A supported cerium-zirconium solid solution photocatalyst, a preparation method thereof and application thereof in catalytic reaction of dehydrogenation of organic liquid hydride for storing solar energy

Abstract

This invention relates to a supported cerium-zirconium solid solution photocatalyst, its preparation method, and its application in the catalytic reaction of organic liquid hydride dehydrogenation for solar energy storage, belonging to the field of solid solution photocatalyst technology. The invention first prepares a cerium-zirconium solid solution using an alkaline solution co-precipitation method or a reducing agent combustion method, and then prepares a supported cerium-zirconium solid solution photocatalyst using a chemical deposition method or a photodeposition method. The invention also relates to a conversion device for capturing and storing solar energy. In the solar-driven cyclohexane dehydrogenation catalytic reaction, the supported cerium-zirconium solid solution photocatalyst prepared in this invention exhibits excellent catalytic activity and stability, with a hydrogen production rate as high as 2.89 mol·g⁻¹. Pt ‑1 ·min ‑1 The system has a turnover rate exceeding 100,000 times and a hydrogen purity exceeding 99.99%. The dehydrogenation catalytic reaction system described in this invention can effectively absorb ultraviolet, visible, and near-infrared light from sunlight, opening up new avenues for the widespread application of solar energy.

Description

Technical Field

[0001] This invention belongs to the field of solid solution photocatalyst technology, specifically relating to a supported cerium-zirconium solid solution photocatalyst, its preparation method, and its application in the storage of solar energy in the dehydrogenation catalytic reaction of organic liquid hydrides. It also relates to a conversion device for capturing and storing solar energy in the dehydrogenation catalytic reaction of organic liquid hydrides. This device utilizes the dehydrogenation catalytic reaction triggered by sunlight irradiation to efficiently capture and store solar energy. Background Technology

[0002] With the increasing depletion of fossil fuel resources and the continuous deterioration of the ecological environment, solar energy, as a clean and renewable energy source, has been widely studied in the hope of solving the global energy crisis and mitigating environmental pollution. However, the utilization of solar energy faces challenges such as low density, discontinuity, and instability, which limit its widespread application in energy supply. Traditional solar thermal storage technology, while providing a pathway for solar energy capture and utilization, still has significant shortcomings in terms of energy density, storage period, and conversion efficiency.

[0003] Solar thermal energy storage technologies are mainly classified into three categories: sensible heat storage, latent heat storage, and thermochemical energy storage. While sensible and latent heat storage technologies have applications in certain fields, their relatively low energy density and limited operating temperature range make long-term, efficient energy storage a challenge. In contrast, thermochemical energy storage (TCES) technology achieves efficient energy capture and release through the endothermic and exothermic processes of chemical reactions, demonstrating high energy density and long-term storage potential, particularly in cross-regional heat transfer.

[0004] In recent years, organic liquid hydrides have attracted attention due to their great potential in hydrogen storage and energy conversion. These materials demonstrate promising applications in thermochemical energy storage technologies through the reversibility of hydrodehydrogenation catalytic reactions. For example, photocatalytic dehydrogenation of cyclohexane at low temperatures was achieved using titanium dioxide catalysts supported on nano-Pt particles. Although these preliminary studies have made some progress, the reaction activity still lags behind that of thermal catalysts, and the hydrogen production capacity is limited by the relatively low loading of noble metals.

[0005] This invention significantly improves the efficiency and stability of liquid cycloalkane dehydrogenation catalytic reactions by developing and preparing a supported cerium-zirconium solid solution photocatalyst and designing a device for storing solar energy in the dehydrogenation catalytic reaction of organic liquid hydrides, thus achieving a highly efficient conversion of solar energy into chemical energy. This technology not only provides a low-cost, high-energy-density, and excellent cycle stability thermochemical energy storage solution, but also solves the problem of low energy conversion efficiency by generating heterogeneous products that are easy to separate, transport, and store. Therefore, this invention has significant practical application value and broad development prospects in the field of thermochemical energy storage technology. Summary of the Invention

[0006] The purpose of this invention is to provide a supported cerium-zirconium solid solution photocatalyst, its preparation method, and its application in storing solar energy in the dehydrogenation catalytic reaction of organic liquid hydrides. This invention also provides a conversion device for capturing and storing solar energy in the dehydrogenation catalytic reaction of organic liquid hydrides, thereby achieving efficient storage of solar energy in the dehydrogenation catalytic reaction of organic liquid hydrides by utilizing a supported cerium-zirconium solid solution photocatalyst.

[0007] The preparation method of the supported cerium-zirconium solid solution photocatalyst of the present invention comprises the following steps:

[0008] (1) Preparation of cerium-zirconium solid solution by alkaline coprecipitation method: Weigh cerium salt and zirconium salt, disperse them evenly in water and stir continuously; then add alkaline aqueous solution to adjust the pH of the solution to 8-12, stir the reaction for 0.5-1 hours to form a precipitate; filter the precipitate using a vacuum filtration device, wash with water until the pH of the filtrate is neutral, and dry in an oven to obtain the cerium-zirconium solid solution precursor; finally, treat the cerium-zirconium solid solution precursor at high temperature to obtain the cerium-zirconium solid solution, denoted as 1-C. x Z y ;

[0009] The molar ratio of cerium salt to zirconium salt is x : y, and x / (x+ y) = 0.1~0.9, the total molar amount is 0.01~100 mmol, and it is dispersed in 5~500 mL of water;

[0010] The cerium salt mentioned is one of Ce(NO3)3·6H2O, CeCl3·7H2O, and Ce2(CO3)3·5H2O;

[0011] The zirconium salt is one of ZrO(NO3)2·2H2O, ZrOCl2·8H2O, and Zr(NO3)4·5H2O;

[0012] The stirring was performed using magnetic stirring at 100-1000 r / min for 0.5-12 hours;

[0013] The alkaline aqueous solution is one or a mixture of several of the following: sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonium carbonate aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution, lithium bicarbonate aqueous solution, and ammonia solution.

[0014] The concentration of the alkaline aqueous solution is 0.01~10 mol / L;

[0015] The drying temperature in the oven is 30~80 ℃, and the processing time is 1~10 hours;

[0016] The high-temperature treatment is performed at a temperature of 500~1200 ℃ for a duration of 1~10 hours.

