阅读说明：本技术 一种硫掺杂碳负载的铂基金属氧化物界面材料、其制备方法及应用 (Sulfur-doped carbon-loaded platinum-based metal oxide interface material, and preparation method and application thereof ) 是由 梁海伟 南航 于 2020-12-17 设计创作，主要内容包括：本发明提供了一种硫掺杂碳负载的铂基金属氧化物界面材料的制备方法,包括：S1)将硫掺杂介孔碳纳米材料、铂前驱体与第一过渡金属盐在第一溶剂中混合,除去第一溶剂后,得到混合物；S2)将所述混合物进行高温还原,得到硫掺杂碳负载铂基合金材料；S3)将所述硫掺杂碳负载铂基合金材料在氧化气氛中进行退火处理,得到硫掺杂碳负载的铂基金属氧化物界面材料。与现有技术相比,本发明铂基金属氧化物界面材料中富含大量的金属/氧化物界面位点,使其在多种催化加氢反应中拥有优秀的催化活性；同时,作为载体的硫掺杂多孔碳具有高比表面积和高硫含量,与负载的金属具有强相互作用,可以提高催化反应中的稳定性。(The invention provides a preparation method of a sulfur-doped carbon-loaded platinum-based metal oxide interface material, which comprises the following steps: s1) mixing the sulfur-doped mesoporous carbon nanomaterial, the platinum precursor and the first transition metal salt in a first solvent, and removing the first solvent to obtain a mixture; s2) carrying out high-temperature reduction on the mixture to obtain a sulfur-doped carbon-loaded platinum-based alloy material; s3) annealing the sulfur-doped carbon-loaded platinum-based alloy material in an oxidizing atmosphere to obtain the sulfur-doped carbon-loaded platinum-based metal oxide interface material. Compared with the prior art, the platinum-based metal oxide interface material is rich in a large amount of metal/oxide interface sites, so that the platinum-based metal oxide interface material has excellent catalytic activity in various catalytic hydrogenation reactions; meanwhile, the sulfur-doped porous carbon used as the carrier has high specific surface area and high sulfur content, has strong interaction with the loaded metal, and can improve the stability in the catalytic reaction.)

1. A preparation method of a sulfur-doped carbon-supported platinum-based metal oxide interface material is characterized by comprising the following steps of:

s1) mixing the sulfur-doped mesoporous carbon nanomaterial, the platinum precursor and the first transition metal salt in a first solvent, and removing the first solvent to obtain a mixture;

s2) carrying out high-temperature reduction on the mixture to obtain a sulfur-doped carbon-loaded platinum-based alloy material;

s3) annealing the sulfur-doped carbon-loaded platinum-based alloy material in an oxidizing atmosphere to obtain the sulfur-doped carbon-loaded platinum-based metal oxide interface material.

2. The method according to claim 1, wherein the volume content of oxygen in the oxidizing atmosphere in step S3) is 15% to 25%; the temperature of the annealing treatment is 150-250 ℃; the annealing time is 1-8 h; the temperature rise rate of the annealing treatment is 1-10 ℃/min.

3. The preparation method according to claim 1, wherein the temperature of the high-temperature reduction in the step S2) is 800-1000 ℃; the high-temperature reduction time is 1-3 h; the temperature rise rate and the temperature drop rate of the high-temperature reduction are respectively and independently 3-8 ℃/min.

4. The preparation method according to claim 1, wherein the molar ratio of the platinum precursor to the first transition metal salt is (1-8): 1.

5. the preparation method according to claim 1, wherein the sulfur-doped mesoporous carbon nanomaterial is prepared by the following method:

A1) mixing the organic sulfur-containing micromolecules, the template and a second transition metal salt in a second solvent, and removing the second solvent to obtain a carbon material precursor mixture;

A2) carrying out high-temperature pyrolysis on the carbon material precursor mixture to obtain a carbon nano material;

A3) and etching the carbon nano material to remove the template and the metal particles to obtain the sulfur-doped mesoporous carbon nano material.

6. The preparation method of claim 5, wherein the organic sulfur-containing small molecule is selected from one or more of 2,2' -bithiophene, 5' -dibromo-2, 2' -bithiophene, 2':5',2 "-trithiophene and 5, 5" -dibromo- [2,2':5',2 "] trithiophene;

the first transition metal salt is selected from one or more of nitrate and chloride of titanium, iron, zirconium and nickel;

the second transition metal salt is selected from one or more of cobalt nitrate, ferric nitrate, silver nitrate, copper nitrate and nickel nitrate.

7. The preparation method according to claim 5, wherein the temperature of the high-temperature pyrolysis is 800-1000 ℃; the high-temperature pyrolysis time is 1-3 h; the temperature rise rate and the temperature drop rate of the high-temperature cracking are respectively and independently 3-8 ℃/min.

8. The preparation method according to claim 5, wherein the step A3) is specifically as follows:

and carrying out first etching on the carbon nano material in an alkaline solution or hydrofluoric acid to remove the template, then heating in an acidic solution to carry out second etching, and removing the metal particles to obtain the sulfur-doped mesoporous carbon nano material.

