Photocatalytic material, preparation method and application thereof

Abstract

The application discloses a photo-thermal catalyst and a preparation method and application thereof. The photo-thermal catalyst comprises indium oxide and bismuth vanadate grown in situ on the indium oxide, and further comprises phosphorus. In the photo-thermal catalyst, the bismuth vanadate is grown in situ on the surface of the indium oxide, and the two are in close contact to form a heterojunction structure, which is beneficial to charge transmission between the two. In the heterojunction, the indium oxide can effectively promote adsorption and activation of carbon dioxide molecules, while the bismuth vanadate can activate hydrogen, thereby improving the carbon dioxide hydrogenation conversion efficiency. In the heterojunction, the bismuth vanadate and the indium oxide both have semiconductor characteristics, can effectively respond to sunlight, and can further reduce the reaction temperature and pressure of conventional carbon dioxide hydrogenation, thereby reducing energy consumption. The photo-thermal catalyst is synthesized by using a hydrothermal method, non-noble metal raw materials are used, and noble metals such as Pt and Pd, which are commonly required in conventional photo-catalytic materials, are not used, so that the photo-thermal catalyst has the advantages of low price, simple preparation process, good repeatability and easy scale-up production.

Description

Technical Field

[0001] This invention belongs to the field of carbon dioxide catalytic conversion, specifically relating to a composite photothermal catalytic material, its preparation method, and its application. Background Technology

[0002] The rapid development of the current economy and society is highly dependent on traditional fossil fuels, leading to a series of ecological and environmental problems, including the greenhouse effect. Meanwhile, with the rapid development of clean energy, represented by hydrogen energy, the use of green hydrogen obtained from renewable energy sources to convert greenhouse gases such as carbon dioxide into high-value-added chemicals can not only reduce dependence on traditional fossil fuels but also minimize their impact on the ecological environment. Recently, photocatalysis and thermocatalysis for carbon dioxide reduction have attracted widespread attention from researchers and are generally considered one of the most promising technologies for carbon dioxide utilization. However, this technology is still immature, suffering from problems such as harsh reaction conditions, low conversion efficiency, poor selectivity of target products, and poor stability. Therefore, there is an urgent need to develop efficient and controllable carbon dioxide reduction methods. Photothermal catalysis, as an organic combination of photochemical and thermocatalytic pathways, is a promising carbon dioxide reduction technology.

[0003] Patent CN110479235A discloses an indium oxide catalytic material, its preparation method, and its application. The catalytic material is a hexagonal indium oxide with a nano-level hierarchical structure. This catalytic material, when applied to the reaction of carbon dioxide hydrogenation to methanol, exhibits excellent catalytic performance, high reactivity, high selectivity for the target product, good reaction stability, and a very low deactivation rate. However, this system requires operation under high pressure above 1 MPa, which is highly dangerous and energy-intensive.

[0004] CN110586064A discloses a lithium-doped zirconia-supported indium oxide catalytic material, its preparation method, and its application. This catalytic material is prepared by co-precipitation of zirconia with lithium atoms to obtain a support, on which indium oxide particles are uniformly loaded. In the preparation process, lithium and zirconium precursors are first added using a co-precipitation method, followed by precipitation, drying, and calcination to obtain a lithium-doped monoclinic zirconia support. Subsequently, indium oxide is loaded onto the support using a wet impregnation method, and after another drying and calcination, the final catalytic material is obtained. However, the lithium used in this invention is costly and hazardous, which is not conducive to large-scale application. Summary of the Invention

[0005] The purpose of this invention is to provide a catalytic material for the carbon dioxide reduction reaction, as well as a method for preparing the catalytic material and its applications.

[0006] In one aspect, the present invention provides a photothermal catalytic material comprising indium oxide and bismuth vanadate grown in situ thereon, and further comprising P.

[0007] According to one embodiment of the present invention, based on the total mass of the photothermal catalytic material as 100%, the mass content of bismuth vanadate in the photothermal catalytic material is 20%-80%, and the mass content of indium oxide is 20%-80%; preferably, the mass content of bismuth vanadate in the photothermal catalytic material is 40%-60%, and the mass content of indium oxide is 40%-60%.