[0017] Alternatively, cerium-zirconium solid solution can be prepared by reducing agent combustion: cerium salt, zirconium salt, and reducing agent are weighed and dispersed in water with continuous stirring; after evaporating the solvent, the mixture is heated to initiate a spontaneous combustion reaction to obtain a cerium-zirconium solid solution precursor; finally, the cerium-zirconium solid solution precursor is treated at high temperature to obtain the cerium-zirconium solid solution, denoted as 2-C. x Z y ;

[0018] The molar ratio of the cerium salt to the zirconium salt is x : y, and x / (x+ y) = 0.1~0.9, the total molar mass is 0.01~100 mmol, and it is dispersed in 5~500 mL of water;

[0019] The cerium salt mentioned is one of Ce(NO3)3·6H2O, CeCl3·7H2O, and Ce2(CO3)3·5H2O;

[0020] The zirconium salt is one of ZrO(NO3)2·2H2O, ZrOCl2·8H2O, and Zr(NO3)4·5H2O;

[0021] The reducing agent is one of glycine, tartaric acid, and citric acid;

[0022] The ratio of the total molar number of cerium and zirconium salts to the molar number of reducing agent is 1:0.1~10;

[0023] The stirring was performed using magnetic stirring at 100-1000 r / min for 0.5-12 hours;

[0024] The solvent is evaporated at a temperature of 60-120°C, the temperature for initiating the auto-ignition reaction is 150-250°C, and the auto-ignition reaction time is 0.5-5 min.

[0025] The high-temperature treatment is performed at a temperature of 500~1200 ℃ for a duration of 1~10 hours.

[0026] (2) Preparation of supported cerium-zirconium solid solution photocatalyst by chemical deposition: Cerium-zirconium solid solution is dispersed in water, and metal salt aqueous solution is added while stirring continuously. Then, reducing-alkaline aqueous solution is added to adjust the pH to 8-12. The reaction is carried out for 0.5-2 hours under magnetic stirring at 500-700 r / min, and the metal is chemically deposited on the cerium-zirconium solid solution. Finally, the precipitate is filtered using a vacuum filtration device, washed with water until the pH of the filtrate is neutral, and vacuum dried overnight to obtain the supported cerium-zirconium solid solution photocatalyst, denoted as M. NP / C x Z y (M = Pt, Ru, Rh, Pd, Nb, Mo, Au, Ag, Fe, Co, Ni, Cu, Cd), the metals loaded in this method are mostly nanoparticles (NP).

[0027] The metal salt is one or a combination of several of the following: soluble platinum salt, ruthenium salt, rhodium salt, palladium salt, niobium salt, molybdenum salt, gold salt, silver salt, iron salt, cobalt salt, nickel salt, copper salt, or cadmium salt.

[0028] The cerium-zirconium solid solution has a mass of 100-500 mg and is dispersed in 5-500 mL of water;

[0029] The mass concentration of the metal salt solution is 0.5~10 g / L;

[0030] The total mass of the loaded metal accounts for 0.01% to 10% of the total mass of the catalyst;

[0031] The reducing-alkali aqueous solution is a mixture of one or more of the following: sodium borohydride aqueous solution and sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonium carbonate aqueous solution, potassium carbonate aqueous solution, sodium carbonate aqueous solution, lithium bicarbonate aqueous solution, and ammonia solution.

[0032] The concentration of the reducing-alkali aqueous solution is 0.01~10 mol / L;

[0033] Alternatively, a supported cerium-zirconium solid solution photocatalyst can be prepared by photodeposition: A cerium-zirconium solid solution is dispersed in water, continuously stirred, and an aqueous metal salt solution is added, followed by a sacrificial agent. The mixture is then ultrasonically stirred for 20–40 min to obtain a cerium-zirconium solid solution suspension. Photodeposition is then performed under vacuum, illumination with a 200–400 W light source, and magnetic stirring at 100–1000 r / min. Finally, the precipitate is filtered using a vacuum filtration device, washed with water until the filtrate is neutral in pH, and vacuum dried overnight to obtain the supported cerium-zirconium solid solution photocatalyst, denoted as M / C. x Z y (M=Pt, Ru, Rh, Pd, Nb, Mo, Au, Ag, Fe, Co, Ni, Cu, Cd);

[0034] The aqueous solution of the metal salt is one or a combination of several of the following: soluble platinum salt, ruthenium salt, rhodium salt, palladium salt, niobium salt, molybdenum salt, gold salt, silver salt, iron salt, cobalt salt, nickel salt, copper salt, or cadmium salt.

[0035] The cerium-zirconium solid solution has a mass of 100-500 mg and is dispersed in 5-500 mL of water;

[0036] The mass concentration of the metal salt solution is 0.5~10 g / L;

[0037] The total mass of the loaded metal accounts for 0.01% to 10% of the total mass of the catalyst;

[0038] The sacrificial agent is one of methanol, ethanol, and ethylene glycol;

[0039] The mass ratio of the sacrificial agent to water is 1:1~10, and the total volume of the sacrificial agent and water is 10~1000 mL;

[0040] The light source is a xenon lamp, a mercury lamp, or an LED lamp with a wavelength of 256-390 nm;

[0041] The photodeposition time is 0.5 to 2 hours.

[0042] Low-temperature visible light dehydrogenation catalytic reaction of organic liquid hydrides was carried out in a fixed-bed or batch reactor to screen for highly efficient catalysts. The supported cerium-zirconium solid solution photocatalyst prepared according to this invention was filled into a fixed-bed or batch reactor, and the catalyst was activated by vacuum heating to remove impurities adsorbed on the catalyst surface. After cooling to room temperature, organic liquid hydrides were injected to carry out a low-temperature visible light dehydrogenation catalytic reaction, and the product composition was analyzed by gas chromatography.

[0043] The amount of the supported cerium-zirconium solid solution photocatalyst is 10~1000 mg;

[0044] The vacuum pressure is less than 1 Pa, the activation temperature is 200~300 ℃, and the activation time is 0.5~2 h;

[0045] The visible light source has a wavelength range greater than 400 nm and an optical power density of 0.5~3 W / cm².

[0046] The low-temperature visible light dehydrogenation catalytic reaction is carried out under the control of a constant temperature reaction bath, with a low temperature of 0~60℃ and a low-temperature visible light dehydrogenation catalytic reaction time of 1~60 minutes;

[0047] The organic liquid hydride is C 4+A mixture of one or more of the following: alkanes (such as butane, pentane, hexane, etc.), aromatic hydrocarbons (such as cyclohexane, methylcyclohexane, dimethylcyclohexane, decahydronaphthalene, perhydrobenzyltoluene, perhydrodibenzyltoluene, etc.), and heterocyclic compounds (N-ethyldodecylcarbazole, indoline, decahydroquinoline, octahydrophenazine, etc.).

[0048] This invention designs a conversion device for capturing and storing solar energy in the dehydrogenation catalytic reaction of organic liquid hydrides. It aims to drive the dehydrogenation catalytic reaction of organic liquid hydrides by focusing sunlight and using a supported cerium-zirconium solid solution photocatalyst for efficient energy conversion.

[0049] The device consists of a Fresnel lens, a tracking platform, an optical power meter, a syringe pump, a heat exchanger, a reactor, a gas-liquid separator, and a liquid storage tank. The Fresnel lens, optical power meter, syringe pump, heat exchanger, reactor, gas-liquid separator, and liquid storage tank are all placed on the tracking platform and connected using 3 mm steel pipes and compression fittings.

