Nickel-based photothermal catalyst for selective hydrogenation of carbon dioxide, method for preparing and use thereof

Abstract

The application discloses a preparation method of a nickel-based photothermal catalyst for selective hydrogenation of carbon dioxide, which comprises the following steps: preparing an intermediate mixture by using a nickel source and a carrier metal source through a sol-gel method; pyrolyzing the intermediate mixture to obtain a composite oxide; and performing photoreduction on the composite oxide under light irradiation by using a reducing atmosphere to obtain the nickel-based photothermal catalyst for selective hydrogenation of carbon dioxide. The nickel-based photothermal catalyst for selective hydrogenation of carbon dioxide prepared by the preparation method has high activity, high selectivity and high stability, and the preparation method is simple and low in preparation cost, so that the nickel-based photothermal catalyst can exhibit excellent catalytic performance in a photothermal CO2 hydrogenation reaction.

Description

Technical Field

[0001] This invention belongs to the field of selective hydrogenation catalysts for carbon dioxide, and particularly relates to a nickel-based photothermal catalyst for selective hydrogenation of carbon dioxide, its preparation method and application. Background Technology

[0002] To alleviate dependence on fossil fuels and address the increasingly severe climate problem, developing sustainable technologies to provide clean energy and carbon dioxide (CO2) fixation is crucial for human societal development. Utilizing clean and widely available solar energy to drive the conversion of CO2 into fuels and chemicals is a promising technology. Among these, photothermal catalytic CO2 hydrogenation converts photons into heat energy to raise the catalyst surface temperature, thereby efficiently converting CO2 into high-value-added products such as carbon monoxide (CO) and methane (CH4). Of these products, CH4 has attracted widespread attention because it can be directly injected into established natural gas pipelines.

[0003] However, in the photothermal catalytic synthesis of CH4 from CO2, the catalysts used are still limited to expensive noble metal-based catalysts, such as ruthenium (Ru) and rhodium (Rh). Using noble metal-based catalysts increases the cost of CO2 hydrogenation to CH4, hindering large-scale application. Nickel (Ni), compared to noble metals like Ru and Rh, is relatively abundant and inexpensive. However, nickel catalysts exhibit low catalytic performance in selective CO2 hydrogenation. Therefore, how to prepare a low-cost, highly active, and highly selective nickel catalyst for the hydrogenation of CO2 to CH4 is a pressing technical problem that needs to be solved in this field. Summary of the Invention

[0004] In view of the above, in order to at least partially solve at least one of the aforementioned technical problems, the present invention provides a nickel-based photothermal catalyst for selective hydrogenation of CO2, its preparation method and application. The nickel-based photothermal catalyst prepared by the method of the present invention not only has high activity, high selectivity and stability, but also has a simple preparation method and low cost.

[0005] To solve the above-mentioned technical problems, the technical solution provided in this disclosure is as follows:

[0006] According to embodiments of this disclosure, a method for preparing a nickel-based photothermal catalyst for selective hydrogenation of CO2 is provided, comprising:

[0007] An intermediate mixture was prepared by sol-gel method using a nickel source and a carrier metal source.

[0008] The intermediate mixture was pyrolyzed to obtain a composite oxide.

[0009] Photoreduction of composite oxides under light using a reducing atmosphere yields a nickel-based photothermal catalyst for the selective hydrogenation of CO2.

[0010] According to embodiments of this disclosure, a nickel-based photothermal catalyst prepared by the above-described method is provided.

[0011] According to embodiments of this disclosure, the application of the above-described nickel-based photothermal catalyst in the photothermal catalytic hydrogenation reaction of carbon dioxide is provided.