9. The sulfur-doped carbon-supported platinum-based metal oxide interface material prepared by the preparation method of any one of claims 1 to 8.

10. The application of the sulfur-doped carbon-loaded platinum-based metal oxide interface material prepared by the preparation method of any one of claims 1 to 8 as a catalyst in catalytic hydrogenation of organic matters.

Technical Field

The invention belongs to the technical field of nano materials, and particularly relates to a sulfur-doped carbon-loaded platinum-based metal oxide interface material, and a preparation method and application thereof.

Background

In catalytic science, heterogeneous catalysis plays a significant role due to its excellent catalytic activity and selectivity, good stability and recyclable property. Among them, a catalyst having a metal oxide as a carrier is an important heterogeneous catalyst. The interaction of the oxide carrier and the loaded metal not only greatly improves the stability of the catalyst, but also greatly improves the selectivity of the catalyst due to the change of the electronic structure.

However, metal/oxide catalysts still suffer from several disadvantages, such as: firstly, the specific surface area of the oxide is not high, and the size of metal particles is difficult to control; ② the activity of the metal/oxide catalyst still needs to be improved, which limits the application in the practical production. To this end, scientists first studied the active centers of metal/oxide catalysts. Through research on model catalysts, scientists have discovered that the metal/oxide interface is critical to the adsorptive conversion of reactants. Furthermore, by comparing the catalytic activity with the number of different sites, it can be found that there is a correlation between the catalytic activity and the number of metal/oxide interface sites. Scientists have used the density functional theory to calculate the adsorption energy of different sites of metal/oxide catalysts and have found that there is a significant change in adsorption energy at the metal/oxide interface, thereby affecting catalytic activity and selectivity. In summary, the active center of the metal/oxide catalyst is the metal/oxide interface, which is the key to the promotion of catalytic activity and selectivity. Therefore, the key to the next step in the development of metal/oxide catalysts is to maximize the number of metal/oxide interface sites.

To this end, scientists have developed new strategies for constructing metal/oxide interfaces. For example: the oxide is deposited onto the prepared metal using a deposition process. However, these methods still have the disadvantages of higher cost or poor universality. Therefore, it is a research hotspot to develop a method for constructing a metal/oxide interface with high universality and practicability.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a sulfur-doped carbon-supported platinum-based metal oxide interface material rich in a large number of metal/oxide interface sites, and a preparation method and an application thereof.

The invention provides a preparation method of a sulfur-doped carbon-loaded platinum-based metal oxide interface material, which comprises the following steps:

s1) mixing the sulfur-doped mesoporous carbon nanomaterial, the platinum precursor and the first transition metal salt in a first solvent, and removing the first solvent to obtain a mixture;

s2) carrying out high-temperature reduction on the mixture to obtain a sulfur-doped carbon-loaded platinum-based alloy material;

s3) annealing the sulfur-doped carbon-loaded platinum-based alloy material in an oxidizing atmosphere to obtain the sulfur-doped carbon-loaded platinum-based metal oxide interface material.

Preferably, the volume content of the oxygen in the oxidizing atmosphere in the step S3) is 15% to 25%; the temperature of the annealing treatment is 150-250 ℃; the annealing time is 1-8 h; the temperature rise rate of the annealing treatment is 1-10 ℃/min.

Preferably, the temperature of the high-temperature reduction in the step S2) is 800-1000 ℃; the high-temperature reduction time is 1-3 h; the temperature rise rate and the temperature drop rate of the high-temperature reduction are respectively and independently 3-8 ℃/min.

Preferably, the molar ratio of the platinum precursor to the first transition metal salt is (1-8): 1.

preferably, the sulfur-doped mesoporous carbon nanomaterial is prepared by the following method:

A1) mixing the organic sulfur-containing micromolecules, the template and a second transition metal salt in a second solvent, and removing the second solvent to obtain a carbon material precursor mixture;

A2) carrying out high-temperature pyrolysis on the carbon material precursor mixture to obtain a carbon nano material;

A3) and etching the carbon nano material to remove the template and the metal particles to obtain the sulfur-doped mesoporous carbon nano material.

Preferably, the organic sulfur-containing small molecule is selected from one or more of 2,2 '-bithiophene, 5' -dibromo-2, 2 '-bithiophene, 2':5', 2' -trithiophene and 5,5 '-dibromo- [2,2':5', 2' ] trithiophene;

the first transition metal salt is selected from one or more of nitrate and chloride of titanium, iron, zirconium and nickel;

the second transition metal salt is selected from one or more of cobalt nitrate, ferric nitrate, silver nitrate, copper nitrate and nickel nitrate.

Preferably, the temperature of the high-temperature pyrolysis is 800-1000 ℃; the high-temperature pyrolysis time is 1-3 h; the temperature rise rate and the temperature drop rate of the high-temperature cracking are respectively and independently 3-8 ℃/min.

