Three-dimensional ordered macroporous nitrogen-doped carbon-loaded CoPt nanocluster material as well as preparation method and application thereof

Abstract

The invention discloses a three-dimensional ordered macroporous nitrogen-doped carbon-loaded CoPt nanocluster material as well as a preparation method and application thereof. The method comprises the following steps: by taking a three-dimensional structure stacked by polymer microspheres as a template, firstly filling precursors 2-methylimidazole and cobalt nitrate in the three-dimensional template, then placing the three-dimensional template containing the precursors in a mixed solution of ammonia water and methanol for crystallization, and after crystallization, carrying out high-temperature pyrolysis, thereby obtaining the cobalt-based composite material. And finally, carrying out vapor deposition by using platinum acetylacetonate to obtain the three-dimensional ordered macroporous nitrogen-doped carbon-supported cobalt-platinum material. According to the invention, Co is presented as a nanocluster by using a template method and a pyrolysis method, and the nanocluster is anchored on a highly regular three-dimensional ordered macroporous nitrogen-doped carbon carrier; meanwhile, Pt introduced by vapor deposition brings a hydrogen overflow effect by activating hydrogen, so that the material shows excellent activity and selectivity in a carbon dioxide hydrogenation reaction and has a good application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of catalytic conversion of carbon dioxide hydrogenation, and particularly relates to a three-dimensional ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material for synthesizing methane by carbon dioxide hydrogenation, a preparation method thereof, and an application thereof. Background Art

[0002] Carbon dioxide is a greenhouse gas, and its large-scale emission has an increasingly serious impact on the climate. At the same time, carbon dioxide is also a potential chemical material, and high-value chemical products such as methane and carbon monoxide can be prepared by reducing carbon dioxide. Photothermal catalytic conversion of carbon dioxide is a catalytic reaction driven by the photothermal effect. This scheme combines the advantages of photocatalytic strategies and thermal catalytic strategies, can effectively utilize solar energy and achieve high catalytic efficiency, and thus has attracted great interest from the research community and the industrial community.

[0003] Metal-organic framework materials (MOFs) are porous zeolite-like materials with a periodic network structure formed by the coordination bond assembly of organic ligands and metal atoms or metal atom clusters. Compared with traditional porous materials, MOFs materials have a high specific surface area, controllable pore size, and adjustable morphology. Porous metal-carbon composite materials with good thermal stability and chemical stability can be prepared by pyrolyzing MOFs materials, and catalyst materials with different light absorption ranges and photothermal catalytic activities can be obtained through treatment, having broad application prospects in photothermal catalysis.

[0004] Among them, Co-based zeolitic imidazolate framework structure (ZIF-67) is widely used as an ideal precursor in the synthesis of catalysts. However, ZIF-67 is one of the most typical materials rich in micropores, and the derived catalysts are usually also composite carbon-based materials containing only micropores. The high molecular diffusion resistance inside the micropores not only hinders the long-range mass transfer of reactant molecules, but also hinders the interaction between reactants and active sites. Therefore, introducing a new type of hierarchical pore structure (mesopores or macropores) into the material to make it exhibit characteristics superior to those of other single-microporous structure MOFs in terms of diffusion, mass transfer, etc. This is a higher requirement put forward by the needs of social development to the field of MOFs materials.

[0005] In addition, the existing photothermal catalytic carbon dioxide conversion technology has less research on infrared light. Because the carrier energy excited by infrared light on the catalyst surface is relatively low, resulting in a low catalytic efficiency of the material in the infrared band. And the infrared band accounts for 47% of the total solar radiation energy. Therefore, how to design and prepare a catalyst that can efficiently utilize the light energy in the infrared band to activate the reaction substrate is a major problem faced by photothermal catalytic material workers. Summary of the Invention

[0006] The object of the present invention is to overcome the deficiencies of the existing preparation strategies of photothermal catalytic materials, and to provide a three-dimensionally ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material prepared from MOFs as a precursor and a preparation method thereof.

[0007] The object of the present invention is achieved by at least one of the following technical solutions.

