A Ce-La composite carrier loaded Cu-Ni bimetallic photo-thermal catalyst and a preparation method thereof

Abstract

The application discloses a kind of Ce-La composite carrier load Cu-Ni bimetallic photo-thermal catalyst and its preparation method, for the defects of existing pure carrier oxygen vacancy concentration fixed, active metal is easy high-temperature agglomeration, catalytic activity and stability are insufficient, the Ce-La composite carrier is constructed by La doping modification in the application, and Cu-Ni bimetallic is formed 8Cu2Ni / aCebLa catalyst.La exists in the form of La-Ce-O solid solution, significantly improves the carrier oxygen vacancy concentration and activation capacity, while strengthening metal-carrier interaction, anchoring bimetallic particles to inhibit sintering, improve catalyst stability.

Description

Technical Field

[0001] This invention relates to solar-powered systems. Photothermal catalysts for hydrogenation of water gas reaction and their preparation methods, specifically involving a Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst and its preparation method. Background Technology

[0002] In light and heat In the hydrogenated reverse-flow gas supported catalyst system, the support can not only perform the functions of dispersing and anchoring active metal components, but also affect the catalytic activity by regulating reactant adsorption and optimizing interfacial interactions. Because it is rich in oxygen vacancies, it can enhance... Adsorption and activation make it a high-performance carrier material for this system. However, pure... The oxygen vacancy concentration in the carrier is relatively fixed and difficult to increase further. Activation efficiency limits the improvement of catalytic reaction activity. Furthermore, active metals are prone to agglomeration and sintering at high temperatures during the reaction, leading to insufficient catalyst stability. Summary of the Invention

[0003] Purpose of the invention: The first purpose of this invention is to address the shortcomings of existing... The limitations of limited oxygen vacancy sites on the support, insufficient catalyst activity, and poor stability necessitate a solution with high oxygen vacancy concentration... A photothermal catalyst of Cu-Ni bimetallic supported on a Ce-La composite support with good activation ability and strong stability; the second objective of this invention is to provide a method for preparing the photothermal catalyst.

[0004] Technical solution: The present invention provides a Ce-La composite support for Cu-Ni bimetallic photothermal catalyst, which is a catalyst 8Cu2Ni / aCebLa with a Ce-La composite support and Cu-Ni bimetallic active metal component, wherein a takes the value of 9, 6, 3 or 0, and b = 10-a.

[0005] The method for preparing the Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst of the present invention includes:

[0006] S1: Dissolve cerium nitrate hexahydrate, lanthanum nitrate hexahydrate, acrylic acid, and anhydrous glucose in deionized water at room temperature and stir continuously; then slowly add ammonia water dropwise to the solution to adjust the pH value to 8-12, and continue stirring.

[0007] S2: The stirred solution will be placed in a hydrothermal reactor for hydrothermal reaction;

[0008] S3: After the solution that has completed the hydrothermal reaction is cooled to room temperature, it is centrifuged and washed to obtain the sample precipitate. The precipitate is dried and placed in an alumina crucible. The alumina crucible is then placed in a muffle furnace for calcination to obtain the Ce-La composite support aCebLa.

[0009] S4: Dissolve the Ce-La composite carrier aCebLa, nickel nitrate hexahydrate and copper nitrate trihydrate in a mixed solution of anhydrous ethanol and deionized water, stir continuously, and slowly add ammonia dropwise to adjust the pH value to 9-13.

[0010] S5: Continue stirring and heating until the pH value drops to 7. After centrifugation and washing, dry the precipitate and place it in an alumina crucible. Place the alumina crucible in a muffle furnace for calcination. The resulting sample is then thoroughly ground to obtain precursor powder.

[0011] S6: The precursor powder is then... The catalyst was obtained by high-temperature reduction in an atmosphere to produce 8Cu2Ni / aCebLa catalyst.

[0012] Further, in step S1, the molar ratio of cerium nitrate hexahydrate and lanthanum nitrate hexahydrate is 9:1 to 0:10, the stirring time is 1-30 min, the ammonia concentration is 25-28 wt%, and the stirring time is 2-4 h.

[0013] Furthermore, in step S2, the hydrothermal temperature is 180℃ and the reaction time is 72h.

[0014] Furthermore, in step S3, the calcination heating rate is 5℃ / min, the calcination temperature is 600℃, and the calcination time is 6h.