Preferably, the step a3) is specifically:

and carrying out first etching on the carbon nano material in an alkaline solution or hydrofluoric acid to remove the template, then heating in an acidic solution to carry out second etching, and removing the metal particles to obtain the sulfur-doped mesoporous carbon nano material.

The invention also provides a sulfur-doped carbon-loaded platinum-based metal oxide interface material prepared by the preparation method.

The invention also provides application of the sulfur-doped carbon-loaded platinum-based metal oxide interface material prepared by the preparation method as a catalyst in catalytic hydrogenation of organic matters.

The invention provides a preparation method of a sulfur-doped carbon-loaded platinum-based metal oxide interface material, which comprises the following steps: s1) mixing the sulfur-doped mesoporous carbon nanomaterial, the platinum precursor and the first transition metal salt in a first solvent, and removing the first solvent to obtain a mixture; s2) carrying out high-temperature reduction on the mixture to obtain a sulfur-doped carbon-loaded platinum-based alloy material; s3) annealing the sulfur-doped carbon-loaded platinum-based alloy material in an oxidizing atmosphere to obtain the sulfur-doped carbon-loaded platinum-based metal oxide interface material. Compared with the prior art, the preparation method provided by the invention is simple, can be applied to transition metal elements, has good universality, and the obtained platinum-based metal oxide interface material is rich in a large amount of metal/oxide interface sites, so that the platinum-based metal oxide interface material has excellent catalytic activity in various catalytic hydrogenation reactions; meanwhile, the sulfur-doped porous carbon used as the carrier has high specific surface area and high sulfur content, has strong interaction with the loaded metal, and can improve the stability in the catalytic reaction, so that the obtained sulfur-doped carbon-loaded platinum-based metal oxide interface material has better catalytic activity and stability in the catalytic hydrogenation reaction as a catalyst.

Drawings

FIG. 1 is a schematic flow chart of the preparation process of the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material provided by the invention;

fig. 2 is an X-ray diffraction pattern of the sulfur-doped carbon-supported platinum-titanium alloy material and the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material obtained in example 1 of the present invention;

FIG. 3 is a scanning transmission microscope photograph of the spherical aberration correction of the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material obtained in example 1 of the present invention;

FIG. 4 is a photograph of a spherical aberration corrected scanning transmission microscope of the sulfur-doped carbon-supported platinum titanium alloy material and the sulfur-doped carbon-supported platinum titanium bimetallic oxide interface material provided in example 1 of the present invention;

fig. 5 is a bar graph of catalytic activity of the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material and the sulfur-doped carbon-supported platinum-titanium alloy material in a benzaldehyde hydrogenation reaction, which are provided in example 1 of the present invention;

fig. 6 is a bar graph of catalytic activity and selectivity of the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material and the sulfur-doped carbon-supported platinum-titanium alloy material in a furfural hydrogenation reaction, which are provided in example 1 of the present invention;

FIG. 7 is a bar graph of the catalytic activity of the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material and the sulfur-doped carbon-supported platinum-titanium alloy material in the nitrobenzene hydrogenation reaction, which is provided in example 1 of the present invention;

fig. 8 is a bar chart of the activity of the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material in the benzaldehyde hydrogenation reaction, which is obtained in example 1 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a preparation method of a sulfur-doped carbon-loaded platinum-based metal oxide interface material, which comprises the following steps: s1) mixing the sulfur-doped mesoporous carbon nanomaterial, the platinum precursor and the first transition metal salt in a first solvent, and removing the first solvent to obtain a mixture; s2) carrying out high-temperature reduction on the mixture to obtain a sulfur-doped carbon-loaded platinum-based alloy material; s3) annealing the sulfur-doped carbon-loaded platinum-based alloy material in an oxidizing atmosphere to obtain the sulfur-doped carbon-loaded platinum-based metal oxide interface material.

Referring to fig. 1, fig. 1 is a schematic view of a preparation process of a sulfur-doped carbon-supported platinum-based metal oxide interface material provided by the present invention.

The present invention is not particularly limited in terms of the source of all raw materials, and may be commercially available.

In the present invention, the sulfur-doped mesoporous carbon nanomaterial is preferably prepared according to the following method: A1) mixing the organic sulfur-containing micromolecules, the template and a second transition metal salt in a second solvent, and removing the second solvent to obtain a carbon material precursor mixture; A2) carrying out high-temperature pyrolysis on the carbon material precursor mixture to obtain a carbon nano material; A3) and etching the carbon nano material to remove the template and the metal particles to obtain the sulfur-doped mesoporous carbon nano material.

