Bi2S3-In2S3 semiconductor heterojunction photo-thermal catalyst as well as preparation method and application thereof

Abstract

The invention discloses a Bi2S3-In2S3 semiconductor heterojunction photo-thermal catalyst as well as a preparation method and application of the Bi2S3-In2S3 semiconductor heterojunction photo-thermal catalyst. According to the technical scheme, the Bi2S3-In2S3 semiconductor heterojunction photo-thermal catalyst with wide spectral response is prepared by adopting a method for carrying out in-situ high-temperature vulcanization on Bi-doped amino In-MOF (Metal-Organic Framework); according to the catalyst, photocatalysis and thermocatalysis are combined, the photo-thermal synergistic effect is achieved, the synergistic effect promotes the catalyst to show excellent photocatalytic activity under visible light irradiation, meanwhile, desorption of products on the surface of the catalyst can be accelerated under the heating condition, effective utilization of photo-induced electrons and holes is promoted, and the photocatalytic activity of the catalyst is improved. The hydrogen production amount under the photo-thermal concerted catalysis condition is obviously increased, and a certain hydrogen production amount can also be achieved at low temperature.

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 issues for improving the hydrogen production efficiency of methanol reforming, inhibiting the formation of by-products and reducing the reaction energy consumption. This paper will review the latest research progress and mechanism understanding of methanol hydrogen production catalysts, which are the cornerstone of the methanol-H2 energy system, discuss the difficulties and challenges faced by the research and development of methanol hydrogen production catalysts, and look forward to the development direction of catalyst development.

[0003] Against the backdrop of increasingly serious global climate change caused by excessive carbon emissions, the development of clean alternative energy is urgent. At present, the widely-watched clean energy includes solar energy and secondary energy derived from solar energy, such as wind energy, hydropower, ocean energy, biomass energy, etc. Compared with traditional fossil energy, clean energy has a relatively low energy density, and its distribution is greatly restricted by the geographical environment. It inevitably 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 (142MJ kg -1 ), good utilization efficiency and eco-friendly properties, it has long been considered an ideal renewable energy carrier, so achieving sustainable hydrogen production is one of the most attractive and competitive technologies. Methanol is one of the best hydrogen carriers due to its high proton density and easy liquid phase transportation.

[0004] In traditional thermal catalytic processes, high temperature and pressure are required for reaction driving, high reaction energy consumption and many byproducts. The introduction of light energy can reduce the requirements of high energy input and activation of stable chemical bonds (CH and OH), thereby reducing the activation barrier and conducting more efficient catalytic reactions under mild conditions. Compared with the bandgap-limited spectral efficiency of pure photocatalytic systems, photothermal catalysis can make full use of the solar spectrum and increase the reaction rate. Photothermally driven reforming of methanol solution to hydrogen effectively reduces the activation energy barrier and overcomes the challenges associated with slow kinetics. At the same time, it uses photon energy to improve reaction kinetics while reducing the activation energy prerequisites of the process. This breakthrough approach promotes efficient production of hydrogen at lower temperatures and high selectivity. However, most current photocatalysts still have problems such as low efficiency, poor light absorption, and low efficiency in separating electrons and holes. Metal-organic frameworks (MOFs) have adjustable porosity, high specific surface area and synthetic versatility, and have recently become new porous crystalline materials that play an important role in the field of photothermal catalysis.

[0005] The prior art discloses a semiconductor photocatalyst (such as TiO2, Fe2O3, CdS, etc.) used in the field of hydrogen production. These inorganic catalysts have the disadvantages of low solar energy conversion efficiency, easy photocorrosion, easy agglomeration, difficult post-separation, limited catalytic activity, etc., and high energy consumption and high hydrogen production cost during the hydrogen production reaction. Therefore, it is urgent to explore a stable, efficient, and low-energy consumption photothermal catalyst for methanol liquid phase reforming hydrogen production. 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 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, which 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 generated in situ in Bi-doped amino In-MOF.

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

[0009] The first object of the present invention is achieved by 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 the indium source and the organic ligand into the organic solvent, disperse and dissolve them to obtain the precursor solution of the 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 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 to 500 rpm, a temperature of 20 to 30° C., and a time of 30 to 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: after the reaction product is completely cooled to room temperature, the obtained product is washed with anhydrous ethanol until the supernatant is clear, and then the obtained product is dispersed in anhydrous ethanol, and purified in a constant temperature forced air drying oven at 60 to 80° C. for 3 to 6 hours, and then continue to purify in anhydrous ethanol under the same conditions as the above purification, and finally perform vacuum drying at room temperature for 12 to 24 hours.

[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, the method comprising 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°C to produce hydrogen.

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

[0031] Preferably, the alkali 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 solvothermal method, which can better combine photocatalysis and solar energy and realize 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 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 the present invention has a high specific surface area, high porosity, and strong light response ability. The NH2-H2BDC used as a ligand, the amino group in the organic ligand as a chromophore can reduce the energy band gap and thus realize 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, which can accelerate the reaction by maximizing the collection of solar energy to provide a high surface temperature; 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, the formed heterojunction is conducive to suppressing the recombination of photogenerated electrons and holes, and 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 is a rod-shaped 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 the light utilization rate. 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, and adopts MOFs in situ sulfurization to construct heterojunction photocatalysts. The close contact at the heterojunction caused by the in situ generation ensures a faster electron transfer rate and a more robust interface with 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 performance 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 performance 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 is further described below in conjunction with the accompanying drawings and specific examples, but the examples do not limit the present invention in any form. 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 are commercially available.