[0050] Fresnel lenses: with a lens area of ​​0.2 to 10 square meters and a focal length of 0.1 to 2.0 meters, they are used to efficiently focus sunlight onto a designated area to maximize the utilization of light energy;

[0051] Sun tracking platform: Employs a dual-axis solar tracker to ensure that the Fresnel lens is always pointed at the sun in order to continuously capture sunlight;

[0052] Optical power meter: measures the optical power density at the focal point of the Fresnel lens to ensure it is within the range of 0.1~20 W / cm², in order to optimize the dehydrogenation catalytic reaction conditions;

[0053] Injection pump: controls the injection rate of organic liquid hydride into the reactor from 0.01 to 150 ml / min to meet the needs of different scale reactions;

[0054] Heat exchanger: Regulates the temperature inside the reactor to ensure that the low-temperature visible light dehydrogenation catalytic reaction of organic liquid hydrides proceeds at the optimal temperature, while recovering the heat generated by the reaction;

[0055] Reactor: Contains organic liquid hydrides and photocatalysts, and is the site where dehydrogenation catalytic reactions occur; It has a quartz glass window.

[0056] Gas-liquid separator: Separates hydrogen gas and dehydrogenation products generated in the dehydrogenation catalytic reaction, achieving efficient product collection;

[0057] Liquid storage unit: Safely stores dehydrogenation products generated by the dehydrogenation catalytic reaction.

[0058] Solar energy is captured and used to drive the dehydrogenation reaction of cyclohexane using a solar energy conversion device. The reactor is filled with a supported cerium-zirconium solid solution photocatalyst prepared according to this invention, and sunlight is focused using a Fresnel lens adjusted by a light-tracking platform. Organic liquid hydrides are continuously injected into the reactor using an injection pump to trigger the dehydrogenation catalytic reaction. The gases produced during the reaction are separated by a gas-liquid separator; hydrogen and other possible gaseous products are collected, while liquid products are stored in a liquid storage tank. Throughout the process, gas chromatography is used to collect and quantitatively analyze the catalytic products online.

[0059] The amount of the supported cerium-zirconium solid solution photocatalyst is 10~1000 mg;

[0060] The area of ​​the focused solar spot is between 0.01 m × 0.01 m and 0.1 m × 0.1 m, the spot temperature is maintained between 50 and 500 ℃, and the light power density is in the range of 0.1 to 20 W / cm².

[0061] The injection pump injects the material into the reactor at a rate of 0.01~150 ml / min;

[0062] The organic liquid hydride is C 4+ A mixture of one or more of the following: alkanes (such as butane, pentane, hexane, etc.), aromatic hydrocarbons (such as cyclohexane, methylcyclohexane, dimethylcyclohexane, decahydronaphthalene, perhydrobenzyltoluene, perhydrodibenzyltoluene, etc.), and heterocyclic compounds (N-ethyldodecylcarbazole, indoline, decahydroquinoline, octahydrophenazine, etc.).

[0063] The present invention has the following advantages:

[0064] (1) Efficient and economical photocatalyst preparation method: This invention successfully developed a uniformly dispersed and stable sub-nanometer metal cluster supported cerium-zirconium solid solution photocatalyst through a unique preparation process. This preparation process is not only highly energy efficient, but also simple to operate, low in cost, short in preparation cycle, and has good reproducibility. This innovation not only reduces the production cost of photocatalysts, but also improves their feasibility in practical applications;

[0065] (2) Energy storage potential of organic liquid hydrides: In the field of thermochemical energy storage technology (TCES), the selected organic liquid hydrides exhibit excellent reversibility, cost-effectiveness and high energy density; making them an ideal energy storage and transportation medium, especially suitable for long-term storage and efficient utilization of solar energy.

[0066] (3) High efficiency and stability of the photocatalyst: In the solar-driven cyclohexane dehydrogenation catalytic reaction, the supported cerium-zirconium solid solution photocatalyst exhibits excellent catalytic activity and stability. Specifically, the hydrogen production rate reaches as high as 2.89 mol·g⁻¹.Pt -1 ·min -1 With a turnover rate exceeding 100,000 and a hydrogen purity exceeding 99.99%, this performance indicator is among the leading in similar technologies.

[0067] (4) Full spectrum utilization of solar energy: The dehydrogenation catalytic reaction system described in this invention can effectively absorb ultraviolet, visible, and near-infrared light from sunlight. In addition, the conversion efficiency of solar energy to chemical energy is higher than 5%, opening up new avenues for the widespread application of solar energy. Attached Figure Description

[0068] Figure 1 The XRD patterns are of the products of Examples 1, 2, 3, 4, 5, 8 and Comparative Examples 1 and 2 of the present invention.

[0069] Figure 2 This is a TEM image of the product of Example 5 of the present invention;

[0070] Figure 3 The image shown is a HAADF-STEM image of the product of Example 8 of this invention.

[0071] Figure 4 This is a bar chart showing the catalytic evaluation results of photodeposition of different metals loaded on a 2-C5Z5 support in Example 10 of the present invention;

[0072] Figure 5 This is a bar graph showing the catalytic evaluation results of photodepositing different platinum contents on a 2-C5Z5 support in Example 11 of the present invention.

[0073] Figure 6 The catalytic stability curve is shown in Example 12 of this invention.

[0074] Figure 7 Raman experimental curves of the samples after the experiment in Example 12 of the present invention;

[0075] Figure 8 This is a schematic diagram of the solar energy conversion device described in this invention;

[0076] Figure 9 This is a schematic diagram of the reactor described in this invention. Detailed Implementation

[0077] The embodiments of the present invention are described in detail below. In this study, conventional reagents and methods were used, unless otherwise specified. These embodiments are all based on the technical solution of the present invention and provide specific implementation methods and operating procedures. It should be noted that the scope of protection of the present invention is not limited to the following embodiments.

[0078] In the following examples and comparative examples, we employed a catalyst evaluation method involving low-temperature visible-light dehydrogenation catalysis in a fixed-bed or batch reactor to screen for highly efficient catalysts. The specific procedure was as follows: 20 mg of supported cerium-zirconium solid solution photocatalyst was packed into a fixed-bed or batch reactor, then evacuated (pressure less than 1 Pa) and heated to 200 °C for 0.5 hours to remove impurities adsorbed on the catalyst surface. After the system cooled to room temperature, 500 μmol of cyclohexane was injected. Next, a 300 W xenon lamp (wavelength > 400 nm, light power density 1.2 W / cm²) was used for irradiation for 5 minutes, and the reactor temperature was maintained at 25 °C using a water-cooling system. Simultaneously, the catalytic products were collected online using gas chromatography and quantitatively analyzed to calculate the hydrogen production rate (defined as the amount of hydrogen produced per unit active site per unit time; calculation: hydrogen production rate (mmol)). H2 g met. -1 min -1 = Total hydrogen production (mmol) / Total molar amount of metal in catalyst (g) met。 () / total reaction time (min) and conversion rate (defined as the ratio of the mass of the substance participating in the reaction to the total mass of the substance, calculated as: conversion rate (%) = amount of converted raw material (mmol) / total amount of raw material (mmol) × 100%).