[0008] A three-dimensionally ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material, comprising the following steps:

[0009] (1) Dispersing polymer microspheres polymerized by an emulsifier in a solvent, and then filtering through a double-layer filter paper to prepare a three-dimensionally ordered template with periodic pores;

[0010] (2) Adding the three-dimensionally ordered template obtained in step (1) to a solution C formed by mixing a methanol solution A of 2-methylimidazole and a methanol solution B of cobalt nitrate, performing vacuum treatment for 0-2 h, and then taking out the three-dimensional template and drying it to obtain a three-dimensionally ordered template containing 2-methylimidazole and cobalt nitrate;

[0011] (3) Adding the three-dimensionally ordered template containing 2-methylimidazole and cobalt nitrate obtained in step (2) to a mixed solution of ammonia water and methanol, then performing vacuum treatment for 0-10 min and standing for 1-48 h, and then washing and drying to obtain ZIF-67@PS;

[0012] (4) Performing high-temperature pyrolysis treatment on the three-dimensionally ordered macroporous ZIF-67@PS material obtained in step (3) to obtain a three-dimensionally ordered macroporous nitrogen-doped carbon-supported Co nanocluster material.

[0013] (5) Performing gas-phase deposition treatment on the three-dimensionally ordered macroporous nitrogen-doped carbon-supported cobalt cluster material obtained in step (4) with platinum acetylacetonate to obtain the three-dimensionally ordered macroporous nitrogen-doped carbon-supported CoPt cluster material.

[0014] Preferably, the polymer microspheres in step (1) are polymer microspheres such as polystyrene, polymethyl methacrylate, chitosan, and polylactic acid with uniform sizes.

[0015] Preferably, the solvent in step (1) is one or a mixture of several of methanol, ethanol, acetone, deionized water, dichloromethane, and ethyl acetate.

[0016] Preferably, the dosage of the three-dimensional template in step (2) is 5 g.

[0017] Preferably, the molar ratio of 2-methylimidazole to cobalt nitrate in step (2) is (5-10):1.

[0018] Preferably, the mass ratio of 2-methylimidazole to the mixed solution C in the solution in step (2) is 0.1-1.0 g / mL.

[0019] Preferably, the volume ratio of methanol to ammonia water in step (3) is (1-2):1.

[0020] Preferably, the high-temperature pyrolysis treatment in step (4) is carried out in a hydrogen atmosphere, the pyrolysis temperature is 430 °C, the time of the high-temperature treatment is 2 h, and the heating rate is 5 °C / min.

[0021] Preferably, the chemical vapor deposition treatment in step (5) is carried out in an argon atmosphere, the temperature is 250 °C, the treatment time is 2 h, and the heating rate is 5 °C / min.

[0022] A three-dimensional ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material prepared by the above-described preparation method, with three-dimensional ordered macroporous nitrogen-doped carbon as the carrier, and cobalt-platinum metal nanoclusters loaded on the surface of the carrier; the loading amount of the cobalt nanoclusters is 30 wt%-40 wt%; the loading amount of the platinum nanoclusters is 0.5 wt%-5 wt%; wherein Pt and Co exist in the form of clusters, and the two elements are dispersed in the activated carbon framework; the material has a uniform tetrakaidecahedron morphology and an interconnected ordered macroporous structure, the average size of the tetrakaidecahedron is between 4-6 μm, and the diameter of the macropores is between 220-320 nm.

[0023] On the other hand, the present invention also discloses the application of the three-dimensional ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material in the photocatalytic hydrogenation of carbon dioxide to prepare methane, and the reaction raw material gas of the application is composed of carbon dioxide and hydrogen.

[0024] Preferably, the volume ratio of carbon dioxide to hydrogen in the reaction raw material gas is (4:1)-(1:4), preferably 1:4, the reaction temperature is 200-400 °C, preferably 250-350 °C, and the reaction pressure is 0.1-0.4 MPa. The temperature is measured by directly contacting the surface of the catalyst with a thermistor probe. In the present invention, the three-dimensional ordered macroporous nitrogen-doped carbon-supported cobalt-platinum nanocluster material needs to be activated before the photocatalytic reaction, and the activation conditions are: heating in a reducing atmosphere at 250-350 °C for 1-2 h.

