medium pore zeolite comprises an MFI framework type, a FAU framework type, a MOR framework type, or a BEA framework type.

An eighth aspect may include any of the first to sixth aspects, wherein the medium pore zeolite comprises beta zeolite.

A ninth aspect may include any of the first to eighth aspects, wherein the quaternary amine comprises tetraethylammonium hydroxide, tetraethylammonium alkoxide, tetrapropylammonium alkoxide, other basic materials containing ammonium, or combinations thereof.

The tenth aspect may include any one of the first to ninth aspects, wherein the quaternary amine comprises tetraethylammonium hydroxide.

An eleventh aspect can include any of the first through tenth aspects, wherein the organosilane mesoporous template has a total loading in the organosilane with respect to the silicon-containing material of 0.5 mol% to 25 mol%.

A twelfth aspect may include any one of the first to eleventh aspects, wherein the crystallizing is accomplished at a crystallization temperature above 140 ℃.

In a thirteenth aspect, an organosilane mesoporous template is provided. The mesoporous template in the organosilane includes structures according to wherein R is aliphatic, aromatic or a heteroatom containing group.

The fourteenth aspect may include the thirteenth aspect, wherein R is H.

The fifteenth aspect may include the thirteenth aspect, wherein R is a phenyl (Ph) group.

A sixteenth aspect can include the thirteenth aspect, wherein R is CH ═ CHPh. In a seventeenth aspect, there is provided a method of forming a mesoporous template in an organosilane comprising a structure according to, wherein R is an aliphatic, aromatic, or heteroatom-containing group. The process comprises reacting 1 equivalent of an aniline derivative in the presence of ethanolAnd 1 to 1.5And (5) structure.

An eighteenth aspect may include the seventeenth aspect, wherein the stirring and heating of the reaction mixture is accomplished in a schlenk flask by stirring the reaction mixture under reflux for 4 to 24 hours.

A nineteenth aspect can include the seventeenth aspect, wherein the stirring and heating of the reaction mixture is accomplished in a sealed container by stirring the reaction mixture at 130 to 220 ℃ for 5 to 90 minutes.

A twentieth aspect may include the eighteenth or nineteenth aspect, wherein R is H, R is phenyl (Ph), or R is CH ═ CHPh.

It is noted that one or more of the following claims utilize the term "wherein" as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open transition phrase used to introduce a recitation of a series of features of a structure and is to be interpreted in the same manner as the more commonly used open leading term "comprising".

It should be understood that any two quantitative values assigned to a characteristic may constitute a range for the characteristic, and all combinations of ranges formed from all specified quantitative values for a given characteristic are encompassed by the present disclosure.

Having described the subject matter of the present disclosure in detail and by reference to specific embodiments, it should be noted that the various details described in the present disclosure should not be taken as implying that such details relate to elements that are essential components of the various embodiments described in the present disclosure, even where specific elements are illustrated in each of the figures accompanying the description of the present disclosure. Rather, the appended claims should be construed broadly and in a manner that uniquely identifies the respective scope of the various embodiments described in this disclosure. Further, it should be apparent that modifications and variations are possible without departing from the scope of the appended claims.