[0015] Further, in step S4, the mass of Ce-La composite carrier aCebLa is 50 mg, the mass of copper nitrate trihydrate is 1-50 mg, the mass of nickel nitrate hexahydrate is 1-50 mg, the mixed solution consists of 35 mL of anhydrous ethanol and 5 mL of deionized water, and the stirring time is 15 min.

[0016] Furthermore, in step S5, the heating temperature is 60-80℃, the drying temperature is 50-70℃, the drying time is 5-7h, the calcination heating rate is 5℃ / min, the calcination temperature is 550℃, and the calcination time is 6h.

[0017] Furthermore, in steps S3 and S5, deionized water and anhydrous ethanol are used alternately for washing several times.

[0018] Furthermore, in step S6, the heating rate is 5℃ / min, the reduction temperature is 500℃, and the high-temperature reduction time is 1h.

[0019] Furthermore, in step S6, The atmosphere is 10 vol% at a flow rate of 100 mL / min. atmosphere.

[0020] Technical principle of the invention:

[0021] This invention obtains an 8Cu₂Ni / aCebLa catalyst by loading Cu-Ni bimetallic nanoparticles onto a Ce-La composite support aCebLa. The La-doped Ce-La composite support has a high oxygen vacancy concentration, which increases the catalyst's affinity for reactants. Its activation ability, thereby enhancing photothermal activity. Hydrogenation of water gas reaction Conversion rate; Because the La-doped Ce-La composite support provides strong metal-support interaction, it can anchor Cu-Ni bimetallic particles, preventing their aggregation at high temperatures and ensuring the stable existence of active sites, thus enabling photothermal conversion. The hydrogenation reverse water gas reaction operates stably for a long time.

[0022] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0023] (1) The doping element La is doped in the form of La-Ce-O solid solution to form Ce-La composite support, which significantly increases the oxygen vacancy concentration on the support surface and strengthens the support. Adsorption and activation capabilities, solving The bottleneck of a fixed number of oxygen vacancies in the carrier;

[0024] (2) La doping optimizes the interface between the support and Cu-Ni bimetal, effectively anchors the bimetal particles, and inhibits the migration and sintering of metal particles at high temperature. The catalyst operates stably for 430 hours under photothermal reaction conditions, showing excellent structural stability and catalytic stability. Attached Figure Description

[0025] Figure 1 This is a SEM image of the catalyst 8Cu2Ni / 6Ce4La in the embodiments of the present invention;

[0026] Figure 2 These are the XRD patterns of catalysts 8Cu2Ni / 9Ce1La, 8Cu2Ni / 6Ce4La, and 8Cu2Ni / 3Ce7La in the embodiments of the present invention;

[0027] Figure 3 The hydrogen temperature-programmed reduction of catalysts 8Cu2Ni / 9Ce1La, 8Cu2Ni / 6Ce4La, and 8Cu2Ni / 3Ce7La in the embodiments of this invention ( -TPR) diagram;

[0028] Figure 4 This is the EPR diagram of the catalyst 8Cu2Ni / 6Ce4La in the embodiments of the present invention;

[0029] Figure 5 This is the UV-Vis-NIR spectral absorbance diagram of the catalysts 8Cu2Ni / 9Ce1La, 8Cu2Ni / 6Ce4La, and 8Cu2Ni / 3Ce7La in the embodiments of the present invention;

[0030] Figure 6 This is a temperature rise diagram of catalysts 8Cu2Ni / 9Ce1La, 8Cu2Ni / 6Ce4La, and 8Cu2Ni / 3Ce7La under simulated sunlight irradiation by a xenon lamp in an embodiment of the present invention;

[0031] Figure 7 In the embodiments of this invention, the catalyst 8Cu2Ni / aCebLa is used in photothermal driving... Catalytic performance diagrams of hydrogenation in the reverse water gas reaction, where (a) is catalyst 8Cu2Ni / 9Ce1La, (b) is catalyst 8Cu2Ni / 6Ce4La, (c) is catalyst 8Cu2Ni / 3Ce7La, and (d) is catalyst 8Cu2Ni / 10La.