[0025] Compared with the prior art, the present invention has the following advantages and values:

[0026] (1) The preparation method provided by the present invention is simple to operate, green and environmentally friendly, safe and controllable, and has high efficiency. The "template method" adopted uses a polymer microsphere array as a pore template, and the pore template can be removed by one-step high-temperature pyrolysis, and the Pt element is introduced by chemical vapor deposition. On the basis of constructing a three-dimensional ordered macroporous structure, uniformly distributed Co and Pt nanoclusters are formed, further effectively improving the activity and selectivity of the photocatalytic conversion of carbon dioxide, and having high practical application value;

[0027] (2) The catalyst of the present invention can make full use of the light energy in each band of sunlight, and the light absorption ability in the visible and near-infrared bands is enhanced through the structure of three-dimensionally ordered macroporous nitrogen-doped carbon. This strategy enables the material of the present invention to control the surface temperature of the catalyst to reach 200-400 °C by regulating the light intensity when only using focused sunlight, thereby achieving efficient solar energy utilization and photothermal conversion. Description of the Drawings

[0028] Figure 1 SEM image of polystyrene microspheres (PS) prepared in Example 1 of the present invention.

[0029] Figure 2 SEM image of the 1# three-dimensionally ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material prepared in Example 2 of the present invention.

[0030] Figure 3 TEM image of the 1# three-dimensionally ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material prepared in Example 2 of the present invention.

[0031] Figure 4 HRTEM image of the 1# three-dimensionally ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material prepared in Example 2 of the present invention.

[0032] Figure 5 HAADF-STEM image and corresponding EDX elemental distribution map of the 1# three-dimensionally ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material prepared in Example 2 of the present invention.

[0033] Figure 6 Comparison chart of the absorption spectrum of the 1# three-dimensionally ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material prepared in Example 2 of the present invention and the solar spectrum.

[0034] Figure 7 HAADF-STEM image and corresponding EDX elemental distribution map of the 2# three-dimensionally ordered macroporous nitrogen-doped carbon-supported Co nanocluster material prepared in Example 3 of the present invention.

[0035] Figure 8 HAADF-STEM image and corresponding EDX elemental distribution map of the 3# activated carbon-supported CoPt nanocluster material prepared in Example 4 of the present invention.

[0036] Figure 9 Photothermal catalytic carbon dioxide hydrogenation reaction performance test result chart of the 1# three-dimensionally ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material, 2# three-dimensionally ordered macroporous nitrogen-doped carbon-supported Co nanocluster material, and 3# activated carbon-supported CoPt nanocluster material prepared in Examples 2, 3, and 4 of the present invention. Detailed Description of the Invention

[0037] The following further illustrates the specific implementation of the present invention in conjunction with examples, but the implementation and protection of the present invention are not limited thereto. It should be noted that for the processes not specifically described in detail below, those skilled in the art can implement or understand them with reference to the prior art. Reagents or instruments without indicating the manufacturer are regarded as conventional products that can be obtained through commercial purchase.

[0038] Example 1

[0039] 500 mL of deionized water, 65 mL of styrene, and 2.5 g of polyvinylpyrrolidone (PVP) were successively added to a 1-L round-bottom flask, mechanically stirred at room temperature, and purged with nitrogen for 15 min. Subsequently, the system was heated to 75 °C under nitrogen protection. After maintaining for 30 min, 50 mL of an aqueous solution dissolving 1 g of K2S2O8 was slowly poured into the round-bottom flask to initiate the polymerization reaction of styrene. After 24 h, the reaction ended. The resulting milky white reaction solution was filtered and washed, and the collected filter cake was placed in a vacuum oven at 60 °C for drying for 24 h. The dried white filter cake was the three-dimensional template (PS) stacked by polystyrene microspheres, and the size of the polystyrene microspheres was about 270 nm.

[0040] Figure 1 is the SEM image of the three-dimensional template (PS) stacked by polystyrene microspheres obtained in this example. It can be seen from the figure that the three-dimensional template has uniform size (diameter about 270 nm) and is arranged orderly.