[0079] Example 1: Preparation of 1-C5Z5

[0080] 0.217 g (0.5 mmol) of Ce(NO3)3·6H2O and 0.115 g (0.5 mmol) of ZrO(NO3)2·2H2O were weighed and uniformly dispersed in 20 mL of water. The mixture was magnetically stirred at 600 r / min for 0.5 h. The pH of the solution was adjusted to 8.5 by adding 1 mol / L sodium hydroxide aqueous solution, and the mixture was stirred for 1 h. The precipitate was filtered using a vacuum filtration apparatus, washed with water until the pH of the filtrate was neutral, and dried in a 70 ℃ oven for 6 h to obtain the cerium-zirconium solid solution precursor. Subsequently, the precursor was reacted in a muffle furnace at 650 ℃ (heating rate 5 ℃ / min) for 4 h to obtain 0.140 g of 1-C5Z5 cerium-zirconium solid solution. X-ray diffraction (XRD) was performed on the 1-C5Z5 cerium-zirconium solid solution prepared in this example. The results are shown in the figure. Figure 1 .

[0081] Example 2: Preparation of 2-C3Z7

[0082] 0.130 g (0.3 mmol), 0.162 g (0.7 mmol), and 0.075 g (1 mmol) of Ce(NO3)3·6H2O, ZrO(NO3)2·2H2O, and glycine were weighed out respectively and uniformly dispersed in 20 mL of water. The mixture was magnetically stirred at 600 r / min for 0.5 hours. The solvent was evaporated at 90 °C, and the temperature was raised to 190 °C to initiate a spontaneous combustion reaction, which lasted for 1 minute to obtain a fluffy powder. The fluffy powder was placed in a muffle furnace at 650 °C (heating rate 5 °C / min) for 4 hours to obtain 0.137 g of 2-C3Z7 cerium-zirconium solid solution. X-ray diffraction (XRD) was performed on the 2-C3Z7 cerium-zirconium solid solution prepared in this example. The results are shown in the figure. Figure 1 .

[0083] Example 3: Preparation of 2-C5Z5

[0084] 0.217 g (0.5 mmol), 0.115 g (0.5 mmol), and 0.075 g (1 mmol) of Ce(NO3)3·6H2O, ZrO(NO3)2·2H2O, and glycine were weighed out respectively and uniformly dispersed in 20 mL of water. The mixture was magnetically stirred at 600 r / min for 0.5 hours. The solvent was evaporated at 90 °C, and the temperature was raised to 190 °C to initiate a spontaneous combustion reaction, which lasted for 1 minute to obtain a fluffy powder. The fluffy powder was placed in a muffle furnace at 650 °C (heating rate 5 °C / min) for 4 hours to obtain 0.147 g of 2-C5Z5 cerium-zirconium solid solution. The X-ray diffraction (XRD) test results of the 2-C5Z5 cerium-zirconium solid solution prepared in this example are shown in the figure. Figure 1 .

[0085] Example 4: Preparation of 2-C7Z3

[0086] 0.304 g (0.7 mmol), 0.069 g (0.3 mmol), and 0.075 g (1 mmol) of Ce(NO3)3·6H2O, ZrO(NO3)2·2H2O, and glycine were weighed out respectively and uniformly dispersed in 20 mL of water. The mixture was magnetically stirred at 600 r / min for 0.5 hours. The solvent was evaporated at 90 °C, and the temperature was raised to 190 °C to initiate a spontaneous combustion reaction, which lasted for 1 minute to obtain a fluffy powder. The fluffy powder was placed in a muffle furnace at 650 °C (heating rate 5 °C / min) for 4 hours to obtain 0.157 g of 2-C7Z3 cerium-zirconium solid solution. X-ray diffraction (XRD) was performed on the 2-C7Z3 cerium-zirconium solid solution prepared in this example. The results are shown in the figure. Figure 1 .

[0087] Example 5: PtNP Preparation of / 2-C5Z5

[0088] (1) Preparation of 2-C5Z5: Same as in Example 3;

[0089] (2) Pt NP Preparation of 2-C5Z5: 300 mg of 2-C5Z5 was dispersed in 20 mL of water, and 1000 μL of a 3 g / L aqueous solution of H2PtCl6·6H2O metal salt was added while stirring continuously. The pH was adjusted to 10 by adding a mixed solution of 0.2 mol / L sodium borohydride and 0.05 mol / L sodium hydroxide. The reaction was carried out at 600 r / min with magnetic stirring for 30 minutes, chemically depositing metallic Pt onto the cerium-zirconium solid solution. The precipitate was filtered using a vacuum filtration apparatus, washed three times with water until the pH of the filtrate was neutral, and dried under vacuum overnight to obtain 0.300 g of Pt. NP / 2-C5Z5 photocatalyst (1% Pt mass loading). Catalytic evaluation results are shown in Table 1. X-ray diffraction (XRD) and transmission electron microscopy (TEM) results of the supported cerium-zirconium solid solution prepared in this example are shown in Table 1. Figure 1 and Figure 2 .

[0090] Example 6: Preparation of Pt / 1-C5Z5

[0091] (1) Preparation of 1-C5Z5: Same as in Example 1;

[0092] (2) Preparation of Pt / 1-C5Z5: 300 mg of 1-C5Z5 was dispersed in 50 mL of water, and 1000 μL of 3 g / L H2PtCl6·6H2O metal salt aqueous solution was added while stirring continuously. 10 mL of methanol sacrificial agent was added, and the mixture was stirred and sonicated for 30 min to obtain a cerium-zirconium solid solution suspension. The suspension was placed in a sealed quartz jar, and a diaphragm pump was used to create a vacuum. Subsequently, a photodeposition reaction was carried out for 0.5 hours using a 300 W xenon lamp under magnetic stirring at 600 r / min. The precipitate was filtered using a vacuum filtration device, washed three times with water until the pH of the filtrate was neutral, and dried under vacuum overnight to obtain 0.295 g of Pt / 1-C5Z5 photocatalyst (with a metal Pt mass loading of 1%). The catalytic evaluation results are shown in Table 1.