[0032] Figure 8 In the embodiments of this invention, the catalyst 8Cu2Ni / 6Ce4La is used in photothermal driving... Catalytic stability diagram of hydrogenation of water gas;

[0033] Figure 9 This refers to the catalyst 8Cu2Ni / 6Ce4La in the embodiments of the present invention under light and dark conditions. The catalytic performance diagram in the hydrogenation of water gas reaction is shown, where (a) represents the catalytic performance. Conversion rate comparison, (b) is Selective comparison. Detailed Implementation

[0034] The invention will now be further described with reference to the accompanying drawings.

[0035] Example 1: A Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst, using a Ce-La composite support, with the active metal component being a Cu-Ni bimetallic catalyst 8Cu2Ni / aCebLa, where a takes the value of 9, 6, 3, or 0, and b = 10⁻⁶a. In subsequent preparation, the molar ratio of cerium nitrate hexahydrate and lanthanum nitrate hexahydrate is used. The SEM image of 8Cu2Ni / 6Ce4La is shown below. Figure 1 As shown, no metal particles were clearly observed in the catalyst 8Cu2Ni / 6Ce4La, indicating that the active metal was well dispersed.

[0036] Example 2: A method for preparing a photothermal catalyst of Cu-Ni bimetal supported on a Ce-La composite support, comprising:

[0037] S1: Dissolve 1.955g cerium nitrate hexahydrate, 0.217g lanthanum nitrate hexahydrate, 1.028mL acrylic acid, and 1.982g anhydrous glucose in 60mL deionized water at room temperature and stir continuously for 15min. Then slowly add ammonia dropwise to the solution to control the pH to 10 and continue stirring for 3h.

[0038] S2: The stirred solution is placed in a hydrothermal reactor for hydrothermal reaction at a temperature of 180°C for 72 hours.

[0039] S3: After the hydrothermal reaction solution has cooled to room temperature, the sample is centrifuged and washed three times alternately with deionized water and anhydrous ethanol. The centrifuged and washed sample is then dried at 60°C for 6 hours. After drying, the sample is placed in an alumina crucible, which is then placed in a muffle furnace and calcined at 600°C for 6 hours to obtain the Ce-La composite support 9Ce1La.

[0040] S4: Take 50 mg of 9Ce1La carrier powder, 15.13 mg of copper nitrate trihydrate and 4.93 mg of nickel nitrate hexahydrate, dissolve them in a mixed solution of 35 mL of anhydrous ethanol and 5 mL of deionized water, stir for 15 min to mix thoroughly, and then slowly add ammonia dropwise until pH=11.

[0041] S5: Continue stirring and heat at 70℃ until the pH value drops to 7. After centrifugation and washing, wash the precipitate three times alternately with deionized water and anhydrous ethanol. Dry the precipitate at 60℃ for 6 hours. Place the sample in an alumina crucible and heat it to 550℃ in a muffle furnace at a heating rate of 5℃ / min. Calcine the sample at 550℃ for 6 hours. Grind the powder thoroughly to obtain the precursor powder.

[0042] S6: The precursor powder was subjected to a 10 vol% solution at a flow rate of 100 mL / min. The catalyst was reduced for 1 h at a heating rate of 5 °C / min and a reduction temperature of 500 °C to obtain 8Cu2Ni / 9Ce1La catalyst.

[0043] Example 3: A method for preparing a photothermal catalyst of Cu-Ni bimetal supported on a Ce-La composite support, comprising:

[0044] S1: Dissolve 1.303 g cerium nitrate hexahydrate, 0.866 g lanthanum nitrate hexahydrate, 1.028 mL acrylic acid, and 1.982 g anhydrous glucose in 60 mL deionized water at room temperature and stir continuously for 15 min. Then slowly add ammonia water dropwise to the solution to control the pH to 10, and continue stirring for 3 h.

[0045] S2: The stirred solution is placed in a hydrothermal reactor for hydrothermal reaction at a temperature of 180°C for 72 hours.

[0046] S3: After the hydrothermal reaction solution has cooled to room temperature, the sample is centrifuged and washed three times alternately with deionized water and anhydrous ethanol. The centrifuged and washed sample is then dried at 60°C for 6 hours. After drying, the sample is placed in an alumina crucible, which is then placed in a muffle furnace and calcined at 600°C for 6 hours to obtain the Ce-La composite support 6Ce4La.

[0047] S4: Take 50 mg of 6Ce4La carrier powder, 15.13 mg of copper nitrate trihydrate and 4.93 mg of nickel nitrate hexahydrate, dissolve them in a mixed solution of 35 mL of anhydrous ethanol and 5 mL of deionized water, stir for 15 min to mix thoroughly, and then slowly add ammonia dropwise until pH=11.