[0012] According to embodiments of the present invention, the method uses a sol-gel method to prepare an intermediate mixture, which is then pyrolyzed in air to obtain a composite oxide. Simultaneously, photoreduction is performed under a reducing atmosphere to replace traditional high-temperature calcination. The resulting nickel-based photothermal catalyst differs from common doped oxide forms, allowing for uniform coordination of ligands and metals, resulting in uniform dispersion of nickel nanoparticles on the support, making them less prone to polymerization, and exhibiting a high nickel metal loading. Due to its high loading and unique bonding mechanism, the resulting nickel catalyst exhibits high reactivity, good selectivity, and strong stability in the photothermal CO2 selective hydrogenation reaction. Furthermore, the use of photoreduction results in a low-cost and simple preparation method, possessing potential for industrial production. Attached Figure Description

[0013] Figure 1 This is a flowchart of the preparation method of the nickel-based photothermal catalyst for selective hydrogenation of CO2 according to the present invention;

[0014] Figure 2 This is the X-ray diffraction pattern of the nickel-based photothermal catalyst prepared in Example 1 of this invention;

[0015] Figure 3 This is a transmission electron microscope image of the nickel-based photothermal catalyst prepared in Example 1 of the present invention;

[0016] Figure 4 This is a graph showing the yield of the target product CH4 in the repeated use of the nickel-based photothermal catalyst prepared in Example 1 of this invention.

[0017] Figure 5 This is a transmission electron microscope image of the nickel-based photothermal catalyst prepared in Comparative Example 1 of this invention.

[0018] Figure 6 This is a comparison chart of the yield and recovery rate of the target product CH4 in photothermal catalytic CO2 hydrogenation between Comparative Example 1 and Example 1 of the present invention. Detailed Implementation

[0019] The embodiments of the present disclosure will now be described with reference to the accompanying drawings. However, it should be understood that these descriptions are exemplary only and are not intended to limit the scope of the disclosure. In the following detailed description, numerous specific details are set forth to provide a thorough understanding of the embodiments of the present disclosure for ease of explanation. However, it will be apparent that one or more embodiments may be practiced without these specific details. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concepts of the present disclosure.

[0020] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit this disclosure. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0021] Glossary of terms in this invention:

[0022] Doped oxides: Doped metal oxides refer to metal A being doped into the lattice of metal B oxide. There will be phases of B oxide, but no phases of metal A oxide will appear, and the content of metal A is low.

[0023] Composite oxides: Composite oxides are oxides formed by the combination of metal A and metal B. They contain both oxide phases of metal A and metal B, and can be described using a core-shell structure, such as A@BO. x Meanwhile, the content of metal A is relatively high.

[0024] Austenite ripening, also known as grain refinement, is a process that describes the changes in a non-uniform structure over time. In solid solutions or sols, smaller crystal or sol particles dissolve and redeposit onto larger crystal or sol particles. This process can lead to grain refinement, improving the material's mechanical properties and corrosion resistance.

[0025] Ligands: also known as surfactants, ligands coordinate with metals to prevent metal aggregation and make particles more uniform.

[0026] The traditional method for preparing nickel-based photothermal catalysts is the impregnation method. However, the metal particles prepared by the traditional impregnation method are not uniform in size and are prone to sintering and agglomeration. In order to solve this technical problem, we prepared nickel-based photothermal catalysts by sol-gel method, pyrolysis method and photoreduction method. By coordinating ligands with metal, the metal particles are more uniformly distributed. At the same time, there is a strong interaction between metal and support, which reduces the agglomeration of metal particles, in order to solve the above-mentioned technical problems.

[0027] According to embodiments of this disclosure, a method for preparing a nickel-based photothermal catalyst for selective hydrogenation of CO2 is provided, such as... Figure 1 As shown, steps S1 to S3 are included:

[0028] In step S1: An intermediate mixture is prepared using a nickel source and a carrier metal source via a sol-gel method;

[0029] Step S2: Pyrolyze the intermediate mixture to obtain the composite oxide;

[0030] Step S3: Photoreduction of the composite oxide under light using a reducing atmosphere to obtain a nickel-based photothermal catalyst for the selective hydrogenation reaction of CO2.

[0031] According to embodiments of the present invention, the method of the present invention uses the sol-gel method to prepare an intermediate mixture, which is then pyrolyzed in air to obtain a composite oxide. Unlike common doped oxide forms, this method allows for uniform coordination of ligands and metals, resulting in a high nickel metal loading. Simultaneously, the method uses photo-irradiation for reduction in a reducing atmosphere to replace traditional high-temperature calcination, reducing preparation costs and simplifying the process. Due to its high loading and special bonding mode, the prepared nickel catalyst exhibits advantages such as high reactivity, good selectivity, and strong stability in the photothermal CO2 selective hydrogenation reaction.