[0008] According to another embodiment of the present invention, the phosphorus content in the photothermal catalytic material is 0.5-5% by mass, preferably 2.5-3.5%.

[0009] Another aspect of the present invention provides a method for preparing the above-mentioned photothermal catalytic material, comprising: S1, mixing a bismuth salt with a dilute acid solution to form a mixture A, wherein the concentration of the dilute acid solution is 0.5-4 mol / L; S2, mixing a metavanadate with a dilute alkali solution to form a mixture B, wherein the molar amount of alkali is equal to the molar amount of acid used in step S1, and the concentration of the dilute alkali solution is 0.5-4 mol / L; S3, based on the weight of 100g of the mixture A, dissolving the mixture A at 1-5 ml / s at 40-80°C. Add the product to the mixture B at a certain rate, stir for 3-24 hours, and then centrifuge to recover the product; S4, disperse the product obtained in S3 in an alcohol solvent, add indium salt and stir thoroughly; S5, adjust the pH of the product obtained in S4 to 10-11; S6, subject the mixture obtained in S5 to a hydrothermal reaction, and centrifuge, wash and dry the resulting solid after the reaction; S7, disperse the product obtained in S6 in water, add phosphorus source, stir and freeze dry; S8, calcine the powder obtained in S7 to obtain the bismuth vanadate and indium oxide composite material.

[0010] According to one embodiment of the present invention, in step S1, the bismuth salt is one or more of bismuth nitrate, bismuth oxynitrate, bismuth chloride, bismuth oxychloride, bismuth acetate, and bismuth formate.

[0011] According to another embodiment of the present invention, in step S2, the metavanadate is one or more of sodium metavanadate, potassium metavanadate, and ammonium metavanadate.

[0012] According to another embodiment of the present invention, in step S2, the dilute alkaline solution is an aqueous solution of one or both of sodium hydroxide and potassium hydroxide.

[0013] According to another embodiment of the present invention, in step S4, the alcohol is one or more of ethanol, isopropanol and glycerol.

[0014] According to another embodiment of the present invention, in step S5, the indium salt is selected from one or more of its nitrates and chlorides.

[0015] According to another embodiment of the present invention, in step S5, the pH value is adjusted using one or more of urea, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0016] According to another embodiment of the present invention, in step S6, the hydrothermal reaction temperature is 120-200°C and the time is 6-48h.

[0017] According to another embodiment of the present invention, in step S7, the phosphorus source is sodium hypophosphite.

[0018] According to another embodiment of the present invention, in step S7, the freeze-drying temperature is -50 to -20°C, and the time is not less than 24 hours.

[0019] According to another embodiment of the present invention, in step S8, calcination is carried out at a temperature of 300 to 800°C for 2 to 10 hours, with a heating rate of 2 to 10°C per minute, and the calcination atmosphere is one or more of argon, nitrogen, or helium; optionally, the gas flow rate of the calcination atmosphere is 20 to 100 mL / min.

[0020] A third aspect of the present invention provides an application of the above-mentioned photothermal catalytic material in the catalytic reduction reaction of carbon dioxide.

[0021] The present invention also provides the application of the above-mentioned photothermal catalytic material in the catalytic carbon dioxide reduction reaction.

[0022] This invention relates to a photothermal catalytic material in which bismuth vanadate is grown in situ on the surface of indium oxide, forming a heterojunction structure with close contact between the two, which facilitates charge transport between them. Indium oxide in the heterojunction effectively promotes the adsorption and activation of carbon dioxide molecules, while bismuth vanadate activates hydrogen, improving the efficiency of carbon dioxide hydrogenation. Both bismuth vanadate and indium oxide in the heterojunction possess semiconductor properties, effectively responding to sunlight, thereby reducing the reaction temperature and pressure of conventional carbon dioxide hydrogenation and lowering energy consumption. Furthermore, the phosphorus contained in the photothermal catalytic material further promotes the adsorption and activation of reactants. This invention uses a hydrothermal method to synthesize the photothermal catalytic material, employing non-precious metal raw materials, free from precious metals such as Pt and Pd commonly required in conventional photocatalytic materials. It is inexpensive, has a simple preparation process, good reproducibility, and is easy to scale up for mass production. Attached Figure Description

[0023] Figure 1A and Figure 1B This is an electron microscope image of the photothermal catalytic material prepared in Example 1. Detailed Implementation

[0024] The present invention will now be described in detail with reference to specific embodiments.