[0048] S5: Continue stirring and heat at 70℃ until the pH value drops to 7. After centrifugation and washing, wash the precipitate three times alternately with deionized water and anhydrous ethanol. Dry the precipitate at 60℃ for 6 hours. Place the sample in an alumina crucible and heat it to 550℃ in a muffle furnace at a heating rate of 5℃ / min. Calcine the sample at 550℃ for 6 hours. Grind the powder thoroughly to obtain the precursor powder.

[0049] S6: The precursor powder was subjected to a 10 vol% solution at a flow rate of 100 mL / min. The catalyst was reduced for 1 h at a heating rate of 5 °C / min and a reduction temperature of 500 °C to obtain 8Cu2Ni / 6Ce4La catalyst.

[0050] Example 4: A method for preparing a photothermal catalyst of Cu-Ni bimetal supported on a Ce-La composite support, comprising:

[0051] S1: Dissolve 0.652 g cerium nitrate hexahydrate, 1.516 g lanthanum nitrate hexahydrate, 1.028 mL acrylic acid, and 1.982 g anhydrous glucose in 60 mL deionized water at room temperature and stir continuously for 15 min. Then slowly add ammonia water dropwise to the solution to control the pH to 10, and continue stirring for 3 h.

[0052] S2: The stirred solution is placed in a hydrothermal reactor for hydrothermal reaction at a temperature of 180°C for 72 hours.

[0053] S3: After the hydrothermal reaction solution has cooled to room temperature, the sample is centrifuged and washed three times alternately with deionized water and anhydrous ethanol. The centrifuged and washed sample is then dried at 60°C for 6 hours. After drying, the sample is placed in an alumina crucible, which is then placed in a muffle furnace and calcined at 600°C for 6 hours to obtain the Ce-La composite support 3Ce7La.

[0054] S4: Take 50 mg of 3Ce7La carrier powder, 15.13 mg of copper nitrate trihydrate and 4.93 mg of nickel nitrate hexahydrate, dissolve them in a mixed solution of 35 mL of anhydrous ethanol and 5 mL of deionized water, stir for 15 min to mix thoroughly, and then slowly add ammonia dropwise until pH=11.

[0055] S5: Continue stirring and heat at 70℃ until the pH value drops to 7. After centrifugation and washing, wash the precipitate three times alternately with deionized water and anhydrous ethanol. Dry the precipitate at 60℃ for 6 hours. Place the sample in an alumina crucible and heat it to 550℃ in a muffle furnace at a heating rate of 5℃ / min. Calcine the sample at 550℃ for 6 hours. Grind the powder thoroughly to obtain the precursor powder.

[0056] S6: The precursor powder was subjected to a 10 vol% solution at a flow rate of 100 mL / min. The catalyst was reduced for 1 h at a heating rate of 5 °C / min and a reduction temperature of 500 °C to obtain 8Cu2Ni / 3Ce7La catalyst.

[0057] Example 5: A method for preparing a photothermal catalyst of Cu-Ni bimetal supported on a Ce-La composite support, comprising:

[0058] S1: Dissolve 2.166 g of lanthanum nitrate hexahydrate, 1.028 mL of acrylic acid, and 1.982 g of anhydrous glucose in 60 mL of deionized water at room temperature and stir continuously for 15 min. Then, slowly add ammonia dropwise to the solution to control the pH to 10 and continue stirring for 3 h.

[0059] S2: The stirred solution is placed in a hydrothermal reactor for hydrothermal reaction at a temperature of 180°C for 72 hours.

[0060] S3: After the hydrothermal reaction solution has cooled to room temperature, the sample is centrifuged and washed three times alternately with deionized water and anhydrous ethanol. The centrifuged and washed sample is then dried at 60°C for 6 hours. After drying, the sample is placed in an alumina crucible, which is then placed in a muffle furnace and calcined at 600°C for 6 hours to obtain the Ce-La composite support 10La.

[0061] S4: Take 50 mg of 10La carrier powder, 15.13 mg of copper nitrate trihydrate and 4.93 mg of nickel nitrate hexahydrate, dissolve them in a mixed solution of 35 mL of anhydrous ethanol and 5 mL of deionized water, stir for 15 min to mix thoroughly, and then slowly add ammonia dropwise until pH=11.