[0032] According to an embodiment of this disclosure, in step S1, the sol-gel method involves uniformly mixing a nickel source, a carrier metal source, and additives to obtain a mixed sol solution.

[0033] Acid was added to the mixed sol solution and stirred to obtain a nickel support precursor solution;

[0034] The nickel-supported precursor solution was aged to obtain an intermediate mixture.

[0035] According to an embodiment of this disclosure, in step S3, the light source for light reduction is at least one of a xenon lamp, an LED lamp, a tungsten lamp, or a mercury lamp, and the light intensity is 0.5–5 W / cm². –2 For example, it could be 0.5w cm –2 1w cm –2 2w cm –2 3wcm –2 4w cm –2 5w cm –2 The reduction time is 5 to 30 minutes, for example, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes.

[0036] According to an embodiment of this disclosure, in step S3, the reducing atmosphere for photoreduction under illumination is at least one of H2 / CO2, H2 / Ar, and H2 / N2 mixture.

[0037] According to embodiments of this disclosure, using a reducing atmosphere for photoreduction reaction instead of high-temperature calcination in the traditional preparation process not only simplifies the process but also reduces preparation costs, enabling large-scale industrial production.

[0038] According to an embodiment of this disclosure, in step S1, the nickel source is at least one of a nickel soluble salt and its hydrate, and the nickel soluble salt includes nickel nitrate, nickel chloride, nickel sulfate, and nickel acetate; the concentration of the nickel source is 0.01 mol / L to 5 mol / L, for example, it can be 0.01 mol / L, 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L, or 5 mol / L.

[0039] According to embodiments of this disclosure, the concentration of nickel metal salt affects the metal loading and dispersion, thereby affecting the hydrogenation catalytic activity.

[0040] According to embodiments of this disclosure, in step S1, the carrier source is at least one of tetrabutyl titanate, cerium nitrate, aluminum nitrate, and tetraethyl silicate.

[0041] According to an embodiment of this disclosure, in step S1, the molar ratio of the nickel source to the carrier metal source is 1:10 to 10:1, preferably 4:1 to 1:1.

[0042] According to embodiments of this disclosure, the molar ratio of nickel source to support metal source is 1:10 to 10:1, and the nickel metal loading of the obtained nickel-based photothermal catalyst is (5 to 80) wt%. When the molar ratio of support source to nickel metal salt is 1:1, the nickel metal loading of the obtained nickel-based catalyst is 60 wt%. When the molar ratio of support to nickel metal salt is 10:1, the nickel metal loading of the obtained nickel-based catalyst is 5 wt%. The molar ratio of nickel metal salt to support salt affects the nickel loading, dispersion and particle size, thereby affecting the CO2 hydrogenation reaction activity.

[0043] According to embodiments of this disclosure, in step S1, the additive comprises a surfactant and an organic solvent;

[0044] The surfactant includes at least one of polyether, polyvinylpyrrolidone, and polyethylene glycol;

[0045] The organic solvent includes at least one of methanol, ethanol, isopropanol, acetonitrile, and N,N-dimethylformamide;

[0046] The molar ratio of nickel source to surfactant is 1:1 to 10:1, for example, it can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1.

[0047] According to embodiments of this disclosure, surfactants can make metal particles more evenly distributed and prevent them from agglomerating during annealing; the ratio of nickel metal salt to surfactant affects nickel dispersion and particle size, thereby affecting the activity of CO2 hydrogenation.

[0048] According to an embodiment of the present disclosure, in step S1, an acid is added to the mixed sol solution to make the pH of the mixed sol solution less than 7, and the acid includes at least one of hydrochloric acid, glacial acetic acid, and nitric acid.

[0049] The aging temperature of the nickel support precursor solution is 30 to 100°C, for example, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, and the aging time is 4 to 24 hours, for example, 4 hours, 8 hours, 12 hours, 16 hours, 20 hours, 24 hours.