[0093] Example 7: Preparation of Pt / 2-C3Z7

[0094] (1) Preparation of 2-C3Z7: Same as in Example 2;

[0095] (2) Preparation of Pt / 2-C3Z7: 300 mg of 2-C3Z7 was dispersed in 50 mL of water, and 1000 μL of 3 g / L H2PtCl6·6H2O metal salt solution was added while stirring continuously. 10 mL of methanol sacrificial agent was added, and the mixture was stirred and sonicated for 30 min to obtain a cerium-zirconium solid solution suspension. The suspension was placed in a sealed quartz jar, and a diaphragm pump was used to create a vacuum. Subsequently, a photodeposition reaction was carried out for 0.5 hours using a 300 W xenon lamp under magnetic stirring at 600 r / min. The precipitate was filtered using a vacuum filtration device, washed three times with water until the pH of the filtrate was neutral, and dried under vacuum overnight to obtain 0.300 g of Pt / 2-C3Z7 photocatalyst (with a Pt mass loading of 1%). The catalytic evaluation results are shown in Table 1.

[0096] Example 8: Preparation of Pt / 2-C5Z5

[0097] (1) Preparation of 2-C5Z5: Same as in Example 3;

[0098] (2) Preparation of Pt / 2-C5Z5: 300 mg of 2-C5Z5 was dispersed in 50 mL of water, and 1000 μL of 3 g / L H2PtCl6·6H2O metal salt solution was added while stirring continuously. 10 mL of methanol sacrificial agent was added, and the mixture was stirred and sonicated for 30 min to obtain a cerium-zirconium solid solution suspension. The suspension was placed in a sealed quartz jar, and a diaphragm pump was used to create a vacuum. Subsequently, a photodeposition reaction was carried out for 0.5 hours using a 300 W xenon lamp under magnetic stirring at 600 r / min. The precipitate was filtered using a vacuum filtration device, washed three times with water until the pH of the filtrate was neutral, and dried under vacuum overnight to obtain 0.296 g of Pt / 2-C5Z5 photocatalyst (with a Pt mass loading of 1%). The illumination time was set to 5 minutes and 1 minute, respectively, for low-temperature visible light dehydrogenation catalysis. The catalytic evaluation results are shown in Table 1. X-ray diffraction (XRD) was performed on the Pt / 2-C5Z5 sample prepared in this embodiment. The results are shown in [Figure number missing]. Figure 1 The Pt / 2-C5Z5 prepared in this embodiment was tested using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), and the results are shown in [Figure number missing]. Figure 3 .

[0099] Example 9: Preparation of Pt / 2-C7Z3

[0100] (1) Preparation of 2-C7Z3: Same as in Example 4;

[0101] (2) Preparation of Pt / 2-C7Z3: 300 mg of 2-C7Z3 was dispersed in 50 mL of water, and 1000 μL of 3 g / L H2PtCl6·6H2O metal salt solution was added while stirring continuously. 10 mL of methanol sacrificial agent was added, and the mixture was stirred and sonicated for 30 min to obtain a cerium-zirconium solid solution suspension. The suspension was placed in a sealed quartz jar, and a diaphragm pump was used to create a vacuum. Subsequently, a photodeposition reaction was carried out for 0.5 hours using a 300 W xenon lamp under magnetic stirring at 600 r / min. The precipitate was filtered using a vacuum filtration device, washed three times with water until the pH of the filtrate was neutral, and dried under vacuum overnight to obtain 0.298 g of Pt / 2-C7Z3 photocatalyst (with a Pt mass loading of 1%). The catalytic evaluation results are shown in Table 1.

[0102] Example 10: Preparation of M / 2-C5Z5

[0103] (1) Preparation of 2-C5Z5: Same as in Example 3;

[0104] (2) Preparation of M / 2-C5Z5: 300 mg of 2-C5Z5 was dispersed in 50 mL of water, and 1000 μL of ruthenium salt, rhodium salt, palladium salt, niobium salt, molybdenum salt, gold salt, silver salt, iron salt, cobalt salt, nickel salt, copper salt, or cadmium salt solution was added continuously. 10 mL of methanol sacrificial agent was added, and the mixture was stirred and sonicated for 30 min to obtain a cerium-zirconium solid solution suspension. The suspension was placed in a sealed quartz jar, and a diaphragm pump was used to create a vacuum. Subsequently, a photodeposition reaction was carried out for 0.5 hours using a 300 W xenon lamp under magnetic stirring at 600 r / min. The precipitate was filtered using a vacuum filtration apparatus, washed three times with water until the pH of the filtrate was neutral, and then vacuum dried overnight to obtain M / 2-C5Z5 photocatalysts (with a Pt mass loading of 1%, M = Pt, Ru, Rh, Pd, Nb, Mo, Au, Ag, Fe, Co, Ni, Cu, Cd) in quantities of 0.300, 0.297, 0.298, 0.293, 0.294, 0.296, 0.300, 0.296, 0.291, 0.296, 0.299, 0.300, and 0.295 g, respectively. The catalytic evaluation results are shown in […]. Figure 4 .

[0105] Example 11: Preparation of n% Pt / 2-C5Z5

[0106] (1) Preparation of 2-C5Z5: Same as in Example 3;

[0107] (2) Preparation of Pt / 2-C5Z5: 300 mg of 2-C5Z5 was dispersed in 50 mL of water, and 100 μL, 200 μL, 500 μL, 1000 μL, 2000 μL, 3000 μL and 4000 μL of 3 g / L H2PtCl6·6H2O metal salt solution were added continuously. 10 mL of methanol sacrificial agent was added, and the mixture was stirred and sonicated for 30 min to obtain a cerium-zirconium solid solution suspension. The suspension was placed in a sealed quartz jar, and a diaphragm pump was used to create a vacuum. Subsequently, a photodeposition reaction was carried out for 0.5 hours using a 300 W xenon lamp under magnetic stirring at 600 r / min. The precipitate was filtered using a vacuum filtration apparatus, washed three times with water until the pH of the filtrate was neutral, and vacuum dried overnight to obtain n% Pt / 2-C7Z3 photocatalysts (n = 0.1, 0.2, 0.5, 1, 2, 3, and 4, i.e., Pt mass loadings of 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, and 4%, respectively). Catalytic evaluation results are shown in […]. Figure 5 .

[0108] Example 12: Catalyst stability experiment

[0109] 20 mg of the photocatalysts from Examples 5 and 8 were respectively packed into fixed-bed or batch reactors, then evacuated and heated to 200 °C for 0.5 hours to remove impurities adsorbed on the catalyst surface. After the system cooled, 500 μmol of cyclohexane was injected. Next, the system was irradiated for 5 minutes using a 300 W xenon lamp (wavelength > 400 nm, light power density 1.2 W / cm²), and the system temperature was maintained at 25 °C using a water cooling system. Simultaneously, the catalytic products were collected online using gas chromatography and quantitatively analyzed. This process was repeated multiple times, and the cyclic performance results of the catalysts are shown in [Figure showing cyclic performance results]. Figure 6 Raman spectroscopy was performed on the cyclically cycled samples, and the results are shown in [Figure number missing]. Figure 7 .