[0062] S5: Continue stirring and heat at 70℃ until the pH value drops to 7. After centrifugation and washing, wash the precipitate three times alternately with deionized water and anhydrous ethanol. Dry the precipitate at 60℃ for 6 hours. Place the sample in an alumina crucible and heat it to 550℃ in a muffle furnace at a heating rate of 5℃ / min. Calcine the sample at 550℃ for 6 hours. Grind the powder thoroughly to obtain the precursor powder.

[0063] S6: The precursor powder was subjected to a 10 vol% solution at a flow rate of 100 mL / min. The catalyst was reduced for 1 h at a heating rate of 5 °C / min and a reduction temperature of 500 °C to obtain 8Cu2Ni / 10La catalyst.

[0064] The catalysts 8Cu2Ni / aCebLa prepared in Examples 2 to 5 were tested as follows:

[0065] I. Photothermal Physicochemical characterization of hydrogenation counter-current gas reaction catalyst

[0066] (1) XRD test: XRD analysis was performed on the catalysts 8Cu2Ni / 9Ce1La, 8Cu2Ni / 6Ce4La and 8Cu2Ni / 3Ce7La, and the results are as follows. Figure 2 As shown: 8Cu2Ni / 9Ce1La, 8Cu2Ni / 6Ce4La, and 8Cu2Ni / 3Ce7La exhibit... The diffraction peaks of the Cu-Ni alloy indicate that Ce and La elements exist in the form of La-Ce-O solid solution, while the bimetal exists in the form of an alloy.

[0067] (2) Hydrogen temperature-programmed reduction ( -TPR) test and EPR test: Hydrogen temperature-programmed reduction (TPR) of 8Cu2Ni / 9Ce1La, 8Cu2Ni / 6Ce4La and 8Cu2Ni / 3Ce7La -TPR) test curve as follows Figure 3 As shown, the reduction temperature of the metal increases with the increase of La addition, indicating that the interaction force between the metal and the support is enhanced with the increase of La addition. Figure 4 The EPR spectrum of 8Cu2Ni / 6Ce4La shows that there are obvious oxygen vacancies in the catalyst.

[0068] (3) Ultraviolet-Visible-Near Infrared Spectral Absorption Rate Test and Photothermal Catalyst Heating Test: by Figure 5 It can be seen that 8Cu2Ni / 9Ce1La, 8Cu2Ni / 6Ce4La, and 8Cu2Ni / 3Ce7La exhibit good light absorption properties across the entire spectral range. Figure 6 It can be seen that 8Cu2Ni / 9Ce1La, 8Cu2Ni / 6Ce4La, and 8Cu2Ni / 3Ce7La can all reach relatively high temperatures under simulated sunlight irradiation by a xenon lamp, indicating that the catalysts have excellent photothermal conversion capabilities, enabling them to efficiently drive photothermal coupling. Hydrogenation of water gas in reverse reaction.

[0069] II. Photothermal Hydrogenation of water gas reaction catalytic activity test

[0070] 20 mg of 8Cu2Ni / aCebLa catalyst was packed into a self-built photothermal catalytic reactor with an inner diameter of 8 mm, and the catalyst was subjected to 6.18 W concentrated light irradiation at a rate of 50 °C. The flow rate is used to introduce a volume fraction of 20% / 60% / 20% into the photothermal reactor. / / Mixed gas. The tail gas from the photothermal catalytic reactor outlet is passed into a gas chromatograph for gas type and content analysis, and quantification is performed based on the peak area in the chromatogram. Photothermal catalytic reactors with 8Cu2Ni / 9Ce1La, 8Cu2Ni / 6Ce4La, 8Cu2Ni / 3Ce7La, and 8Cu2Ni / 10La are used. Hydrogenation of water gas reaction Conversion rate and CO selectivity, such as Figure 7 (a) to Figure 7 As shown in (d), 8Cu2Ni / 6Ce4La exhibits outstanding photothermal catalytic activity under simulated sunlight under a xenon lamp, with an average... The conversion rate was 51.54%, and the average CO selectivity was 98.72%. Figure 8 The reaction showed stability after 430 hours, with no significant decrease in catalytic activity.

