Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst and its preparation method and application

Abstract

The present invention discloses a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst, a preparation method and an application thereof. The technical solution is to prepare a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst with a wide spectral response by in-situ high-temperature sulfurization of Bi-doped amino In-MOF. The catalyst can combine photocatalysis and thermal catalysis to achieve a photothermal synergistic effect. The synergistic effect enables it to exhibit excellent photocatalytic activity under visible light irradiation. At the same time, under heating conditions, it can accelerate the desorption of products on the catalyst surface and promote the effective utilization of photogenerated electrons and holes. The hydrogen production under the conditions of photothermal synergistic catalysis is significantly improved, and a certain hydrogen production can also be achieved at low temperatures.

Description

Technical Field

[0001] The present invention belongs to the technical field of photothermal catalytic materials and relates to the preparation of a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst and research on its application in photothermal catalytic methanol liquid phase reforming to produce hydrogen. Background Art

[0002] The development and performance improvement of catalysts are fundamental to increasing hydrogen production efficiency, suppressing byproduct formation, and reducing reaction energy consumption in methanol reforming. This article reviews the latest research progress and mechanistic understanding of methanol-to-hydrogen catalysts, the cornerstone of the methanol-H2 energy system. It also discusses the difficulties and challenges facing the development of methanol-to-hydrogen catalysts and offers prospects for the future of catalyst development.

[0003] Against the backdrop of increasingly serious global climate change caused by excessive carbon emissions, the development of clean alternative energy sources is urgent. At present, the clean energy sources that have attracted widespread attention include solar energy and secondary energy derived from solar energy, such as wind energy, hydropower, ocean energy, biomass energy, etc. Compared with traditional fossil energy, the energy density of clean energy is relatively low, and its distribution is greatly restricted by the geographical environment. It is inevitable that it needs to be further converted into other forms of secondary energy for easy transportation and utilization. Among the many secondary energy sources, hydrogen is a clean secondary energy carrier. Compared with traditional fossil energy, hydrogen energy is simple, easy to obtain, and environmentally friendly. Hydrogen energy converted from renewable energy is essentially a "negative carbon emission" energy. Hydrogen has a high energy density (142 MJ kg -1 ), good utilization efficiency, and eco-friendly properties have long been considered an ideal renewable energy carrier, making sustainable hydrogen production one of the most attractive and competitive technologies. Methanol, due to its high proton density and ease of liquid phase transport, is one of the best hydrogen carriers.

[0004] Traditional thermal catalytic processes require high temperatures and pressures to drive reactions, resulting in high energy consumption and numerous byproducts. The introduction of light energy can reduce the requirement for high energy input and activation of stable chemical bonds (CH and OH), thereby lowering the activation barrier and enabling more efficient catalytic reactions under mild conditions. Compared to the bandgap-limited spectral efficiency of pure photocatalytic systems, photothermal catalysis can fully utilize the solar spectrum and increase reaction rates. Photothermal-driven reforming of methanol solutions to hydrogen effectively lowers the activation energy barrier, overcoming the challenges associated with sluggish kinetics. Simultaneously, it utilizes photon energy to improve reaction kinetics while reducing the activation energy prerequisite for the process. This groundbreaking approach facilitates efficient hydrogen production at lower temperatures and with high selectivity. However, most current photocatalysts still suffer from low efficiency, poor light absorption, and inefficient electron and hole separation. Metal-organic frameworks (MOFs), with their tunable porosity, high surface area, and synthetic versatility, have recently emerged as porous crystalline materials, playing an important role in photothermal catalysis.