[0044] Example 1

[0045] This embodiment provides a method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in situ generated in Bi-doped amino In-MOF, and 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 mixed to obtain a 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 the 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, respectively. Subsequently, a solution containing 400 mg of thiourea and 15 mL of ethanol was dripped into the above suspension. The resulting mixture was added to an autoclave with a polytetrafluoroethylene liner 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 a vacuum condition of -0.08 MPa at 60 ° C to obtain a light yellow Bi2S3-In2S3 powder.

[0052] Example 2

[0053] This embodiment provides a preparation method for in-situ generation of Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in Bi-doped amino In-MOF, which is different from the embodiment 1 in that the mass of bismuth nitrate pentahydrate in step S2 is 0.048g. Other parameters and operations refer to the embodiment 1.

[0054] Example 3

[0055] This embodiment provides a preparation method for in-situ generation of Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in Bi-doped amino In-MOF, which is different from Example 1 in that the mass of bismuth nitrate pentahydrate in step S2 is 0.06 g. Other parameters and operations refer to Example 1.

[0056] Example 4

[0057] This embodiment provides a preparation method for in-situ generation of Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in Bi-doped amino In-MOF, which is different from the embodiment 1 in that the reaction time in step S3 is 18 hours. Other parameters and operations refer to the embodiment 1.

[0058] Example 5

[0059] This embodiment provides a preparation method for in-situ generation of Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst in Bi-doped amino In-MOF, which is different from the embodiment 1 in that the reaction time in step S3 is 24 hours. Other parameters and operations refer to the embodiment 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 structure of amino In-MOf (a), Bi-doped amino In-MOF (b), In2S3 (c), and Bi2S3-In2S3 (d) described in Example 1 was 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 less Bi doping; Figure 1 (c) and (d) show that after in situ sulfurization, the crystal structure of MOF remains stable, and Bi2S3-In2S is successfully derived by hydrothermal method. 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 a smooth tubular surface; Figure 2 (b) Bi2S3-In2S3 is generated in situ in Bi-doped amino-In-MOF, which better maintains the hexagonal tube morphology, but the surface is rougher than that of amino-In-MOF and has a hollow tubular structure, which also indicates the successful synthesis of Bi2S3-In2S3 catalyst. The TEM images of Bi2S3-In2S3 photothermal catalysts generated in situ in Bi-doped amino-In-MOF in Examples 2 to 5 are basically consistent with those in Example 1, and hollow tubular structures are observed in all of them.

[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] (1) Dissolve 0.625 g of KOH in 12.5 g of methanol-water solution (methanol-water solution mass ratio is 9:16), and sonicate until KOH is dissolved to obtain reaction substrate A.

[0068] (2) 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 the photothermal reactor, and then the reaction substrate A of step (1) was added. After the reactor was loaded, the nitrogen was pressurized to 2 MPa and the air was repeatedly purged three times to ensure that the air was completely removed. At 210°C and 2 MPa, the reactor was irradiated with a 300WXe lamp (CEL-HXF300-T3 and / or CEL-HXUV300-T3) 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] (1) Dissolve 0.625 g of KOH in 12.5 g of methanol-water solution (methanol-water solution mass ratio is 9:16), and sonicate until KOH is dissolved to obtain reaction substrate A.

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

[0072] In Test Example 1, the photothermal / thermal catalytic methanol liquid phase reforming hydrogen production performance of amino In-MOF, Bi-doped amino In-MOF, and Bi2S3-In2S3 were respectively compared. The results are as follows Figure 3 As shown in Figure 2, by doping Bi metal, the photothermal hydrogen production rate of Bi-In-MOF increased by 14207 μmol·g -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 is not much different, but under photothermal action, its hydrogen production performance reaches 68164.62 μmol·g -1 ·h -1, which is 4.5 times the pure thermal hydrogen production rate and 2.6 times that of amino In-MOF. This shows that the synergistic effect of photocatalysis and thermal catalysis can promote each other to accelerate the conversion of adsorbates on the catalyst surface. Light energy is used to promote the activation of the catalyst or the in-situ reduction of the active center, and thermal energy is used to provide the heat required for the reaction. The two interact with each other to synergistically improve the efficiency of methanol liquid phase reforming hydrogen production and reduce the temperature required for the reaction.

[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 and thus realize 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, so that it can 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 Bi2S3-In2S3. The unique hollow tubular structure is conducive to adjusting the refractive index in the pores 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, when the reaction temperature is 100°C, the catalyst of the present application can reach 206 μmol·g Cat -1 ·h -1 The hydrogen production rate is 2.5%, while at a temperature of 100°C, 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 catalyst 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 hydrogen production by liquid phase reforming of methanol.

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

Claims

1. A method for preparing a Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst, characterized in that: The steps are as follows: S1. Adding the indium source and the organic ligand to the organic solvent, stirring and dispersing them uniformly to obtain a precursor solution of the amino In-MOF material; S2. Add the bismuth source to the precursor solution of the amino In-MOF material obtained in step S1, stir and disperse thoroughly, and react at 100 to 150° C. for 2 to 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 them sufficiently, and reacting them at 180 to 200° C. for 12 to 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).

2. The method for preparing the 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 the Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst according to claim 1, characterized in that: The organic ligand is 2-amino-terephthalic acid.

4. The method for preparing the 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.

5. The method for preparing the 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.

6. The method for preparing the 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.

7. The method for preparing the 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 is 300-500 rpm, temperature is 20-30° C., and time is 30-60 min.

8. A Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst, characterized in that: The method is prepared according to any one of claims 1 to 8.

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

10. A method for producing hydrogen by photothermal catalytic methanol liquid phase reforming, characterized in that: The Bi2S3-In2S3 semiconductor heterojunction photothermal catalyst described in claim 8 is mixed with water and alkali, and reacted under anaerobic, light and heating conditions to obtain hydrogen.

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