[0050] According to embodiments of this disclosure, acidic conditions can form a more stable sol system and make it less likely for metal salts to precipitate and disperse evenly in the sol solution.

[0051] According to an embodiment of this disclosure, in step S3, the intermediate mixture is pyrolyzed in air at a temperature of 300–600°C, for example, 300°C, 400°C, 500°C, or 600°C, for a time of 4–12 hours, for example, 4 hours, 6 hours, 8 hours, 10 hours, or 12 hours.

[0052] According to embodiments of this disclosure, a nickel-based photothermal catalyst prepared by a method for preparing a nickel-based photothermal catalyst for selective hydrogenation of CO2 is provided.

[0053] According to embodiments of this disclosure, an application of a nickel-based photothermal catalyst prepared by a method for preparing a nickel-based photothermal catalyst for selective hydrogenation of CO2 in the photothermal catalytic reaction of CO2 hydrogenation is provided.

[0054] The nickel-based photothermal catalyst for selective CO2 hydrogenation prepared by the method of the present invention not only has high activity, high selectivity and high stability, but also has a simple preparation method and low preparation cost.

[0055] The present disclosure will be further described in detail below with reference to specific embodiments and accompanying drawings. The following embodiments are merely illustrative examples and are not intended to limit the scope of the disclosure. Unless otherwise specified, the experimental methods in the following embodiments are standard experimental procedures. All instruments, consumables, and reagents used in the following embodiments are commercially available unless otherwise specified.

[0056] Example 1

[0057] A nickel-based photothermal CO2 selective hydrogenation catalyst is prepared by the following steps:

[0058] Step S1: Dissolve 0.58g of nickel nitrate hexahydrate (Ni(NO3)2·6H2O) (nickel source), 2.72mL of tetrabutyl titanate (carrier metal source), and 2.4g of polyether (surfactant) in 24mL of anhydrous ethanol (organic solvent). The molar ratio of nickel to titanium carrier is 4:1. Stir for 30min to obtain a mixed sol solution.

[0059] Under vigorous stirring, 2 mL of glacial acetic acid and 2 mL of hydrochloric acid were slowly added to the above solution to obtain the nickel support precursor solution. The solution was then transferred to a petri dish and aged at 50 degrees Celsius for 24 hours to obtain the intermediate mixture.

[0060] Step S2: The intermediate mixture obtained in step S1 is annealed in air at 450 degrees for 5 hours to achieve pyrolysis, and then naturally cooled to room temperature to obtain the composite oxide.

[0061] Step S3: The composite oxide obtained in step S2 is placed in a reducing atmosphere of H2 / N2 (1:1) mixture at 2w cm⁻¹. -2 Under the illumination intensity of a xenon lamp, which is a photoreduction light source, a nickel-based photothermal catalyst for the selective hydrogenation reaction of CO2 can be obtained by photoreduction for 5 minutes.

[0062] The catalyst prepared in Example 1 of this invention was tested, and the following test results were obtained:

[0063] X-ray diffraction was used to characterize nickel-based catalysts in existing technologies, thereby obtaining... Figure 2 The X-ray diffraction pattern shown.

[0064] Depend on Figure 2 It can be seen that the nickel-based catalyst prepared in Example 1 of the present invention has obvious metallic nickel diffraction peaks and TiO2 support diffraction peaks at 2θ, confirming that it is in the state of nickel-supported TiO2.

[0065] The nickel-based catalyst prepared in the embodiments of the present invention was observed using transmission electron microscopy. Figure 3 Transmission electron microscope image.

[0066] Depend on Figure 3 It can be seen that the nickel-based catalyst prepared in Example 1 of the present invention has nickel nanoparticles uniformly dispersed on the TiO2 support, with an average particle size of about 25 nm.

[0067] The nickel-based photothermal catalyst for the selective hydrogenation of CO2 prepared in Example 1 of this invention was used to perform a hydrogenation reaction, and the reaction performance was tested. The yield of the target product CH4 was as follows: Figure 4 As shown.