[0041] Example 2

[0042] This example provides a preparation method of a three-dimensional ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material, including the following steps:

[0043] (1) 10 g of 2-methylimidazole was added to 10 mL of methanol and ultrasonically dissolved for 5 min to obtain solution A;

[0044] (2) 4 g of cobalt nitrate was added to 10 mL of methanol and ultrasonically dissolved for 5 min to obtain solution B;

[0045] (3) 5 g of the three-dimensional ordered template in Example 1 was added to the mixed solution C formed by solution A and solution B, vacuum-treated for 1 h, the three-dimensional template was taken out of the solvent, and dried at 50 °C to obtain precursor@PS;

[0046] (4) The polystyrene microsphere three-dimensional template containing cobalt nitrate and 2-methylimidazole obtained was placed in a mixed solution of ammonia water (25 wt%, the same below) and methanol with a volume ratio of 1:2, vacuum-treated for 3 min and then left standing for 24 h, filtered, washed, and dried to obtain ZIF-67@PS;

[0047] (5) Place the obtained ZIF-67@PS material with an ordered macropore size of 270 nm in a quartz boat, put it into a tube furnace, use hydrogen as the calcination atmosphere, heat it to 430 °C at a rate of 5 °C / min, calcine it at 430 °C for 2 h, after cooling to room temperature, switch the atmosphere to argon and purge for 60 min. Take out the material, place it in a quartz boat together with platinum acetylacetonate and put it into the tube furnace, use argon as the gas deposition atmosphere, heat it to 250 °C at a rate of 5 °C / min, heat it at 250 °C for 2 h, and take it out after cooling to room temperature. The obtained three-dimensional ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material (denoted as 1# material) is a black solid. After the prepared 1# material is heated in a hydrogen atmosphere at 300 °C for 1 h, it can be applied to the photothermal catalytic carbon dioxide conversion reaction.

[0048] Figure 2 is the SEM image of the 1# material obtained in this example. It can be seen from Figure 2 that the material has a uniform tetrakaidecahedral morphology and an interconnected ordered macroporous structure, and the average size of the tetrakaidecahedron is between 4 - 6 μm.

[0049] Figure 3 is the TEM image of the 1# material obtained in this example. It can be further seen from Figure 3 that the material has an interconnected ordered macroporous structure, and the diameter of the macropores is about 270 nm.

[0050] Figure 4 is the HRTEM image of the 1# material obtained in this example. It can be seen from Figure 3 that there are obvious Co and Pt nanoparticles in the material, indicating that Co and Pt elements exist in the form of nanoclusters on the surface of the material.

[0051] Figure 5 is the HAADF-STEM image and the corresponding EDX element distribution map of the 1# material obtained in this example. It can be seen from Figure 5 that the four elements Co, Pt, C, and N are uniformly dispersed in the three-dimensional ordered framework.

[0052] Figure 6 is the comparison diagram of the absorption spectrum of the 1# material obtained in this example and the solar spectrum. It can be seen from Figure 6 that the material has a wide spectral absorption range and has a strong absorption effect on the solar spectrum.

[0053] Example 3

[0054] This example provides a preparation method of a three-dimensional ordered macroporous nitrogen-doped carbon-supported Co nanocluster material, including the following steps:

[0055] (1) Add 10 g of 2-methylimidazole to 10 mL of methanol and ultrasonically dissolve for 5 min to obtain solution A;

[0056] (2) Add 4 g of cobalt nitrate to 10 mL of methanol and ultrasonically dissolve for 5 min to obtain solution B;

[0057] (3) Take 5 g of the three-dimensional ordered template in Example 1 and add it to the mixed solution C formed by solution A and solution B. Perform vacuum treatment for 1 h, take out the three-dimensional template from the solvent, and dry it at 50 °C to obtain precursor@PS;

[0058] (4) Place the obtained polystyrene microsphere three-dimensional template containing cobalt nitrate and 2-methylimidazole in a mixed solution of ammonia water (25 wt%, the same below) and methanol with a volume ratio of 1:2. After vacuum treatment for 3 min, let it stand for 24 h, filter, wash, and dry it to obtain ZIF-67@PS;

[0059] (5) Place the obtained ZIF-67@PS material with an ordered macropore size of 270 nm in a quartz boat, put it into a tube furnace, use hydrogen as the calcination atmosphere, heat it to 430 °C at a rate of 5 °C / min, calcine it at 430 °C for 2 h, cool it to room temperature, then switch the atmosphere to argon and purge for 60 min and take it out. Obtain a three-dimensional ordered macroporous nitrogen-doped carbon-supported Co nanocluster material (denoted as 2# material, as a comparative material), which is a black solid. After the prepared 2# material is heated in a hydrogen atmosphere at 300 °C for 1 h, it can be applied to the photothermal catalytic carbon dioxide conversion reaction.