[0005] Prior art discloses semiconductor photocatalysts (such as TiO2, Fe2O3, and CdS) for use in hydrogen production. However, these inorganic catalysts suffer from low solar energy conversion efficiency, susceptibility to photocorrosion, easy aggregation, difficulty in subsequent separation, and limited catalytic activity. Furthermore, they consume large amounts of energy during the hydrogen production reaction, leading to high production costs. Therefore, there is an urgent need to develop stable, efficient, and energy-efficient photothermal catalysts for hydrogen production from methanol liquid-phase reforming. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the problems of high energy consumption, high temperature and poor catalyst stability in the liquid-phase reforming reaction of methanol to produce hydrogen. The purpose of the present invention is to provide a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst generated in situ in a Bi-doped amino In-MOF. The catalyst enables photocatalysis and thermal catalysis to produce a synergistic effect, introduces a light source, increases the energy of the reaction system, and further reduces the reaction temperature.

[0007] Another object of the present invention is to provide a method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in situ generated in Bi-doped amino In-MOF.

[0008] Another object of the present invention is to provide an application of a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst generated in situ in Bi-doped amino In-MOF in the photothermal synergistic catalytic liquid-phase reforming of methanol to produce hydrogen.

[0009] The first object of the present invention is achieved through the following technical solutions:

[0010] A method for in-situ generation of a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in a Bi-doped amino In-MOF comprises the following steps:

[0011] S1. Add indium source and organic ligand into organic solvent and disperse and dissolve to obtain precursor solution of amino In-MOF material

[0012] S2. Add the bismuth source to the S1 precursor solution, stir and mix thoroughly, and then react to obtain the bismuth-doped amino In-MOF material.

[0013] S3. Dissolve the Bi-doped amino In-MOF and the sulfur source obtained in S2 in an organic solvent, stir them thoroughly and react them to obtain a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst.

[0014] Preferably, in step S1, the indium source is one or more of indium nitrate, indium sulfate, and indium acetate.

[0015] Furthermore, in step S1, the organic ligand is 2-amino-terephthalic acid.

[0016] Furthermore, in step Si, the organic solution is any one of N,N-dimethylformamide or methanol.

[0017] Preferably, in step S2, the bismuth source is one or more of bismuth nitrate and bismuth chloride.

[0018] Furthermore, in step S2, the stirring speed is 300-400 rpm, the stirring temperature is 60° C., and the stirring time is 60 min.

[0019] Furthermore, in step S2, the reaction time is 2 to 5 hours.

[0020] Furthermore, in step S2, the reaction temperature is 100-150°C.

[0021] Preferably, in step S3, the sulfur source is one or more of sodium thiosulfate, thiourea, and sodium sulfide.

[0022] Furthermore, in step S3, the stirring conditions are: a speed of 300-500 rpm, a temperature of 20-30° C., and a time of 30-60 min.

[0023] Furthermore, in step S3, the time for the reaction to be complete is 12 to 24 hours; and the reaction temperature is 180-200°C.

[0024] The post-treatment of the present invention specifically includes centrifugation and / or filtration, washing and drying.

[0025] More specifically, the detailed operation of the post-treatment is as follows: after the reaction product is completely cooled to room temperature, the obtained product is washed with anhydrous ethanol until the supernatant is clear, then the obtained product is dispersed in anhydrous ethanol, and purified in a constant temperature forced air drying oven at 60~80°C for 3~6h, and then continued to purify in anhydrous ethanol under the same conditions as the above purification, and finally vacuum dried at room temperature for 12~24h.

[0026] The second technical solution provided by the present invention is a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst generated in situ in a Bi-doped amino In-MOF, which is prepared by the preparation method described in the first technical solution.

[0027] The third technical solution provided by the present invention is the application of the Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst generated in situ in the Bi-doped amino In-MOF described in the second technical solution in the photothermal catalytic liquid-phase reforming of methanol to produce hydrogen.

[0028] The present invention also provides a method for producing hydrogen by photothermal catalytic liquid-phase reforming of methanol, which comprises the following steps:

[0029] The Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst is mixed with methanol, water and alkali, and reacted under anaerobic and light conditions at 100~210℃ to produce hydrogen.

[0030] The Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst: alkali: water: methanol 1:25~625:450~1800:800~3200.