[0068] Depend on Figure 4 It can be seen that the nickel-based catalyst prepared in this embodiment can achieve a certain performance under xenon lamp irradiation intensity of 2.5 W / cm².-2 The reaction was carried out under a CO2 / H2 (1:4) mixed gas for 0.5 h, and the methane with a selectivity greater than 95% was obtained by gas chromatography analysis. The methane yield was 91%, and there was no decay after 5 cycles.

[0069] Example 2

[0070] The specific material preparation process was the same as in Example 1, except that 1.77 g of cerium nitrate hexahydrate (Ce(NO3)3·6H2O) was used instead of tetrabutyl titanate as the support source. The resulting material was a nickel-based supported CeO2 photothermal CO2 hydrogenation catalyst. The reaction performance test was the same as in Example 1, with a methane yield greater than 90%.

[0071] Example 3

[0072] The specific material preparation process was the same as in Example 1, except that polyvinylpyrrolidone was used instead of polyether as the surfactant in the material synthesis. The reaction performance test was the same as in Example 1, with a methane yield of 92%.

[0073] Example 4

[0074] The specific material preparation process was the same as in Example 1, except that polyethylene glycol was used instead of polyether as the surfactant for material synthesis. The molar ratio of nickel source to surfactant remained the same as in Example 1. The reaction performance test was the same as in Example 1, with a methane yield of 94%.

[0075] Example 5

[0076] The specific material preparation process was the same as in Example 1, except that the ratio of nickel metal source to support source was changed to 1:1. The reaction performance test was the same as in Example 1, with a methane yield of 92%.

[0077] Example 6

[0078] The specific material preparation process was the same as in Example 1, except that the annealing temperature of the intermediate mixture in air was changed to 500°C. The reaction performance test was the same as in Example 1, with a methane yield of 95%.

[0079] Example 7

[0080] The specific material preparation process was the same as in Example 1, except that the annealing time of the intermediate mixture in air was changed to 8 hours. The reaction performance test was the same as in Example 1, with a methane yield of 95%.

[0081] Example 8

[0082] The specific material preparation process was the same as in Example 1, except that the mass of the surfactant was changed to 3.6 g for material synthesis. The reaction performance test was the same as in Example 1, with a methane yield of 93%.

[0083] Example 9

[0084] The specific material preparation process was the same as in Example 1, except that nickel acetate was used instead of nickel nitrate hexahydrate as the nickel source for material synthesis. The reaction performance testing was the same as in Example 1, with a methane yield of 92%.

[0085] Example 10

[0086] The specific material preparation process is the same as in Example 1, except that acetonitrile is used instead of ethanol as the organic solvent for material synthesis. The reaction performance test is the same as in Example 1, with a methane yield of 91%.

[0087] Example 11

[0088] The specific material preparation process is the same as in Example 1, except that an LED lamp is used instead of a xenon lamp as the light source for photoreduction. The reaction performance test is the same as in Example 1, with a methane yield of 92%.

[0089] Example 12

[0090] The specific material preparation process was the same as in Example 1, except that the photoreduction time was changed to 20 min. The reaction performance test was the same as in Example 1, with a methane yield of 96%.

[0091] Example 13

[0092] The specific material preparation process is the same as in Example 1, only the light intensity of photoreduction is changed to 3 W / cm². -2 Photoreduction was performed. Reaction performance testing was the same as in Example 1, with a methane yield of 94%.

[0093] Example 14

[0094] The specific material preparation process was the same as in Example 1, except that the reducing atmosphere for photoreduction was changed to H2 / Ar (1:1). The reaction performance test was the same as in Example 1, with a methane yield of 94%.

[0095] Example 15

[0096] The specific material preparation process is the same as in Example 1. The reaction performance test only involved using CO2 / H2 (1:6) reaction gas to carry out a photothermal CO2 hydrogenation reaction, with a methane yield of 98%.

[0097] Example 16

[0098] The specific material preparation process is the same as in Example 1; the only difference in reaction performance testing is that the light intensity for photothermal CO2 hydrogenation is changed to 3.5 W / cm². -2 A photothermal CO2 hydrogenation reaction was carried out, with a methane yield of 94%.

[0099] Comparative Example 1

[0100] Nickel-based photothermal catalysts were prepared using a conventional impregnation method, and the nickel-based catalysts prepared in Comparative Example 1 of this invention were observed using transmission electron microscopy. Figure 5 Transmission electron microscope image.