Mixing the organic sulfur-containing micromolecules, the template and a second transition metal salt in a second solvent, and removing the second solvent to obtain a carbon material precursor mixture; the organic sulfur-containing small molecule is preferably 2,2 '-bithiophene, 5' -dibromo-2, 2 '-bithiophene, 2':5', 2' -trithiophene and 5,5 '-dibromo- [2,2':5', 2']One or more of a trithiophene; the template is preferably silicon dioxide; the second transition metal is preferably one or more of cobalt nitrate, iron nitrate, silver nitrate, copper nitrate and nickel nitrate, and more preferably Co (NO)₃)₂·6H₂O、Fe(NO₃)₃·9H₂O、AgNO₃、Cu(NO₃)₂·3H₂O and Ni (NO)₃)₂·6H₂One or more of O; the second transition metal salt is added, so that volatilization of the organic sulfur-containing micromolecules in the high-temperature pyrolysis process can be effectively prevented, and the organic sulfur-containing micromolecules are promoted to form a carbon-based material; the mass ratio of the organic sulfur-containing micromolecules to the template to the second transition metal salt is preferably (0.8-1.5): (0.8-1.5): (0.4-0.8), more preferably (0.8-1.2): (0.8-1.2): (0.4-0.8), and more preferably (0.8-1.2): (0.8-1.2): (0.4 to 0.6), most preferably 1: 1: (0.4-0.6); in some embodiments provided herein, the mass ratio of the organic sulfur-containing small molecule, the template, and the second transition metal salt is preferably 1: 1: 0.4; in some embodiments provided herein, the mass ratio of the organic sulfur-containing small molecule, the template, and the second transition metal salt is preferably 1: 1: 0.5; in other embodiments provided herein, the mass ratio of the organic sulfur-containing small molecule, the template, and the second transition metal salt is preferably 1: 1: 0.6; the second solvent is not particularly limited as long as it is an organic solvent well known to those skilled in the art, and tetrahydrofuran is preferable in the present invention; the purpose of this step is to mix the raw materials thoroughly to get a homogeneous mixture; the method for removing the second solvent is a method well known to those skilled in the art and is not particularly limitedIn the present invention, rotary evaporation is preferable.

Carrying out high-temperature pyrolysis on the carbon material precursor mixture to obtain a carbon nano material; in the step, the carbon material precursor mixture is directly pyrolyzed, and with the rise of pyrolysis temperature, the organic sulfur-containing micromolecules are polymerized to form carbon; the high-temperature pyrolysis is preferably carried out in a protective atmosphere; the protective atmosphere is not particularly limited as long as it is known to those skilled in the art, and nitrogen and/or argon is preferable in the present invention; the flow rate of the protective atmosphere is preferably 0.1-0.5L/min, more preferably 0.2-0.4L/min, and still more preferably 0.3L/min; the temperature of the high-temperature pyrolysis is preferably 800-1000 ℃; the high-temperature pyrolysis time, namely the heat preservation time, is preferably 1-3 h, and more preferably 2 h; the heating rate and the cooling rate of the high-temperature pyrolysis are respectively and independently preferably 3-8 ℃/min, more preferably 4-6 ℃/min, and further preferably 5 ℃/min.

Etching the carbon nano material to remove the template and the metal particles to obtain a sulfur-doped mesoporous carbon nano material; in the process, the template and the residual metal particles are removed by etching with an etching agent, so that the sulfur-doped carbon nanomaterial with mesopores is obtained; in the present invention, this step is preferably embodied as follows: carrying out first etching on the carbon nano material in an alkaline solution or hydrofluoric acid to remove the template, then heating the carbon nano material in an acidic solution to carry out second etching, and removing metal particles to obtain a sulfur-doped mesoporous carbon nano material; the alkaline solution is preferably an alkali metal hydroxide solution, more preferably a potassium hydroxide solution and/or a sodium hydroxide solution; the concentration of the alkaline solution is preferably 1-3 mol/L, and more preferably 2 mol/L; in the first etching process, the alkaline solution and hydrofluoric acid react with the template to realize the purpose of etching; the first etching time is preferably 48-72 hours; in the invention, the first etching is preferably carried out by stirring and etching the carbon nano material in alkaline solution or hydrofluoric acid for 48h, then carrying out suction filtration to separate solid, then adding the alkaline solution or hydrofluoric acid, stirring and etching for 24h, and carrying out suction filtration; the acid solution is preferably a sulfuric acid solution; the concentration of the acidic solution is preferably 0.5-1 mol/L; the temperature of the second etching is preferably 80-100 ℃, and more preferably 90 ℃; the time of the second etching is preferably 4-8 h.

Mixing a sulfur-doped mesoporous carbon nano material, a platinum precursor and a first transition metal salt in a first solvent, and removing the first solvent to obtain a mixture; the platinum precursor is a platinum-containing inorganic substance, preferably chloroplatinic acid; the first transition metal salt is preferably a transition metal salt in the fourth period and the fifth period, more preferably a nitrate and/or chloride of a transition metal, and still more preferably one or more of nitrate and chloride of titanium, iron, zirconium and nickel; the mole ratio of the platinum precursor to the first transition metal salt is preferably (1-8): 1, more preferably (1-6): 1, and preferably (1-5): 1, most preferably (1-3.2): 1; the preferable proportion of the sulfur-doped mesoporous carbon nanomaterial to the platinum element in the platinum precursor is (80-95) mg: (0.02 to 0.1) mmol, more preferably (80 to 95) mg: (0.021-0.095) mmol; the first solvent is not particularly limited as long as it is a solvent well known to those skilled in the art, and in the present invention, water is preferred; in the invention, preferably, the platinum precursor and the first transition metal salt are respectively mixed with the first solvent to obtain respective solutions, and then the two solutions are mixed with the sulfur-doped mesoporous carbon nano material; the concentrations of the platinum precursor solution and the transition metal salt solution are respectively and independently preferably 0.005-0.02 mol/L, and more preferably 0.01-0.015 mol/L; the first solvent is removed after mixing, and the method for removing the first solvent is well known to those skilled in the art and is not particularly limited, and in the present invention, rotary evaporation is preferable.