[0025] The photothermal catalytic material of this invention comprises indium oxide and bismuth vanadate grown in situ on it, and also includes phosphorus (P). In this photothermal catalytic material, because bismuth vanadate is grown in situ on the surface of indium oxide, there is close contact between the two, which is beneficial for charge transport between them. Simultaneously, indium oxide and bismuth vanadate form a heterojunction structure. In this heterojunction, indium oxide can effectively promote the adsorption and activation of carbon dioxide molecules, while bismuth vanadate can activate hydrogen gas, improving the carbon dioxide hydrogenation conversion efficiency. Both bismuth vanadate and indium oxide in the heterojunction possess semiconductor properties, effectively responding to sunlight, thereby reducing the reaction temperature and pressure of conventional carbon dioxide hydrogenation and reducing energy consumption. Furthermore, the photothermal catalytic material of this invention also contains phosphorus, which can further promote the adsorption and activation of reactants. The catalyst of this invention uses non-precious metal raw materials, does not contain precious metals such as Pt and Pd commonly required in conventional photocatalysts, and is inexpensive.

[0026] In an optional embodiment, based on the total mass of the photothermal catalytic material as 100%, the mass content of bismuth vanadate and indium oxide in the photothermal catalytic material is 20%-80% by mass and 20%-80% by mass. Preferably, the mass content of bismuth vanadate and indium oxide in the photothermal catalytic material is 40%-60% by mass and 40%-60% by mass.

[0027] In an optional embodiment, the phosphorus content in the photothermal catalytic material is 0.5-5% by mass, preferably 2.5-3.5%.

[0028] The preparation method of the above-mentioned photothermal catalytic material includes: S1, mixing bismuth salt with a dilute acid solution to form a mixture A, wherein the concentration of the dilute acid solution is 0.5-4 mol / L; S2, mixing metavanadate with a dilute alkali solution to form a mixture B, wherein the molar amount of alkali is equal to the molar amount of acid used in step S1, and the concentration of the dilute alkali solution is 0.5-4 mol / L; S3, adding mixture A to the mixture at a rate of 1-5 ml / s at 40-80℃, based on 100 g of mixture A. In step B, after stirring for 3-24 hours, centrifuge to recover the product; in step S4, disperse the product obtained in step S3 in an alcohol solvent, add indium salt and stir thoroughly; in step S5, adjust the pH of the product obtained in step S4 to 10-11; in step S6, subject the mixture obtained in step S5 to a hydrothermal reaction, and after the reaction, centrifuge, wash and dry the resulting solid; in step S7, disperse the product obtained in step S6 in water, add phosphorus source, stir and freeze dry; in step S8, calcine the powder obtained in step S7 to obtain the bismuth vanadate and indium oxide composite material.

[0029] In step S1, the bismuth salt is one or more of bismuth nitrate, bismuth oxynitrate, bismuth chloride, bismuth oxychloride, bismuth acetate, and bismuth formate.

[0030] In step S2, the metavanadate is one or more of sodium metavanadate, potassium metavanadate, and ammonium metavanadate.

[0031] In step S2, the dilute alkaline solution is an aqueous solution of one or both of sodium hydroxide and potassium hydroxide.

[0032] In step S4, the alcohol is one or more of ethanol, isopropanol, and glycerol.

[0033] In step S5, the indium salt is selected from one or more of its nitrates and chlorides.

[0034] In step S5, the pH value is adjusted using one or more of urea, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

[0035] In step S6, the hydrothermal reaction temperature is 120-200℃ and the time is 6-48h.

[0036] In step S7, the phosphorus source is sodium hypophosphite.