[0101] Depend on Figure 5 It is known that nickel-based photothermal catalysts prepared by the traditional impregnation method will contain Ni phase information.

[0102] The nickel-based photothermal catalysts prepared in Comparative Example 1 and Example 1 were used to carry out the CO2 hydrogenation reaction, and the results were obtained. Figure 6 Comparison chart.

[0103] Depend on Figure 6 It can be seen that the nickel-based catalyst prepared in Example 1 of the present invention has a higher yield and production rate of the target product CH4 in the photothermal catalytic CO2 hydrogenation reaction than the nickel-based catalyst prepared by the conventional impregnation method.

[0104] In summary, the nickel-based photothermal catalyst for selective CO2 hydrogenation prepared by the method of the present invention not only has high activity, high selectivity and high stability, but also has a simple preparation method and low preparation cost, and can exhibit excellent catalytic performance in photothermal CO2 hydrogenation reaction.

[0105] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a nickel-based photothermal catalyst for selective hydrogenation of carbon dioxide, characterized in that, include: An intermediate mixture was prepared by sol-gel method using a nickel source and a carrier metal source. The intermediate mixture was pyrolyzed to obtain a composite oxide; The composite oxide was photo-reduced under light using a reducing atmosphere to obtain a nickel-based photothermal catalyst for the selective hydrogenation of carbon dioxide.

2. The preparation method according to claim 1, characterized in that, The light source for light reduction is at least one of xenon lamps, LED lamps, tungsten lamps, and mercury lamps, with a light intensity of 0.5~5W cm⁻¹. -2 The restoration time is 5~30 minutes.

3. The preparation method according to claim 1 or 2, characterized in that, The reducing atmosphere for photoreduction under illumination is at least one of H2 / CO2, H2 / Ar, and H2 / N2 mixture.

4. The preparation method according to claim 1, characterized in that, The nickel source is at least one of a soluble salt of nickel and its hydrate, wherein the soluble salt of nickel includes nickel nitrate, nickel chloride, nickel sulfate, and nickel acetate; the concentration of the nickel source is 0.01 mol / L to 5 mol / L.

5. The preparation method according to claim 1, characterized in that, The carrier metal source is at least one of tetrabutyl titanate, cerium nitrate, aluminum nitrate, and tetraethyl silicate.

6. The preparation method according to claim 1, characterized in that, The molar ratio of the nickel source to the carrier metal source is 1:10 to 10:

1.

7. The preparation method according to claim 6, characterized in that, The molar ratio of the nickel source to the carrier metal source is 4:1 to 1:

1.

8. The preparation method according to claim 1, characterized in that, The intermediate mixture prepared using the sol-gel method includes: The nickel source, the carrier metal source, and the additives are mixed evenly to obtain a mixed sol solution; Acid is added to the mixed sol solution and stirred to obtain a nickel carrier precursor solution; The nickel carrier precursor solution is aged to obtain the intermediate mixture.

9. The preparation method according to claim 8, characterized in that, The additives include surfactants and organic solvents; The surfactant comprises at least one of polyether, polyvinylpyrrolidone, and polyethylene glycol; The organic solvent comprises at least one of methanol, ethanol, isopropanol, acetonitrile, and N,N-dimethylformamide; The molar ratio of the nickel source to the surfactant is 1:1 to 10:

1.

10. The preparation method according to claim 8, characterized in that, An acid is added to the mixed sol solution to make the pH of the mixed sol solution less than 7, wherein the acid comprises at least one of hydrochloric acid, glacial acetic acid, and nitric acid; The aging temperature of the nickel carrier precursor solution is 30~100℃, and the time is 4~24h.

11. The preparation method according to claim 1, characterized in that, The intermediate mixture is pyrolyzed in air at a temperature of 300-600°C for 4-12 hours.

12. A nickel-based photothermal catalyst prepared by the preparation method according to any one of claims 1 to 11.

13. The application of the nickel-based photothermal catalyst according to claim 12 in the photothermal catalytic hydrogenation reaction of carbon dioxide.

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