Carrying out high-temperature reduction on the mixture to obtain a sulfur-doped carbon-loaded platinum-based alloy material; the volume concentration of the introduced hydrogen in the reducing atmosphere during high-temperature reduction is preferably 3-10%, more preferably 3-8%, and still more preferably 5%; the flow rate of the reducing atmosphere is preferably 0.1-0.5L/min, more preferably 0.2-0.4L/min, and still more preferably 0.3L/min; the temperature of the high-temperature reduction is preferably 800-1000 ℃; the time of high-temperature reduction, namely the heat preservation time, is preferably 1-3 h, and more preferably 2 h; the heating rate and the cooling rate of the high-temperature reduction are respectively and independently preferably 3-8 ℃/min, more preferably 4-6 ℃/min, and further preferably 5 ℃/min; and cooling to room temperature to obtain the sulfur-doped carbon-loaded platinum-based alloy material.

Carrying out annealing treatment on the sulfur-doped carbon-loaded platinum-based alloy material in an oxidizing atmosphere; the volume content of oxygen in the oxidizing atmosphere is preferably 15% to 25%, more preferably 18% to 24%, and still more preferably 20% to 22%; in the present invention, it is preferable to use an air atmosphere as the oxidizing atmosphere; the temperature of the annealing treatment is preferably 150-250 ℃; in some embodiments provided herein, the temperature of the annealing treatment is preferably 200 ℃; in some embodiments provided herein, the temperature of the annealing treatment is preferably 150 ℃; in some embodiments provided herein, the temperature of the annealing treatment is preferably 250 ℃; the annealing treatment time, namely the heat preservation time, is preferably 1-8 h, more preferably 1-5 h, still more preferably 1-3 h, and most preferably 1-2 h; the heating rate of the annealing treatment is preferably 1-10 ℃/min, more preferably 3-8 ℃/min, still more preferably 4-6 ℃/min, and most preferably 5 ℃/min.

And (4) annealing and cooling to room temperature to obtain the sulfur-doped carbon-loaded platinum-based metal oxide interface material.

The preparation method of the carbon-loaded platinum-based metal oxide interface material is simple, can be applied to transition metal elements, has good universality, and the obtained platinum-based metal oxide interface material is rich in a large amount of metal/oxide interface sites, so that the platinum-based metal oxide interface material has excellent catalytic activity in various catalytic hydrogenation reactions; meanwhile, the sulfur-doped porous carbon used as the carrier has high specific surface area and high sulfur content, has strong interaction with the loaded metal, and can improve the stability in the catalytic reaction, so that the obtained sulfur-doped carbon-loaded platinum-based metal oxide interface material has better catalytic activity and stability in the catalytic hydrogenation reaction as a catalyst.

The invention also provides a sulfur-doped carbon-loaded platinum-based metal oxide interface material prepared by the method.

The transition metal salt used in the preparation process of the re-alloy can be selected from common transition metal elements in the fourth period and the fifth period, and has better universality.

The invention also provides application of the sulfur-doped carbon-loaded platinum-based metal oxide interface material prepared by the preparation method as a catalyst in catalytic hydrogenation of organic matters.

The organic catalytic hydrogenation is preferably benzaldehyde hydrogenation, furfural hydrogenation or nitrobenzene hydrogenation.

The sulfur-doped carbon-loaded platinum-based metal oxide interface material prepared by the invention can control the size of a platinum-based alloy in a high-temperature reduction process and improve the atomic proportion exposed on the surface due to the high specific surface area and the high sulfur content of the sulfur-doped mesoporous carbon; in addition, a large number of metal/oxide interfaces are constructed on the surfaces of alloy particles through air annealing, more active centers are provided, and therefore the prepared sulfur-doped carbon-supported platinum-based metal oxide interface material has better catalytic activity and selectivity.

In order to further illustrate the present invention, the following will describe in detail a sulfur-doped carbon-supported platinum-based metal oxide interface material, its preparation method and application with reference to the examples.

The reagents used in the following examples are all commercially available.