[0031] Preferably, the base is one or more of potassium hydroxide and sodium hydroxide.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] 1. The technical solution provided by the present invention first synthesizes bismuth-doped amino In-MOF material, and then generates Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in situ by high-temperature sulfurization by a solvent thermal method, which can better combine photocatalysis and solar energy, realize photothermal synergistic effect, and the synergistic effect enables it to exhibit excellent photocatalytic activity under visible light irradiation. At the same time, under heating conditions, it can accelerate the desorption of products on the catalyst surface and promote the effective utilization of photogenerated electrons and holes. The hydrogen production under the conditions of photothermal synergistic catalysis has been significantly improved, and a certain amount of hydrogen production can be achieved at low temperatures.

[0034] 2. The amino In-MOF prepared by the technical solution provided by this invention has a high specific surface area, high porosity, and strong photoresponsiveness. The NH2-H2BDC ligand is used. The amino groups in the organic ligand act as chromophores, narrowing the energy band gap and thus enabling the utilization of visible light.

[0035] 3. The technical solution provided by the present invention uses Bi-doped amino In-MOF as a self-sacrificial template for in-situ high-temperature sulfurization to prepare an In2S3-Bi2S3 heterojunction with a wide spectral response; Bi2S3 sulfurized after Bi doping is an excellent photothermal material that can accelerate the reaction by providing a high surface temperature by maximizing the collection of solar energy; the formed Bi2S3-In2S3 heterojunction can improve the separation and transport of photogenerated charges and extend the lifetime of photogenerated carriers. The narrow band gap between Bi2S3 and In2S3 is conducive to enhancing the visible light response, and the formed heterojunction is conducive to suppressing the recombination of photogenerated electrons and holes, extending the lifetime of electrons and holes. The tight interface is conducive to the rapid transfer and separation of carriers, and the sufficient S vacancies are conducive to the formation of efficient adsorption-photocatalytic active centers.

[0036] 4. In the technical solution provided by the present invention, the original amino In-MOF has a rod-like structure, and after sulfurization, it becomes a unique hollow tubular structure of Bi2S3-In2S3, which is conducive to adjusting the refractive index in the channel to improve light utilization. The cavity is conducive to shortening the charge transfer length from the inside to the surface, thereby effectively promoting the separation of photogenerated carriers.

[0037] 5. The technical solution provided by the present invention does not add any other surfactants or modification pretreatments. It uses MOFs in situ sulfurization to construct a heterojunction photocatalyst. The close contact at the heterojunction caused by the in situ generation ensures a robust interface with faster electron transfer rate and higher charge carrier separation efficiency. The preparation method is simple and easy to implement. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 XRD patterns of amino In-MOF (a), Bi-doped amino In-MOF (b), In2S3 (c), and Bi2S3-In2S3 (d) prepared in Example 1;

[0039] Figure 2 Transmission electron microscopy images of the Bi-doped amino In-MOF (a) and the in-situ generated Bi2S3-In2S3 semiconductor heterojunction (b) provided in Example 1;

[0040] Figure 3This is a comparison chart of the thermal catalytic methanol liquid phase reforming hydrogen production and photothermal catalytic methanol liquid phase reforming hydrogen production of amino In-MOF (a), Bi-doped amino In-MOF (b), and Bi2S3-In2S3 (c) in Test Example 1.

[0041] Figure 4 This is a comparison chart of the thermal catalytic methanol liquid phase reforming hydrogen production and photothermal catalytic methanol liquid phase reforming hydrogen production of amino In-MOF (a), Bi-doped amino In-MOF (b), and Bi2S3-In2S3 (c) in Test Example 2. DETAILED DESCRIPTION

[0042] The present invention will be further described below with reference to the accompanying drawings and specific examples, but the examples do not limit the present invention in any way. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0043] Unless otherwise specified, the reagents and materials used in the following examples were commercially available.