[0037] In step S7, the freeze-drying temperature is -50 to -20°C, and the time is not less than 24 hours.

[0038] In step S8, calcination is performed at a temperature of 300 to 800°C for 2 to 10 hours, with a heating rate of 2 to 10°C per minute. The calcination atmosphere is one or more of argon, nitrogen, or helium. Optionally, the gas flow rate of the calcination atmosphere is 20 to 100 mL / min.

[0039] The photothermal catalytic material of the present invention is suitable for catalyzing the reduction of carbon dioxide.

[0040] The present invention is further described below through specific examples. However, these examples are merely exemplary and do not constitute any limitation on the scope of protection of the present invention. Unless otherwise specified, the reagents, materials, and instruments used in the following embodiments and comparative examples are commercially available.

[0041] Example 1

[0042] 7.5 g of bismuth nitrate pentahydrate was weighed into 20 mL of 4 mol / L dilute nitric acid to prepare mixture A; 1.8 g of sodium metavanadate was weighed into 40 mL of 2 mol / L sodium hydroxide solution to prepare mixture B; mixture A was added to mixture B at a rate of 2.5 mL / s at 50 °C, and the mixture was stirred thoroughly for 12 h before centrifugation to recover the product. The resulting product was dispersed in 50 mL of anhydrous ethanol, and 10.2 g of indium nitrate was weighed and stirred thoroughly before slowly adding sodium hydroxide to adjust the pH to 11. After stirring for 1 h, the resulting mixture was transferred to a polytetrafluoroethylene-lined hydrothermal reactor and reacted at 180 °C for 24 h. After cooling, the resulting solid was centrifuged, washed, and dried. The resulting solid was dispersed with 8.5 g of sodium hypophosphite in 50 mL of water and stirred thoroughly, then freeze-dried at -30 °C for 24 h. The obtained solid was ground and then calcined at 300°C for 4 hours at a heating rate of 5°C per minute. The calcination atmosphere was argon with a gas flow rate of 40 mL / min. After cooling, the bismuth vanadate and indium oxide composite material was obtained. Figure 1A and Figure 1B This is a transmission electron microscope image of a bismuth vanadate / indium oxide composite material. From... Figure 1A It can be seen that bismuth vanadate and indium oxide form a heterojunction structure in close contact in the composite material. From Figure 1A and Figure 1B It can be seen that the composite material prepared in this embodiment has high crystallinity.

[0043] Example 2

[0044] 6.0 g of bismuth nitrate pentahydrate was weighed into 20 mL of 4 mol / L dilute nitric acid to prepare mixture A; 1.4 g of sodium metavanadate was weighed into 40 mL of 2 mol / L sodium hydroxide solution to prepare mixture B; mixture A was added to mixture B at a rate of 2.5 mL / s at 50 °C, and the mixture was stirred thoroughly for 12 h before centrifugation to recover the product. The resulting product was dispersed in 50 mL of anhydrous ethanol, and 12.3 g of indium nitrate was weighed and stirred thoroughly before slowly adding sodium hydroxide to adjust the pH to 11. After stirring for 1 h, the resulting mixture was transferred to a polytetrafluoroethylene-lined hydrothermal reactor and reacted at 180 °C for 24 h. After cooling, the resulting solid was centrifuged, washed, and dried. The resulting solid was dispersed with 8.5 g of sodium hypophosphite in 50 mL of water and stirred thoroughly, then freeze-dried at -30 °C for 24 h. The obtained solid was ground and then calcined at 300°C for 4 hours at a heating rate of 5°C per minute. The calcination atmosphere was argon with a gas flow rate of 40 mL / min. After cooling, the bismuth vanadate and indium oxide composite material was obtained.