[0060] Figure 7 It is the HAADF-STEM image and the corresponding EDX elemental distribution map of the 2# material obtained in this example. It can be observed that the three elements Co, C, and N are evenly dispersed in the three-dimensional ordered framework.

[0061] Example 4

[0062] This example provides a preparation method of an activated carbon-supported CoPt nanocluster material, including the following steps:

[0063] (1) Add 1.76 g of cobalt nitrate to 20 mL of ethanol and ultrasonically dissolve for 5 min to obtain solution A;

[0064] (2) Add 0.65 g of activated carbon to solution A and stir until the solvent evaporates to obtain mixture B;

[0065] (6) Place the obtained mixture B in a quartz boat, put it into a tube furnace, use hydrogen as the calcination atmosphere, heat it to 430 °C at a rate of 5 °C / min, calcine it at 430 °C for 2 h, after cooling to room temperature, switch the atmosphere to argon and purge for 60 min. Take out the material, place it together with platinum acetylacetonate in a quartz boat and put it into the tube furnace, use argon as the gas deposition atmosphere, heat it to 250 °C at a rate of 5 °C / min, heat it at 250 °C for 2 h, and take it out after cooling to room temperature. Obtain the activated carbon supported CoPt nanocluster material (denoted as Material 3#, as the comparative material), which is a black solid. The prepared Material 3# can be applied to the photothermal catalytic carbon dioxide conversion reaction after being heated in a hydrogen atmosphere at 300 °C for 1 h.

[0066] Figure 8 Figure 4 is the HAADF-STEM image and the corresponding EDX elemental distribution map of Material 3# obtained in this example, and it can be observed that two elements, Pt and Co, are dispersed in the activated carbon framework.

[0067] Example 5

[0068] Performance test of photothermal catalytic hydrogenation of carbon dioxide over three-dimensionally ordered macroporous nitrogen-doped carbon supported CoPt nanocluster materials and their comparative materials

[0069] The photothermal catalytic carbon dioxide hydrogenation reaction test was carried out in a 50 mL batch reactor equipped with a quartz window to allow light irradiation. In the reactor, 20 mg of catalysts (Material 1# prepared in Example 2, Material 2# prepared in Example 3, and Material 3# prepared in Example 4) were added respectively. The materials need to be activated before the photothermal catalytic reaction, and the activation conditions are: heating in a hydrogen atmosphere at 300 °C for 1 h. After activation, the reactor was evacuated to vacuum. After the material surface cooled to room temperature, carbon dioxide and hydrogen with a volume ratio of 1:4 were introduced, and then the reaction was carried out under the irradiation of simulated concentrated sunlight with a xenon lamp as the light source. After the reaction, the gas products were analyzed by gas chromatography (GC).

[0070] Figure 9 Figure 5 is the performance test results of the photothermal catalytic carbon dioxide hydrogenation reaction of Material 1#, Material 2#, and Material 3# used in this example. Figure 9 It shows that Material 1# has high catalytic activity, the methane product yield reaches 338 mmol·g -1 ·h -1 -1 after 20 min, the carbon dioxide conversion rate is close to 80%, and the methane product selectivity reaches 99.39%. It has higher reaction activity and methane product selectivity compared with the comparative materials. This confirms the advantages of the three-dimensionally ordered macroporous nitrogen-doped carbon structure and Co, Pt nanoclusters in the photothermal catalytic carbon dioxide hydrogenation reaction.

[0071] The above embodiments are only the preferred embodiments of the present invention, which are only used to explain the present invention rather than limit the present invention. Any changes, substitutions, modifications, etc. made by those skilled in the art without departing from the spirit and essence of the present invention shall fall within the protection scope of the present invention.