[0044] Example 1

[0045] This embodiment provides a preparation method for in-situ generation of Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in Bi-doped amino In-MOF, the specific steps are as follows:

[0046] S1. Preparation of Amino-In-MOF

[0047] 0.6 g of indium nitrate tetrahydrate and 0.6 g of 2-amino-terephthalic acid were added to 60 mL of DMF, stirred and dispersed, and then mixed to obtain the precursor solution of amino In-MOF material.

[0048] S2. Preparation of Bi-doped Amino-In-MOF

[0049] Add 0.03 g of bismuth nitrate pentahydrate to the precursor solution of amino In-MOF material obtained in step S1, stir and disperse thoroughly, and react at 150 ° C for 3 h to obtain Bi-doped amino In-MOF material.

[0050] S3. Preparation of Bi2S3-In2S3 in Situ in Bi-doped Amino-In-MOF

[0051] 200 mg of aminoIn-MOF catalyst and 15 mL of ethanol were added to a 50 mL beaker. Subsequently, a solution containing 400 mg of thiourea and 15 mL of ethanol was dropped into the above suspension. The entire mixture was added to a polytetrafluoroethylene-lined autoclave and kept at 180 ° C for 12 hours. The reaction solution was then cooled to room temperature, filtered and washed several times with ethanol. Finally, the prepared sample was dried overnight under -0.08 MPa vacuum conditions at 60 ° C to obtain a light yellow Bi2S3-In2S3 powder.

[0052] Example 2

[0053] This example provides a method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in situ generated in a Bi-doped amino In-MOF. This method differs from Example 1 in that the mass of bismuth nitrate pentahydrate in step S2 is 0.048 g. Other parameters and procedures are similar to those in Example 1.

[0054] Example 3

[0055] This example provides a method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in situ generated in a Bi-doped amino In-MOF. This method differs from Example 1 in that the mass of bismuth nitrate pentahydrate in step S2 is 0.06 g. Other parameters and procedures are similar to those in Example 1.

[0056] Example 4

[0057] This example provides a method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in situ generated in a Bi-doped amino In-MOF. The method differs from Example 1 in that the reaction time in step S3 is 18 hours. Other parameters and operations are similar to those in Example 1.

[0058] Example 5

[0059] This example provides a method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in situ generated in a Bi-doped amino In-MOF. This method differs from Example 1 in that the reaction time in step S3 is 24 hours. Other parameters and operations are similar to those in Example 1.

[0060] Characterization Test

[0061] The Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst generated in situ in a Bi-doped amino In-MOF described in Example 1 was characterized and its photothermal catalytic performance was tested.

[0062] The crystal structures of amino In-MOf (a), Bi-doped amino In-MOF (b), In2S3 (c), and Bi2S3-In2S3 (d) described in Example 1 were analyzed by X-ray diffractometer, and the XRD patterns of the obtained samples were measured. Figure 1 As shown in (b), Bi-doped amino In-MOF has good crystallinity. By comparing (a) and (b), it can be observed that the diffraction peak does not change significantly after Bi doping, which can be attributed to the low amount of Bi doped. Figure 1 (c) and (d) show that after in situ sulfurization, the crystal structure of MOF remains stable, and Bi2S3-In2S is successfully derived through hydrothermal treatment. 3。 The XRD patterns of Bi2S3-In2S3 generated in situ in Bi-doped amino In-MOF in Examples 2 to 5 are basically consistent with those in Example 1.

[0063] The transmission electron microscopy spectrum of the obtained sample was measured, and the results were as follows Figure 2 shown. Figure 2 (a) Bi-doped amino In-MOF, showing that Bi-doped amino In-MOF has highly uniform hexagonal tube morphology and smooth tubular surface; Figure 2 (b) shows the in situ generation of Bi2S3-In2S3 in Bi-doped amino-In-MOF. The hexagonal tube morphology is well maintained, but the surface is rougher than that of amino-In-MOF and the hollow tubular structure is observed, indicating the successful synthesis of the Bi2S3-In2S3 catalyst. The TEM images of the in situ generated Bi2S3-In2S3 photothermal catalysts in Bi-doped amino-In-MOF in Examples 2-5 are essentially consistent with those in Example 1, with hollow tubular structures observed in all cases.