[0045] Example 3

[0046] 9.0 g of bismuth nitrate pentahydrate was weighed into 20 mL of 4 mol / L dilute nitric acid to prepare mixture A; 2.2 g of sodium metavanadate was weighed into 40 mL of 2 mol / L sodium hydroxide solution to prepare mixture B; mixture A was added to mixture B at a rate of 3.5 mL / s at 50 °C, and the mixture was stirred thoroughly for 3 h before centrifugation to recover the product. The resulting product was dispersed in 50 mL of anhydrous ethanol, and 8.0 g of indium nitrate was weighed and stirred thoroughly before slowly adding sodium hydroxide to adjust the pH to 11. After stirring for 1 h, the resulting mixture was transferred to a polytetrafluoroethylene-lined hydrothermal reactor and reacted at 180 °C for 24 h. After cooling, the resulting solid was centrifuged, washed, and dried. The resulting solid was dispersed with 8.5 g of sodium hypophosphite in 50 mL of water and stirred thoroughly, then freeze-dried at -30 °C for 24 h. The obtained solid was ground and then calcined at 300°C for 4 hours at a heating rate of 5°C per minute. The calcination atmosphere was argon with a gas flow rate of 40 mL / min. After cooling, the bismuth vanadate and indium oxide composite material was obtained.

[0047] Example 4

[0048] 7.5 g of bismuth nitrate pentahydrate was weighed into 20 mL of 4 mol / L dilute nitric acid to prepare mixture A; 1.8 g of sodium metavanadate was weighed into 40 mL of 2 mol / L sodium hydroxide solution to prepare mixture B; mixture A was added to mixture B at a rate of 1.0 mL / s at 50 °C, and the mixture was stirred thoroughly for 24 h before centrifugation to recover the product. The resulting product was dispersed in 50 mL of anhydrous ethanol, and 10.7 g of indium nitrate was weighed and stirred thoroughly before slowly adding sodium hydroxide to adjust the pH to 11. After stirring for 1 h, the resulting mixture was transferred to a polytetrafluoroethylene-lined hydrothermal reactor and reacted at 180 °C for 24 h. After cooling, the resulting solid was centrifuged, washed, and dried. The resulting solid was dispersed with 1.4 g of sodium hypophosphite in 50 mL of water and stirred thoroughly, then freeze-dried at -30 °C for 24 h. The obtained solid was ground and then calcined at 300°C for 4 hours at a heating rate of 5°C per minute. The calcination atmosphere was argon with a gas flow rate of 40 mL / min. After cooling, the bismuth vanadate and indium oxide composite material was obtained.

[0049] Example 5

[0050] 7.5 g of bismuth nitrate pentahydrate was weighed into 20 mL of 4 mol / L dilute nitric acid to prepare mixture A; 1.8 g of sodium metavanadate was weighed into 40 mL of 2 mol / L sodium hydroxide solution to prepare mixture B; mixture A was added to mixture B at a rate of 5.0 mL / s at 50 °C, and the mixture was stirred thoroughly for 12 h before centrifugation to recover the product. The resulting product was dispersed in 50 mL of anhydrous ethanol, and 9.7 g of indium nitrate was weighed and stirred thoroughly before slowly adding sodium hydroxide to adjust the pH to 11. After stirring for 1 h, the resulting mixture was transferred to a polytetrafluoroethylene-lined hydrothermal reactor and reacted at 180 °C for 24 h. After cooling, the resulting solid was centrifuged, washed, and dried. The resulting solid was dispersed with 14.2 g of sodium hypophosphite in 50 mL of water and stirred thoroughly, then freeze-dried at -30 °C for 24 h. The obtained solid was ground and then calcined at 300°C for 4 hours at a heating rate of 5°C per minute. The calcination atmosphere was argon with a gas flow rate of 40 mL / min. After cooling, the bismuth vanadate and indium oxide composite material was obtained.