Claims

1. Three-dimensional ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material, characterized in that, Using three-dimensional ordered macroporous nitrogen-doped carbon as a carrier, cobalt-platinum metal nanoclusters are loaded on the surface of the carrier; the loading amount of the cobalt nanoclusters is 30wt%-40wt%; the loading amount of the platinum nanoclusters is 0.5wt%-5wt%; wherein Pt and Co exist in the form of clusters, and the two elements are dispersed in the activated carbon framework; this material has a uniform tetrakaidecahedron morphology and an interconnected ordered macroporous structure, the average size of the tetrakaidecahedron is between 4-6μm, and the diameter of the macropores is between 220-320nm.

2. A method for preparing the three-dimensional ordered macroporous nitrogen-doped carbon-supported CoPt nanocluster material as described in claim 1, characterized in that, It includes the following steps: (1) Dispersing polymer microspheres polymerized by an emulsifier in a solvent, and then filtering through a double-layer filter paper to prepare a three-dimensional ordered template with periodic pores; (2) Adding the three-dimensional ordered template obtained in step (1) to a solution C formed by mixing a methanol solution A of 2-methylimidazole and a methanol solution B of cobalt nitrate, performing vacuum treatment for 0-2h, and then taking out the three-dimensional template and drying it to obtain a three-dimensional ordered template containing 2-methylimidazole and cobalt nitrate; (3) Adding the three-dimensional ordered template containing 2-methylimidazole and cobalt nitrate obtained in step (2) to a mixed solution of ammonia water and methanol, then performing vacuum treatment for 0-10min and standing for 1-48h, and then washing and drying to obtain three-dimensional ordered macroporous ZIF-67@PS; (4) Performing high-temperature pyrolysis treatment on the three-dimensional ordered macroporous ZIF-67@PS material obtained in step (3) to obtain a three-dimensional ordered macroporous nitrogen-doped carbon-supported cobalt cluster material; (5) Performing gas-phase deposition treatment on the three-dimensional ordered macroporous nitrogen-doped carbon-supported cobalt cluster material obtained in step (4) with platinum acetylacetonate to obtain the three-dimensional ordered macroporous nitrogen-doped carbon-supported cobalt-platinum cluster material.

3. The preparation method according to claim 2, wherein, In step (1), the polymer microspheres are polystyrene microspheres, poly(methyl methacrylate) microspheres, chitosan microspheres or polylactic acid microspheres with uniform size; the solvent is one or more of methanol, ethanol, acetone, deionized water, dichloromethane and ethyl acetate.

4. The preparation method according to claim 2, characterized in that In step (2), the molar ratio of 2-methylimidazole to cobalt nitrate is (5-10):1; the mass ratio of 2-methylimidazole to the mixed solution C in the solution is 0.1-1.0g / mL.

5. The preparation method according to claim 2, characterized in that, In step (3), the volume ratio of methanol to ammonia water is (1-2):

1.

6. The preparation method according to claim 2, wherein In step (4), the high-temperature thermal bonding treatment is carried out in a hydrogen atmosphere; the temperature of the high-temperature treatment is 400-450°C, the time of the high-temperature treatment is 2-3h, and the heating rate is 3-5°C / min.

7. The preparation method according to claim 2, characterized in that, In step (5), the gas-phase deposition treatment is carried out in an argon atmosphere; the temperature of the high-temperature treatment is 200-250°C, the time of the high-temperature treatment is 2-3h, and the heating rate is 3-5°C / min.

8. Application of the three-dimensional ordered macroporous nitrogen-doped carbon-supported cobalt-platinum nanocluster material described in claim 1 in the photocatalytic reduction of carbon dioxide to methane.

9. The application according to claim 8, characterized in that, A mixed gas of carbon dioxide and hydrogen is introduced in the photocatalytic reaction; the volume ratio of carbon dioxide to hydrogen is (4:1)-(1:4); in the photocatalytic reaction, the reaction temperature is 200-400°C.

10. The application according to claim 13, characterized in that, Before the photothermal catalytic reaction, the three-dimensional ordered macroporous nitrogen-doped carbon-supported cobalt-platinum nanocluster material needs to be activated. The activation conditions are as follows: heating in a reducing atmosphere at 250-350 °C for 1-2 h.

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