[0064] The Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst was in situ generated in Bi-doped amino In-MOF to test the photothermal catalytic liquid-phase reforming of methanol to produce hydrogen.

[0065] Photothermal catalytic methanol liquid phase reforming to produce hydrogen is carried out in a photothermal reactor and heated by a heating furnace equipped with a magnetic stirring device and external lighting.

[0066] Test Case 1

[0067] 0.625 g of KOH was dissolved in 12.5 g of methanol-water solution (methanol-water solution mass ratio was 9:16), and the mixture was sonicated until the KOH dissolved to obtain reaction substrate A.

[0068] 5 mg of the Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst or amino In-MOF or Bi2S3-In2S3 prepared in Example 1 was placed in the lining of a photothermal reactor, and then the reaction substrate A of step (1) was added. After the reactor was filled, nitrogen was pressurized to 2 MPa and purged three times to ensure complete removal of air. The reactor was irradiated with a 300 W Xe lamp (CEL-HXF300-T3 and / or CEL-HXUV300-T3) at 210°C and 2 MPa for 80 minutes. After the reaction, the gas inside the photothermal reactor was collected with an air bag and analyzed by GC (GC9790PLUS) to determine the amount of hydrogen produced.

[0069] Test Case 2

[0070] 0.625 g of KOH was dissolved in 12.5 g of methanol-water solution (methanol-water solution mass ratio was 9:16), and the mixture was sonicated until the KOH dissolved to obtain reaction substrate A.

[0071] 5 mg of the Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst or amino In-MOF or Bi2S3-In2S3 prepared in Example 1 was placed in the lining of a photothermal reactor, and then the reaction substrate A of step (1) was added. After the reactor was filled, nitrogen was pressurized to 2 MPa and purged three times to ensure complete removal of air. The reactor was irradiated with a 300 W Xe lamp (CEL-HXF300-T3 and / or CEL-HXUV300-T3) at 100°C and 2 MPa for 80 minutes. After the reaction, the gas inside the photothermal reactor was collected with an air bag and analyzed by GC (GC9790PLUS) to determine the amount of hydrogen produced.

[0072] The photothermal / thermal catalytic methanol liquid phase reforming hydrogen production performance of amino In-MOF, Bi-doped amino In-MOF, and Bi2S3-In2S3 were tested in Test Example 1. The comparison results are as follows: Figure 3 As shown in Figure 2, the photothermal hydrogen production rate of Bi-In-MOF increased by 14207 μmol·g by doping with Bi metal. -1 ·h -1 It can be observed that the hydrogen production performance of amino In-MOF, Bi-doped amino In-MOF, and Bi2S3-In2S3 photothermal catalysts under thermal catalysis conditions is not much different, while under photothermal action, their hydrogen production performance reaches 68164.62 μmol·g -1 ·h -1, 4.5 times the pure thermal hydrogen production rate and 2.6 times that of amino-In-MOF. This demonstrates that the synergistic effects of photocatalysis and thermocatalysis can mutually promote the accelerated conversion of adsorbates on the catalyst surface. By utilizing light energy to promote catalyst activation or in-situ reduction of active centers, and utilizing thermal energy to provide the heat required for the reaction, the two interact to synergistically improve the efficiency of methanol liquid-phase reforming hydrogen production and reduce the reaction temperature.