[0051] Example 6

[0052] 3.0 g of bismuth nitrate pentahydrate was weighed into 20 mL of 4 mol / L dilute nitric acid to prepare mixture A; 7.2 g of sodium metavanadate was weighed into 40 mL of 2 mol / L sodium hydroxide solution to prepare mixture B; mixture A was added to mixture B at a rate of 2.5 mL / s at 50 °C, and the mixture was stirred thoroughly for 12 h before centrifugation to recover the product. The resulting product was dispersed in 50 mL of anhydrous ethanol, and 16.7 g of indium nitrate was weighed and stirred thoroughly before slowly adding sodium hydroxide to adjust the pH to 11. After stirring for 1 h, the resulting mixture was transferred to a polytetrafluoroethylene-lined hydrothermal reactor and reacted at 180 °C for 24 h. After cooling, the resulting solid was centrifuged, washed, and dried. The resulting solid was dispersed with 8.5 g of sodium hypophosphite in 50 mL of water and stirred thoroughly, then freeze-dried at -30 °C for 24 h. The obtained solid was ground and then calcined at 300°C for 4 hours at a heating rate of 5°C per minute. The calcination atmosphere was argon with a gas flow rate of 40 mL / min. After cooling, the bismuth vanadate and indium oxide composite material was obtained.

[0053] Example 7

[0054] 11.5 g of bismuth nitrate pentahydrate was weighed into 20 mL of 4 mol / L dilute nitric acid to prepare mixture A; 2.8 g of sodium metavanadate was weighed into 40 mL of 2 mol / L sodium hydroxide solution to prepare mixture B; mixture A was added to mixture B at a rate of 2.5 mL / s at 50 °C, and the mixture was stirred thoroughly for 12 h before centrifugation to recover the product. The resulting product was dispersed in 50 mL of anhydrous ethanol, and 4.3 g of indium nitrate was weighed and stirred thoroughly before slowly adding sodium hydroxide to adjust the pH to 11. After stirring for 1 h, the resulting mixture was transferred to a polytetrafluoroethylene-lined hydrothermal reactor and reacted at 180 °C for 24 h. After cooling, the resulting solid was centrifuged, washed, and dried. The resulting solid was dispersed with 8.5 g of sodium hypophosphite in 50 mL of water and stirred thoroughly, then freeze-dried at -30 °C for 24 h. The obtained solid was ground and then calcined at 300°C for 4 hours at a heating rate of 5°C per minute. The calcination atmosphere was argon with a gas flow rate of 40 mL / min. After cooling, the bismuth vanadate and indium oxide composite material was obtained.

[0055] Comparative Example 1

[0056] 7.5 g of bismuth nitrate pentahydrate was weighed into 20 mL of 4 mol / L dilute nitric acid to prepare mixture A; 1.8 g of sodium metavanadate was weighed into 40 mL of 2 mol / L sodium hydroxide solution to prepare mixture B; mixture A was added to mixture B at a rate of 2.5 mL / s at 50 °C, and the mixture was stirred thoroughly for 12 h before centrifugation to recover the product. The resulting product was dispersed in 50 mL of anhydrous ethanol, and 10.2 g of indium nitrate was weighed and stirred thoroughly before slowly adding sodium hydroxide to adjust the pH to 11. After stirring for 1 h, the resulting mixture was transferred to a polytetrafluoroethylene-lined hydrothermal reactor and reacted at 180 °C for 24 h. After cooling, the resulting solid was centrifuged, washed, and dried. The resulting solid was dispersed in 50 mL of water and stirred thoroughly, then freeze-dried at -30 °C for 24 h. The obtained solid was ground and then calcined at 300°C for 4 hours at a heating rate of 5°C per minute. The calcination atmosphere was argon with a gas flow rate of 40 mL / min. After cooling, the bismuth vanadate and indium oxide composite material was obtained.

[0057] Table 1 shows the composition and content of each component in the photothermal catalysts prepared in Examples 1-7 and Comparative Example 1.

[0058] Table 1

[0059]

[0060] Photothermal Co-catalytic Carbon Dioxide Conversion Activity Test

[0061] The composite materials prepared in Examples 1-7 and Comparative Example 1 were used as catalysts to catalyze the reduction reaction of carbon dioxide in order to test the catalytic activity of the composite materials.

[0062] The photothermal synergistic catalytic activity of carbon dioxide conversion was tested using a fixed-bed microreactor with a quartz window. The feed gases were H2, CO2, and Ar in a ratio of 72:24:4, and the space velocity was 60 mL / min. The catalyst loading was 0.5 g, with 4.5 g of quartz sand. The reaction temperature was 150 °C, the pressure was 0.5 MPa, and the light source was a 300 W xenon lamp with a light intensity of 200 mW / cm². -2 Sample analysis was performed using chromatography equipped with a flame ionization detector and a thermal conductivity detector.