[0110] Example 13: Photocatalytic Experiment of Cyclohexane Dehydrogenation under Heating Conditions

[0111] 20 mg of the photocatalyst from Example 5 was packed into a fixed-bed or batch reactor, then evacuated and heated to 200 °C for 0.5 hours to remove impurities adsorbed on the catalyst surface. After the system cooled, 500 μmol of cyclohexane was injected. Next, the system was irradiated for 1 minute using a 300 W xenon lamp (wavelength > 400 nm, light power density 1.2 W / cm²), and the system temperature was maintained at 80 °C using a water-cooling system. Simultaneously, the catalytic products were collected online using gas chromatography and quantitatively analyzed. The catalytic evaluation results are shown in Table 1.

[0112] Example 14: Solar energy capture and driving cyclohexane dehydrogenation experiment

[0113] A solar energy conversion device for photocatalytic dehydrogenation of organic liquid hydrides, such as Figure 8 As shown, it consists of a Fresnel lens 1, a light-tracking platform 2, an optical power meter 3, a syringe pump 4, a heat exchanger 5, a reactor 6, a gas-liquid separator 7, and a liquid storage tank 8.

[0114] A 0.5m x 0.5m Fresnel lens 1 with a focal length of 0.6m is fixed in a groove on the top of a 0.6m x 0.6m x 0.6m stainless steel-aluminum alloy box. The bottom of the box is connected to a light-tracking platform 2, which consists of a dual-axis frame, a photosensitive module, a drive module, and a servo motor, enabling it to track sunlight horizontally from 0 to 180° and vertically from 0 to 180°. A light power meter 3 (Newport, PMKIT-05-01) is installed on the side of the box, positioned so as to be in the same plane as the Fresnel lens, to measure and calculate the intensity of the focused sunlight. To achieve device integration, an injection pump 4 and a heat exchanger 5 are welded to the outside of the box. The injection pump 4 (Yanhang Power, QHLR005) has an injection rate of 0.01 to 150 ml / min and can support the use of 50 to 500 mL syringes. The syringe, with its bayonet-type stainless steel needle (11G, outer diameter 3.06 mm, tube length 211 mm), is connected to heat exchanger 5 (welded plate heat exchanger) via a compression fitting. The outlet of heat exchanger 5 is connected to reactor 6 via a 3 mm steel pipe and a compression fitting. The specific structure of reactor 6 is as follows... Figure 9 As shown, a 70 mm diameter frustum, custom-made from 304 stainless steel, has a light-receiving diameter of 50 mm. The catalyst is placed in a 50 mm diameter, 3 mm high void. The output pipe of reactor 6 is still a 3 mm steel pipe connected to the heat inlet of heat exchanger 5. The heat outlet of heat exchanger 5 is connected to gas-liquid separator 7 (GLS-FLOW), and then connected in series to liquid storage tank 8 (stainless steel liquid storage tank) to ensure effective and rapid gas-liquid separation and product storage.

[0115] 20 mg of the photocatalyst from Example 5 was filled into the bottom of the reactor in the solar energy conversion device of the present invention. The Fresnel lens was adjusted using a biaxial solar tracker on the tracking platform to precisely focus sunlight onto a 0.05 m × 0.05 m spot, maintaining the spot temperature between 70 and 120 °C. A power meter was used to measure and calculate the power density at the focal point, ensuring an ideal intensity of approximately 6 W / cm². Under these conditions, cyclohexane was continuously injected into the reactor (0.1 mL / min) using a syringe pump to trigger the dehydrogenation catalytic reaction. The gases produced during the reaction were separated by a gas-liquid separator; hydrogen and other possible gaseous products were collected, while liquid products were stored in a liquid reservoir. Throughout the process, gas chromatography was used to collect and quantitatively analyze the catalytic products online. The catalytic evaluation results are shown in Table 1.

[0116] According to the catalytic evaluation results, this experiment can efficiently convert solar energy into chemical energy, with a conversion efficiency exceeding 5% and an apparent quantum efficiency of 56% at a wavelength of 390 nm. This result not only verifies the effective synergistic effect of various components in the solar energy conversion device, but also demonstrates the high efficiency and stability of the supported cerium-zirconium solid solution photocatalyst in the solar-driven cyclohexane dehydrogenation catalytic reaction, further confirming the great potential of this technology in solar energy utilization.

[0117] Preparation of Comparative Example 1:2-C

[0118] 0.434 g Ce(NO3)3·6H2O (1 mmol) and 0.075 g (1 mmol) glycine were weighed and uniformly dispersed in 20 mL of water. The mixture was magnetically stirred at 600 r / min for 0.5 hours. The solvent was evaporated at 90 °C, and the temperature was raised to 190 °C to initiate a spontaneous combustion reaction, which lasted for 1 minute to obtain a fluffy powder. The fluffy powder was placed in a muffle furnace at 650 °C (heating rate 5 °C / min) for 4 hours to obtain 0.170 g of 2-C sample. X-ray diffraction (XRD) was performed on the 2-C cerium-zirconium solid solution prepared in this comparative example. The results are shown in the figure. Figure 1 .

[0119] Comparative Example 2: Preparation of 2-Z

[0120] 0.231 g ZrO(NO3)2·2H2O (1 mmol) and 0.075 g (1 mmol) glycine were weighed and uniformly dispersed in 20 mL of water. The mixture was magnetically stirred at 600 r / min for 0.5 hours. The solvent was evaporated at 90 °C, and the temperature was raised to 190 °C to initiate a spontaneous combustion reaction, which lasted for 1 minute to obtain a fluffy powder. The fluffy powder was placed in a muffle furnace at 650 °C (heating rate 5 °C / min) for 4 hours to obtain 0.118 g of 2-Z sample. X-ray diffraction (XRD) was performed on the 2-Z cerium-zirconium solid solution prepared in this comparative example. The results are shown in the figure. Figure 1 .

[0121] Comparative Example 3: Pt NP Preparation of / 2-C

[0122] (1) Preparation of 2-C: Same as Comparative Example 1;

[0123] (2) Pt NP Preparation of 2-C: 300 mg of 2-C was dispersed in 20 mL of water, and 1000 μL of a 3 g / L H₂PtCl₆·6H₂O metal salt solution was added while stirring continuously. The pH was adjusted to 10 by adding sodium borohydride solution, and the reaction was carried out for 30 minutes under magnetic stirring at 600 r / min. The precipitate was filtered using a vacuum filtration apparatus, washed three times with water until the pH of the filtrate was neutral, and dried under vacuum overnight to obtain 0.300 g of Pt. NP / 2-C photocatalyst (1% Pt mass loading). Catalytic evaluation results are shown in Table 1.