Example 1

a. 2g of 2,2' -bithiophene, 2g of silica, 1g of Co (NO)₃)₂·6H₂Mixing O with 150ml of tetrahydrofuran, stirring uniformly, and then removing the solvent by rotary evaporation to obtain a uniformly mixed solid mixture;

b. transferring the obtained solid mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tube furnace, introducing nitrogen serving as protective gas at the flow rate of 0.3L/min, heating the tube furnace to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; then cooling to room temperature at the speed of 5 ℃/min to obtain the carbon nano material;

c. transferring the carbon nano material into a conical flask, adding about 100ml of 2mol/L NaOH solution in the conical flask for the first alkali etching, and stirring for 48 hours; then, carrying out vacuum filtration separation to obtain a solid, and transferring the solid into a conical flask again; adding about 100ml of 2mol/L NaOH solution into the mixture for the second alkali etching, stirring for 24 hours, then carrying out vacuum filtration and separation to obtain a solid, and drying at 80 ℃ to obtain the carbon nano material after silicon dioxide etching;

d. placing the carbon nano material etched with the silicon dioxide into a 50ml round-bottom flask, uniformly mixing the carbon nano material with 0.5mol/L sulfuric acid solution, heating the mixture in an oil bath at 80 ℃, then carrying out vacuum filtration to separate solid, and drying the solid to obtain a sulfur-doped mesoporous carbon nano material;

e. uniformly mixing 80mg of the sulfur-doped mesoporous carbon nano material, 9.5ml of 0.01mol/ml chloroplatinic acid solution and 3ml of 0.01mol/L titanium tetrachloride solution, and removing the solution by rotary evaporation to obtain a solid mixture. Then transferring the obtained solid mixture into a quartz crucible or a corundum crucible, and putting the quartz crucible or the corundum crucible into a tube furnace; argon-hydrogen (composition: 95% Ar + 5% H) was introduced into the tube furnace at a flow rate of 0.3L/min₂) As a protective gas, heating the tubular furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; then cooling to room temperature at the speed of 5 ℃/min to obtain the sulfur-doped carbon-loaded platinum-titanium alloy material;

f. and heating the sulfur-doped carbon-loaded platinum-titanium alloy material to 200 ℃ at the speed of 5 ℃/min in a muffle furnace, annealing, keeping for 2h, and cooling to room temperature to obtain the sulfur-doped carbon-loaded platinum-titanium bimetallic oxide interface material.

The sulfur-doped carbon-supported platinum-titanium alloy material and the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material obtained in example 1 were analyzed by X-ray diffraction, and the X-ray diffraction patterns thereof were obtained as shown in fig. 2.

The sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material obtained in example 1 was analyzed by using a spherical aberration correction scanning transmission microscope, and a photograph of the spherical aberration correction scanning transmission microscope is shown in fig. 3.

As can be seen from fig. 2 and 3, the platinum-titanium nanoparticles of the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material prepared in this example have a small size and are uniformly distributed.

The sulfur-doped carbon-supported platinum-titanium alloy material and the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material obtained in example 1 were analyzed by a spherical aberration correction scanning transmission microscope, and a photograph of the spherical aberration correction scanning transmission microscope is shown in fig. 4. As can be seen from the spherical aberration correction photographs of the individual particles before and after the annealing treatment in fig. 4, when the particles of the sulfur-doped carbon-supported platinum-titanium alloy material have an ordered structure, the particles of the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material after the annealing treatment have a reduced order and a rough and uneven surface, which indicates that titanium segregates to the surface to be oxidized during the annealing treatment to form a platinum-titanium bimetallic oxide interface.

FIG. 5 is a bar chart of the catalytic activity of the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material and the sulfur-doped carbon-supported platinum-titanium alloy material in the benzaldehyde hydrogenation reaction, wherein Pt/C is 5% Pt/C of Alfa Aesar company, CAS number is 7440-06-4, inventory number is A11186, and Pt/TiO is provided in the embodiment of the present invention₂Is a commercially available TiO of type P25₂Supported 5% by mass of a platinum catalyst, Pt₃Ti is a sulfur-doped carbon-loaded platinum-titanium alloy material, Pt-TiO_xIs a sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material. Reaction conditions are as follows: 100 μ l benzaldehyde, 1ml water as solvent, 0.05 mol% catalyst, 1MPa H₂The reaction temperature was 80 ℃ and the reaction time was 15 minutes.

Fig. 6 is a bar graph of catalytic activity and selectivity of the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material and the sulfur-doped carbon-supported platinum-titanium alloy material in a furfural hydrogenation reaction, according to an embodiment of the present invention. Reaction conditions are as follows: 0.5mmol of furfural, 1ml of water as solvent, 0.1 mol% of catalyst, 1MPa of H₂The reaction temperature was 80 ℃ and the reaction time was 4 hours.

Fig. 7 is a bar graph of catalytic activity of the sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material and the sulfur-doped carbon-supported platinum-titanium alloy material in a nitrobenzene hydrogenation reaction, according to the embodiment of the present invention. Reaction conditions are as follows: 2mmol of nitrobenzene, 1ml of ethyl acetate as solvent, 0.025 mol% of catalyst, 1MPa of H₂The reaction temperature was 25 ℃ and the reaction time was 30 minutes.