[0071] III. Thermal catalysis under dark conditions Hydrogenation of water gas reaction activity test

[0072] 20 mg of 8Cu2Ni / aCebLa catalyst was placed in a tube furnace at 50 °C. The flow rate of the influent volume content is / / The mixture of gases is then heated to a temperature similar to that of light and heat using electric heating. The catalytic activity test for the hydrogenation reaction of water and gas was conducted at the same reaction temperature. Gas from the tubular furnace outlet was introduced into a gas chromatograph for gas type and content analysis, and quantification was performed based on the peak area in the chromatogram. Figure 9 As shown, photothermal on 8Cu2Ni / 6Ce4La The hydrogenated water gas reaction activity was significantly higher than the thermocatalytic activity under dark conditions, indicating that photothermal coupling catalysis can enhance the reaction. Catalytic activity of hydrogenation in the reverse reaction of water and coal gas.

Claims

1. A photothermal catalyst for Cu-Ni bimetal supported on a Ce-La composite support, characterized in that, To utilize the Ce-La composite support, the active metal component is a Cu-Ni bimetallic catalyst 8Cu2Ni / aCebLa, where a takes the value of 9, 6, 3 or 0, and b = 10-a.

2. A method for preparing a Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst according to claim 1, characterized in that, include: S1: Dissolve cerium nitrate hexahydrate, lanthanum nitrate hexahydrate, acrylic acid, and anhydrous glucose in deionized water at room temperature, while stirring continuously; Then, slowly add ammonia water dropwise to the solution to adjust the pH value to 8-12, and continue stirring; S2: The stirred solution will be placed in a hydrothermal reactor for hydrothermal reaction; S3: After the solution that has completed the hydrothermal reaction is cooled to room temperature, it is centrifuged and washed to obtain the sample precipitate. The precipitate is dried and placed in an alumina crucible. The alumina crucible is then placed in a muffle furnace for calcination to obtain the Ce-La composite support aCebLa. S4: Dissolve the Ce-La composite carrier aCebLa, nickel nitrate hexahydrate and copper nitrate trihydrate in a mixed solution of anhydrous ethanol and deionized water, stir continuously, and slowly add ammonia dropwise to adjust the pH value to 9-13. S5: Continue stirring and heating until the pH value drops to 7. After centrifugation and washing, dry the precipitate and place it in an alumina crucible. Place the alumina crucible in a muffle furnace for calcination. The resulting sample is then thoroughly ground to obtain precursor powder. S6: The precursor powder is then... The catalyst was obtained by high-temperature reduction in an atmosphere to produce 8Cu2Ni / aCebLa catalyst.

3. The method for preparing the Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst according to claim 2, characterized in that, In step S1, the molar ratio of cerium nitrate hexahydrate to lanthanum nitrate hexahydrate is 9:1 to 0:10, the stirring time is 1-30 min, the ammonia concentration is 25-28 wt%, and the stirring time is 2-4 h.

4. The method for preparing the Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst according to claim 2, characterized in that, In step S2, the hydrothermal temperature is 180℃ and the reaction time is 72h.

5. The method for preparing the Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst according to claim 2, characterized in that, In step S3, the calcination heating rate is 5℃ / min, the calcination temperature is 600℃, and the calcination time is 6h.

6. The method for preparing the Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst according to claim 2, characterized in that, In step S4, the mass of Ce-La composite carrier aCebLa is 50 mg, the mass of copper nitrate trihydrate is 1-50 mg, the mass of nickel nitrate hexahydrate is 1-50 mg, the mixed solution consists of 35 mL of anhydrous ethanol and 5 mL of deionized water, and the stirring time is 15 min.

7. The method for preparing the Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst according to claim 2, characterized in that, In step S5, the heating temperature is 60-80℃, the drying temperature is 50-70℃, the drying time is 5-7h, the calcination heating rate is 5℃ / min, the calcination temperature is 550℃, and the calcination time is 6h.

8. The method for preparing the Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst according to claim 2, characterized in that, In steps S3 and S5, deionized water and anhydrous ethanol are used to wash the product several times alternately.

9. The method for preparing the Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst according to claim 2, characterized in that, In step S6, the heating rate is 5℃ / min, the reduction temperature is 500℃, and the high-temperature reduction time is 1h.

10. The method for preparing the Ce-La composite support-supported Cu-Ni bimetallic photothermal catalyst according to claim 2, characterized in that, In step S6, The atmosphere is 10 vol% at a flow rate of 100 mL / min. atmosphere.

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