[0073] This is because the amino In-MOF material has a high specific surface area, high porosity, and strong photoresponse ability. NH2-H2BDC is used as a ligand. The amino group in the organic ligand acts as a chromophore to narrow the energy band gap, thereby realizing the utilization of visible light. Bi2S3-In2S3 heterojunction with a wide spectral response is prepared by sulfurization using bismuth-doped amino In-MOF as a self-sacrificial template. Bi2S3 sulfurized after Bi doping is an excellent photothermal material. It can accelerate the reaction by maximizing the collection of solar energy to provide a high surface temperature. It can effectively reduce the activation energy of the substrate methanol water under the irradiation of sunlight, enabling it to react at low temperatures. The formed Bi2S3-In2S3 heterojunction can improve the separation and transport of photogenerated charges and extend the lifetime of photogenerated carriers. The original amino In-MOF has a rod-like structure, and after sulfurization, it becomes the unique hollow tubular structure of Bi2S3-In2S3, which is conducive to adjusting the refractive index in the channel to improve light utilization. The cavity is conducive to shortening the charge transfer length from the inside to the surface, thereby effectively promoting the separation of photogenerated carriers.

[0074] It can be seen from Test Example 2 that the catalyst of the present application can also produce a certain amount of hydrogen at 100°C. Figure 4 As shown in the figure, when the reaction temperature is 100℃, the catalyst of the present application can reach 206 μmol·g Cat -1 ·h -1 The hydrogen production rate is 2.5%, while at the temperature of 100℃, amino In-MOF and Bi-doped amino In-MOF no longer produce hydrogen.

[0075] The photothermal catalytic performance results of the Bi2S3-In2S3 semiconductor heterojunction photothermal catalysts in situ generated in Bi-doped amino In-MOF in Examples 2 to 5 are basically consistent with those in Example 1. The prepared catalysts all utilize light energy to promote the activation of the catalyst or the in situ reduction of the active center, and utilize thermal energy to provide the heat required for the reaction. The two interact with each other to synergistically improve the efficiency of methanol liquid phase reforming to produce hydrogen.

[0076] Obviously, the above embodiments of the present invention are merely examples for the purpose of clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the claims of the present invention.

Claims

1. A method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst, characterized in that: The method includes the following steps in sequence: S1. The indium source and the organic ligand are added to an organic solvent and stirred to obtain a precursor solution of an amino In-MOF material; S2. Adding a bismuth source to the precursor solution of the amino In-MOF material obtained in step S1, stirring and dispersing the mixture, and reacting the mixture at 100-150°C for 2-5 hours to obtain a Bi-doped amino In-MOF material. S3. Dissolving the Bi-doped amino In-MOF and the sulfur source obtained in S2 in an organic solvent, stirring and dispersing the mixture, and reacting the mixture at 180-200°C for 12-24 hours to obtain a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst. Wherein: the mass ratio of the bismuth source to the indium source in step S2 is (0.05-0.1):1; In step S3, the mass ratio of the In-MOF to the sulfur source is 1:(1-3); The organic ligand is 2-amino-terephthalic acid.

2. The method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst according to claim 1, characterized in that: The indium source is one or more of indium nitrate, indium sulfate, and indium acetate.

3. The method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst according to claim 1, characterized in that: The organic solvent in step S1 is N,N-dimethylformamide or methanol; the organic solvent in step S3 is ethanol.

4. The method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst according to claim 1, characterized in that: The bismuth source in step S2 is one or more of bismuth nitrate and bismuth chloride.

5. The method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst according to claim 1, characterized in that: The sulfur source in step S3 is one or more of sodium thiosulfate, thiourea, and sodium sulfide.

6. The method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst according to claim 1, characterized in that: The stirring speed in step S2 is 300-400 rpm, and the stirring time is 60 min. The stirring conditions in step S3 are: stirring speed 300-500 rpm, temperature 20-30° C., and time 30-60 min.

7. A Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst, characterized in that: The invention is prepared by the preparation method according to any one of claims 1 to 6.

8. The Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst according to claim 7 is used for photothermal catalytic liquid-phase reforming of methanol to produce hydrogen.

9. A method for producing hydrogen by photothermal catalytic liquid phase reforming of methanol, characterized in that: The Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst according to claim 7 is mixed with water and alkali, and reacted under anaerobic, light and heating conditions to obtain hydrogen.

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