FIG. 8 shows an example of a sulfur-doped carbon-supported platinum-titanium bimetallic oxide interface material on benzeneActive column diagram of circulation experiment in formaldehyde hydrogenation reaction. Reaction conditions are as follows: 100 μ l benzaldehyde, 1ml water as solvent, 0.05 mol% catalyst, 1MPa H₂The reaction temperature was 80 ℃ and the reaction time was 15 minutes.

Example 2

a. 2g of 5,5 '-dibromo-2, 2' -bithiophene, 2g of silica, 0.8g of Co (NO)₃)₂·6H₂Mixing O with 150ml of tetrahydrofuran, stirring uniformly, and then removing the solvent by rotary evaporation to obtain a uniformly mixed solid mixture;

b. transferring the obtained solid mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen serving as protective gas at the flow rate of 0.3L/min, heating the tubular furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; then cooling to room temperature at the speed of 5 ℃/min to obtain the carbon nano material;

c. transferring the carbon nano material into a conical flask, adding about 100ml of 2mol/L NaOH solution in the conical flask for the first alkali etching, and stirring for 48 hours; then, carrying out vacuum filtration separation to obtain a solid, and transferring the solid into a conical flask again; adding about 100ml of 2mol/L NaOH solution into the mixture for the second alkali etching, stirring for 24 hours, then carrying out vacuum filtration and separation to obtain a solid, and drying at 80 ℃ to obtain the carbon nano material after silicon dioxide etching;

d. placing the carbon nano material etched with the silicon dioxide into a 50ml round-bottom flask, uniformly mixing the carbon nano material with 0.5mol/L sulfuric acid solution, heating the mixture in an oil bath at 80 ℃, then carrying out vacuum filtration to separate solid, and drying the solid to obtain a sulfur-doped mesoporous carbon nano material;

e. uniformly mixing 80mg of the sulfur-doped mesoporous carbon nano material, 8.2ml of 0.01mol/ml chloroplatinic acid solution and 8.2ml of 0.01mol/L titanium tetrachloride solution, and removing the solution by rotary evaporation to obtain a solid mixture. Then transferring the obtained solid mixture into a quartz crucible or a corundum crucible, and putting the quartz crucible or the corundum crucible into a tube furnace; argon-hydrogen (composition: 95% Ar + 5% H) was introduced into the tube furnace at a flow rate of 0.3L/min₂) As a protective gas, heating the tubular furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; then cooling to room temperature at the speed of 5 ℃/min to obtain the sulfur-doped carbon-loaded platinum-titanium alloy material;

f. and heating the sulfur-doped carbon-loaded platinum-titanium alloy material to 150 ℃ in a muffle furnace at the speed of 5 ℃/min, annealing, keeping for 2h, and cooling to room temperature to obtain the sulfur-doped carbon-loaded platinum-titanium bimetallic oxide interface material.

Example 3

a. 2g of 2,2' -bithiophene, 2g of silica and 1.2g of Fe (NO)₃)₃·9H₂Mixing O with 150ml of tetrahydrofuran, stirring uniformly, and then removing the solvent by rotary evaporation to obtain a uniformly mixed solid mixture;

b. transferring the obtained solid mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen serving as protective gas at the flow rate of 0.3L/min, heating the tubular furnace to 900 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; then cooling to room temperature at the speed of 5 ℃/min to obtain the carbon nano material;

c. transferring the carbon nano material into a conical flask, adding about 100ml of 2mol/L NaOH solution in the conical flask for the first alkali etching, and stirring for 48 hours; then, carrying out vacuum filtration separation to obtain a solid, and transferring the solid into a conical flask again; adding about 100ml of 2mol/L NaOH solution into the mixture for the second alkali etching, stirring for 24 hours, then carrying out vacuum filtration and separation to obtain a solid, and drying at 80 ℃ to obtain the carbon nano material after silicon dioxide etching;

d. placing the carbon nano material etched with the silicon dioxide into a 50ml round-bottom flask, uniformly mixing the carbon nano material with 0.5mol/L sulfuric acid solution, heating the mixture in an oil bath at 80 ℃, then carrying out vacuum filtration to separate solid, and drying the solid to obtain a sulfur-doped mesoporous carbon nano material;

e. and (2) uniformly mixing 80mg of the sulfur-doped mesoporous carbon nano material, 9.5ml of 0.01mol/ml chloroplatinic acid solution and 3ml of 0.01mol/L nickel nitrate solution, and removing the solution by rotary evaporation to obtain a solid mixture. Then transferring the obtained solid mixture into a quartz crucible or a corundum crucible, and putting the quartz crucible or the corundum crucible into a tube furnace; argon-hydrogen (composition: 95% Ar + 5% H) was introduced into the tube furnace at a flow rate of 0.3L/min₂) As a protective gas, heating the tubular furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; and then cooling to room temperature at the speed of 5 ℃/min to obtain the sulfur-doped carbon-loaded platinum-nickel alloy material.

f. And heating the sulfur-doped carbon-loaded platinum-nickel alloy material to 200 ℃ at the speed of 5 ℃/min in a muffle furnace, annealing, keeping for 2h, and cooling to room temperature to obtain the sulfur-doped carbon-loaded platinum-nickel bimetallic oxide interface material.