[0063] The test data is shown in Table 2.

[0064] Table 2

[0065]

[0066] Comparing the test data of Examples 1-7, it can be seen that the photothermal catalyst of the present invention exhibits good catalytic activity and CO selectivity in the catalytic carbon dioxide reduction reaction. Comparing Examples 1-7 and Comparative Example 1, it can be seen that the catalytic activity and CO selectivity of the catalyst modified with P are significantly improved.

[0067] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A photothermal catalytic material, characterized in that, The photothermal catalytic material includes indium oxide and bismuth vanadate grown in situ thereon, and also includes phosphorus.

2. The photothermal catalytic material according to claim 1, characterized in that, Based on the total mass of the photothermal catalytic material as 100%, the mass content of bismuth vanadate in the photothermal catalytic material is 20%-80%, and the mass content of indium oxide is 20%-80%; preferably, the mass content of bismuth vanadate in the photothermal catalytic material is 40%-60%, and the mass content of indium oxide is 40%-60%.

3. The photothermal catalytic material according to claim 1, characterized in that, The phosphorus content in the photothermal catalytic material is 0.5-5% by mass, preferably 2.5-3.5%.

4. A method for preparing a photothermal catalytic material according to any one of claims 1-3, characterized in that, include: S1, bismuth salt is mixed with dilute acid solution to form mixture A, wherein the concentration of dilute acid solution is 0.5-4 mol / L; S2, mix metavanadate with dilute alkaline solution to form mixture B, the molar amount of alkali is equal to the molar amount of acid used in step S1, and the concentration of the dilute alkaline solution is 0.5-4 mol / L; S3, based on 100g of the mixture A, add the mixture A to the mixture B at a rate of 1-5ml / s at 40-80℃, stir for 3-24h and then centrifuge to recover; S4, disperse the product obtained in S3 in an alcohol solvent, add indium salt and stir thoroughly; S5, adjust the pH of the product obtained in S4 to 10-11; S6. The mixture obtained in S5 is subjected to a hydrothermal reaction. After the reaction, the resulting solid is centrifuged, washed and dried. S7. Disperse the product obtained in S6 in water, add a phosphorus source, stir, and freeze dry. S8, the powder obtained in S7 is calcined to obtain the bismuth vanadate and indium oxide composite material.

5. The preparation method according to claim 4, characterized in that, In step S1, the bismuth salt is one or more of bismuth nitrate, bismuth oxynitrate, bismuth chloride, bismuth oxychloride, bismuth acetate, and bismuth formate; and / or In step S2, the metavanadate is one or more of sodium metavanadate, potassium metavanadate, and ammonium metavanadate; and / or In step S2, the dilute alkaline solution is an aqueous solution of one or both of sodium hydroxide and potassium hydroxide.

6. The preparation method according to claim 4, characterized in that, In step S4, the alcohol is one or more selected from ethanol, isopropanol, and glycerol; and / or In step S5, the indium salt is selected from one or more of its nitrates and chlorides; and / or In step S5, the pH value is adjusted using one or more of urea, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate.

7. The preparation method according to claim 4, characterized in that, In step S6, the hydrothermal reaction temperature is 120-200℃ and the time is 6-48h.

8. The preparation method according to claim 4, characterized in that, In step S7, the phosphorus source is sodium hypophosphite; and / or In step S7, the freeze-drying temperature is -50 to -20°C, and the time is not less than 24 hours.

9. The preparation method according to claim 4, characterized in that, In step S8, calcination is carried out at a temperature of 300 to 800°C for 2 to 10 hours, with a heating rate of 2 to 10°C per minute. The calcination atmosphere is one or more of argon, nitrogen, or helium. Optionally, the gas flow rate of the calcination atmosphere is 20 to 100 mL / min.

10. The application of the photothermal catalytic material according to any one of claims 1-3 in the catalytic reduction reaction of carbon dioxide.

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