[0124] Comparative Example 4: Pt NP Preparation of / 2-Z

[0125] (1) Preparation of 2-Z: Same as Comparative Example 2;

[0126] (2) Pt NP Preparation of 2-Z: 300 mg of 2-Z was dispersed in 20 mL of water, and 1000 μL of a 3 g / L H₂PtCl₆·6H₂O metal salt solution was added while stirring continuously. The pH was adjusted to 10 by adding sodium borohydride solution, and the reaction was carried out for 30 minutes with magnetic stirring at 600 r / min. The precipitate was filtered using a vacuum filtration apparatus, washed three times with water until the pH of the filtrate was neutral, and dried under vacuum overnight to obtain 0.298 g of Pt. NP / 2-Z photocatalyst (1% Pt mass loading). Catalytic evaluation results are shown in Table 1.

[0127] Comparative Example 5: Preparation of Pt / 2-C

[0128] (1) Preparation of 2-C: Same as Comparative Example 1;

[0129] (2) Preparation of Pt / 2-C: 300 mg of 2-C was dispersed in 50 mL of water, and 1000 μL of 3 g / L H2PtCl6·6H2O metal salt solution was added while stirring continuously. 10 mL of methanol sacrificial agent was added, and the mixture was stirred and sonicated for 30 min to obtain a cerium-zirconium solid solution suspension. The suspension was placed in a sealed quartz jar, and a diaphragm pump was used to create a vacuum. Subsequently, a photodeposition reaction was carried out for 0.5 hours using a 300 W xenon lamp under magnetic stirring at 600 r / min. The precipitate was filtered using a vacuum filtration device, washed three times with water until the pH of the filtrate was neutral, and dried under vacuum overnight to obtain 0.299 g of Pt / 2-C photocatalyst (with a Pt mass loading of 1%). The catalytic evaluation results are shown in Table 1.

[0130] Comparative Example 6: Preparation of Pt / 2-Z

[0131] (1) Preparation of 2-Z: Same as Comparative Example 2;

[0132] (2) Preparation of Pt / 2-Z: 300 mg of 2-Z was dispersed in 50 mL of water, and 1000 μL of 3 g / L H2PtCl6·6H2O metal salt solution was added while stirring continuously. 10 mL of methanol sacrificial agent was added, and the mixture was stirred and sonicated for 30 min to obtain a cerium-zirconium solid solution suspension. The suspension was placed in a sealed quartz jar, and a diaphragm pump was used to create a vacuum. Subsequently, a photodeposition reaction was carried out for 0.5 hours using a 300 W xenon lamp under magnetic stirring at 600 r / min. The precipitate was filtered using a vacuum filtration device, washed three times with water until the pH of the filtrate was neutral, and dried under vacuum overnight to obtain 0.300 g of Pt / 2-Z photocatalyst (with a Pt mass loading of 1%). The catalytic evaluation results are shown in Table 1.

[0133] Table 1: Catalytic evaluation results of each example and comparative example

[0134] Example Reaction conditions <![CDATA[Hydrogen production rate (mmol H2 g Pt -1 min -1 )]]> Conversion rate (%) Example 5 The light source wavelength was greater than 400 nm; the optical power density was 1.2 W / cm²; the illumination time was 5 min; 500 μmol of cyclohexane was injected; and the ambient temperature was 25℃. 310.6 20.7 Example 6 Same as above 98.4 6.6 Example 7 Same as above 504.7 33.6 Example 8 Same as above 1191.1 79.4 Example 9 Same as above 737.4 49.2 Comparative Example 3 Same as above 98.1 6.5 Comparative Example 4 Same as above 33.2 2.2 Comparative Example 5 Same as above 202.1 13.5 Comparative Example 6 Same as above 126.9 8.5 Example 8 Light source wavelength greater than 400 nm; optical power density of 1.2 W / cm²; illumination for 1 min; injection of 500 μmol cyclohexane; ambient temperature of 25℃. 2896.9 38.6 Example 13 Light source wavelength greater than 400 nm; optical power density of 1.2 W / cm²; illumination for 1 min; injection of 500 μmol cyclohexane; ambient temperature of 80℃. 4335.0 57.8 Example 14 Concentrated sunlight; cyclohexane injection at 0.1 ml / min; spot temperature between 70 and 120°C. 1946.1 25.9

[0135] As shown in Table 1, a) Examples 7, 8, and 9 are Pt / 2-C3Z7, Pt / 2-C5Z5, and Pt / 2-C7Z3 catalysts, respectively, while Comparative Examples 5 and 6 are Pt / 2-C and Pt / 2-Z catalysts, respectively. Among Ce-Zr solid solutions with different Ce / Zr molar ratios, the Pt / 2-C5Z5 catalyst (cerium-zirconium ratio of 1) in Example 8 exhibits the strongest dehydrogenation activity; b) Examples 8 and 5 are Pt / 2-C5Z5 and Pt / 2-Z catalysts, respectively. NP / 2-C5Z5 catalyst. Pt can be obtained using chemical deposition for different loading methods. NP / 2-C5Z5 catalyst (Pt nanoparticles with an average particle size of 3.63 nm). The Pt / 2-C5Z5 catalyst with sub-nanometer Pt clusters (average particle size of 0.88 nm) obtained by photodeposition is more favorable for the photocatalytic dehydrogenation of cyclohexane; c) Examples 8 and 6 are Pt / 2-C5Z5 and Pt / 1-C5Z5 catalysts, respectively. For the CeO2-ZrO2 two-phase ordered cerium-zirconium solid solution 2-C5Z5, the catalyst supported on the mixed phase 1-C5Z5 has a worse dehydrogenation effect; d) Examples 8 and 13 show the dehydrogenation catalytic reaction of Pt / 2-C5Z5 at ambient temperatures of 25 °C and 80 °C, respectively, indicating that increasing the ambient temperature helps to accelerate the reaction rate; e) Under a single sun, a solar concentrator can be used to carry out the dehydrogenation catalytic reaction and can efficiently convert solar energy into chemical energy, with a conversion efficiency exceeding 5%.

[0136] like Figure 1 As shown, 1-C5Z5 can be observed to be a mixture of cubic CeO2 and quadrilateral ZrO2, while 2-C5Z5 is a cerium-zirconium solid solution with an ordered arrangement of Ce and Zr ions. This is due to the inclusion of Zr... 4+ The ionic radius (0.084) is smaller than that of Ce. 4+ The ionic radius (0.098) and the diffraction peak of 2-C5Z5 show a higher angle shift and a larger half-peak width compared to 2-C. No obvious Pt species peaks were observed in the Pt-loaded sample, and the diffraction peak positions did not shift significantly. This indicates that the loaded noble metal particles have a small particle size, high dispersion, and are loaded onto the support surface rather than entering the interlayer.