Example 4

a. 2g of 2,2' -bithiophene, 2g of silica and 1g of Cu (NO)₃)₂·3H₂Mixing O with 150ml of tetrahydrofuran, stirring uniformly, and then removing the solvent by rotary evaporation to obtain a uniformly mixed solid mixture;

b. transferring the obtained solid mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tube furnace, introducing nitrogen serving as protective gas at the flow rate of 0.3L/min, heating the tube furnace to 800 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; then cooling to room temperature at the speed of 5 ℃/min to obtain the carbon nano material;

c. transferring the carbon nano material into a conical flask, adding about 100ml of 2mol/L NaOH solution in the conical flask for the first alkali etching, and stirring for 48 hours; then, carrying out vacuum filtration separation to obtain a solid, and transferring the solid into a conical flask again; adding about 100ml of 2mol/L NaOH solution into the mixture for the second alkali etching, stirring for 24 hours, then carrying out vacuum filtration and separation to obtain a solid, and drying at 80 ℃ to obtain the carbon nano material after silicon dioxide etching;

d. placing the carbon nano material etched with the silicon dioxide into a 50ml round-bottom flask, uniformly mixing the carbon nano material with 0.5mol/L sulfuric acid solution, heating the mixture in an oil bath at 80 ℃, then carrying out vacuum filtration to separate solid, and drying the solid to obtain a sulfur-doped mesoporous carbon nano material;

e. uniformly mixing 95mg of the sulfur-doped mesoporous carbon nano material, 2.1ml of 0.01mol/ml chloroplatinic acid solution and 0.7ml of 0.01mol/L zirconium nitrate solution, and removing the solution by rotary evaporation to obtain a solid mixture. Then transferring the obtained solid mixture into a quartz crucible or a corundum crucible, and putting the quartz crucible or the corundum crucible into a tube furnace; argon and hydrogen (composition: 95% Ar + 5% H) were introduced into the tube furnace at a tassel flow rate of 0.3L/min₂) As a protective gas, heating the tubular furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; then cooling to room temperature at the speed of 5 ℃/min to obtain the sulfur-doped carbon-loaded platinum-zirconium alloy material;

f. and heating the sulfur-doped carbon-loaded platinum-zirconium alloy material to 250 ℃ at a speed of 5 ℃/min in a muffle furnace, annealing, keeping for 1h, and cooling to room temperature to obtain the sulfur-doped carbon-loaded platinum-zirconium bimetallic oxide interface material.

Example 5

a. 2g of 2,2', 5', 2' -trithiophene, 2g of silica, 1g of Co (NO)₃)₂·6H₂Mixing O with 150ml of tetrahydrofuran, stirring uniformly, and then removing the solvent by rotary evaporation to obtain a uniformly mixed solid mixture;

b. transferring the obtained solid mixture into a quartz crucible or a corundum crucible, putting the quartz crucible or the corundum crucible into a tubular furnace, introducing nitrogen serving as protective gas at the flow rate of 0.3L/min, heating the tubular furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; then cooling to room temperature at the speed of 5 ℃/min to obtain the carbon nano material;

c. transferring the carbon nano material into a conical flask, adding about 100ml of 2mol/L NaOH solution in the conical flask for the first alkali etching, and stirring for 48 hours; then, carrying out vacuum filtration separation to obtain a solid, and transferring the solid into a conical flask again; adding about 100ml of 2mol/L NaOH solution into the mixture for the second alkali etching, stirring for 24 hours, then carrying out vacuum filtration and separation to obtain a solid, and drying at 80 ℃ to obtain the carbon nano material after silicon dioxide etching;

d. placing the carbon nano material etched with the silicon dioxide into a 50ml round-bottom flask, uniformly mixing the carbon nano material with 0.5mol/L sulfuric acid solution, heating the mixture in an oil bath at 80 ℃, then carrying out vacuum filtration to separate solid, and drying the solid to obtain a sulfur-doped mesoporous carbon nano material;

e. and uniformly mixing 80mg of the sulfur-doped mesoporous carbon nano material, 8.0ml of 0.01mol/ml chloroplatinic acid solution and 8.0ml of 0.01mol/L ferric nitrate solution, and performing rotary evaporation to remove the solution to obtain a solid mixture. Then transferring the obtained solid mixture into a quartz crucible or a corundum crucible, and putting the quartz crucible or the corundum crucible into a tube furnace; argon-hydrogen (composition: 95% Ar + 5% H) was introduced into the tube furnace at a flow rate of 0.3L/min₂) As a protective gas, heating the tubular furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; then cooling to room temperature at the speed of 5 ℃/min to obtain the sulfur-doped carbon-loaded platinum-iron alloy material;

f. and heating the sulfur-doped carbon-loaded platinum-iron alloy material to 200 ℃ at the speed of 5 ℃/min in a muffle furnace, annealing, keeping for 2h, and cooling to room temperature to obtain the sulfur-doped carbon-loaded platinum-iron bimetallic oxide interface material.