[0137] like Figure 2 As shown, Pt prepared by chemical reduction can be observed. NP The average particle size of Pt on / 2-C5Z5 is 3.63 nm, exposing the Pt(111) crystal plane;

[0138] like Figure 3 As shown, sub-nanometer Pt clusters with an average particle size of 0.88 nm can be observed, uniformly dispersed on 2-C5Z5.

[0139] like Figure 4 As shown in the bar chart of catalytic evaluation results for photodeposited loading of different metals on the 2-C5Z5 support, the hydrogen yield is Pt > Pd > Rh > Ru > Au >> Nb, Mo, Ag, Fe, Co, Ni, Cu, Cd. This indicates that catalysts with Pt clusters loaded on cerium-zirconium solid solutions are beneficial for the photocatalytic dehydrogenation of cyclohexane.

[0140] like Figure 5As shown in the bar chart of catalytic evaluation results for photodeposited Pt with different contents on the 2-C5Z5 support, the catalyst exhibits the highest turnover frequency (TOF) when the Pt loading is 1.0 wt%. (TOF is defined as the number of reactions per unit active site per unit time, calculated as: total hydrogen production (mol) / total molar amount of Pt in the catalyst (mol)). Pt () / total reaction time). As the Pt loading further increases, aggregation gradually occurs, leading to a decrease in Pt atom utilization. On the other hand, as the Pt loading decreases, the TOF also gradually decreases until complete loss of activity (0.1 wt%) is observed after the formation of single-atom Pt.

[0141] like Figure 6 As shown, Pt / 2-C5Z5 with smaller platinum nanoclusters exhibits good cycling stability.

[0142] like Figure 7 As shown, according to the Raman diagram, 1325 and 1580 cm -1 The D and G bands of nearby carbon (amorphous carbon and graphitic carbon) can indicate the carbon deposition on the catalyst surface after the reaction. The figure suggests that due to Pt... NP / 2-C5Z5 contains large Pt nanoparticles, which strongly adsorb benzene molecules, leading to further dehydrogenation of benzene and the formation of coke deposits that cover the active Pt sites, resulting in catalyst poisoning. In contrast, Pt / 2-C5Z5, with its smaller platinum nanoclusters, exhibits good resistance to coke deposition.

[0143] like Figure 8 As shown, the names of each part are: Fresnel lens 1, tracking platform 2, optical power meter 3, syringe pump 4, heat exchanger 5, reactor 6, gas-liquid separator 7, and liquid storage tank 8.

[0144] like Figure 9 As shown, reactor 6 is a truncated cone with a diameter of 70 mm, custom-made from 304 stainless steel. The upper cover contains a quartz disc with a diameter of 50 mm and a thickness of 5 mm, allowing light to pass through within a diameter of 50 mm. The catalyst is placed in a 50 mm diameter and 3 mm high cavity.

Claims

1. A method for preparing a supported cerium-zirconium solid solution photocatalyst, comprising the following steps: (1) Preparation of cerium-zirconium solid solution by reducing agent combustion method: Weigh cerium salt, zirconium salt and reducing agent, disperse in water and stir continuously; after evaporating the solvent, heat to initiate a spontaneous combustion reaction to obtain cerium-zirconium solid solution precursor; finally, treat the cerium-zirconium solid solution precursor at high temperature to obtain cerium-zirconium solid solution, denoted as 2-C x Z y The temperature at which the spontaneous combustion reaction is initiated is 150~250 ℃, and the temperature for high-temperature treatment is 500~1200 ℃. The molar ratio of the cerium salt to the zirconium salt is x : y, and x / (x+ y) = 0.1~0.9, the total molar mass is 0.01~100 mmol, and it is dispersed in 5~500 mL of water; The reducing agent is one of glycine, tartaric acid, and citric acid; The ratio of the total molar amount of cerium and zirconium salts to the molar amount of reducing agent is 1:0.1~10; (2) Preparation of supported cerium-zirconium solid solution photocatalyst by photodeposition: Cerium-zirconium solid solution is dispersed in water, and metal salt aqueous solution is added while stirring continuously. Then, a sacrificial agent is added and ultrasonically stirred for 20-40 min to obtain a cerium-zirconium solid solution suspension. Photodeposition is then carried out under vacuum, irradiation with a light source of 200-400 W, and magnetic stirring at 100-1000 r / min. Finally, the precipitate is filtered using a vacuum filtration device, washed with water until the pH of the filtrate is neutral, and vacuum dried overnight to obtain the supported cerium-zirconium solid solution photocatalyst. The cerium-zirconium solid solution has a mass of 100-500 mg and is dispersed in 5-500 mL of water; The metal salt is one or a combination of several of the following: soluble platinum salt, ruthenium salt, rhodium salt, or palladium salt; The mass concentration of the metal salt aqueous solution is 0.5~10 g / L; The total mass of the loaded metal accounts for 0.01% to 10% of the total mass of the catalyst; The sacrificial agent is one of methanol, ethanol, and ethylene glycol; The mass ratio of the sacrificial agent to water is 1:1~10, and the total volume of the sacrificial agent and water is 10~1000 mL; The light source is a xenon lamp, a mercury lamp, or an LED lamp with a wavelength of 256-390 nm; The photodeposition time is 0.5 to 2 hours.

2. The method for preparing a supported cerium-zirconium solid solution photocatalyst as described in claim 1, characterized in that: The cerium salt is one of Ce(NO3)3·6H2O, CeCl3·7H2O, and Ce2(CO3)3·5H2O; the zirconium salt is one of ZrO(NO3)2·2H2O, ZrOCl2·8H2O, and Zr(NO3)4·5H2O; the stirring is performed by magnetic stirring at 100~1000 r / min for 0.5~12 hours; the solvent is evaporated at a temperature of 60~120 ℃, the auto-ignition reaction time is 0.5~5 min, and the high-temperature treatment time is 1~10 hours.

3. A supported cerium-zirconium solid solution photocatalyst, characterized in that: It is prepared by the method described in claim 1 or 2.

4. The application of the supported cerium-zirconium solid solution photocatalyst according to claim 3 in the solar energy storage of organic liquid hydride dehydrogenation catalytic reaction, characterized in that: Organic liquid hydrides are C 4+ A mixture of one or more of alkanes, aromatic hydrocarbons, and heterocyclic compounds.

5. The application of the supported cerium-zirconium solid solution photocatalyst as described in claim 4 in the solar energy storage of organic liquid hydride dehydrogenation catalytic reaction, characterized in that: C 4+ The alkanes are one or a mixture of butane, pentane, and hexane; the aromatic hydrocarbons are one or a mixture of cyclohexane, methylcyclohexane, dimethylcyclohexane, decahydronaphthalene, perhydrobenzyltoluene, and perhydrodibenzyltoluene; the heterocyclic compounds are one or a mixture of N-ethyldodecylcarbazole, indoline, decahydroquinoline, and octahydrophenazine.

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