Transition metal sulfide / oxide modified bimetallic sulfide composite material as well as preparation method and application thereof
By combining transition metal sulfides/oxides MoS2/MoO3-x with ZnIn2S4, a MoS2/MoO3-x@ZnIn2S4 composite material was prepared, which solved the problems of insufficient charge carrier recombination and light capture in the photocatalytic reaction of ZnIn2S4. This resulted in efficient and stable photocatalytic hydrogen evolution performance, reduced costs, and has potential for industrial application.
Patent Information
- Application Number
- CN202410607209.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-05-16
- Publication Date
- 2025-11-18
AI Technical Summary
Existing photocatalytic material ZnIn2S4 suffers from problems such as rapid recombination of photogenerated charge carriers and insufficient light-harvesting ability in photocatalytic reactions. Furthermore, the scarcity and high price of noble metal co-catalysts limit its widespread application.
A MoS2/MoO3-x@ZnIn2S4 composite material was prepared by combining transition metal sulfides/oxides MoS2/MoO3-x with ZnIn2S4 via a solvothermal method, which enhanced the photocatalytic activity and stability.
This study improved the performance of photocatalytic hydrogen evolution, reduced costs, and provided a highly efficient and stable photocatalyst for industrial applications.
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Figure CN120961186A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The material belongs to the field of photocatalytic material preparation and hydrogen evolution application, and specifically proposes a transition metal sulfide / oxide modified double metal sulfide composite material and a preparation method and application thereof. BACKGROUND
[0002] The environmental problems faced by human beings in today's society are becoming increasingly serious. The combustion of fossil resources dominated by coal, oil and natural gas releases harmful gases, causing "greenhouse effect", acid rain and many other environmental pollution problems. Moreover, fossil fuels are non-renewable resources, which makes human beings also face the problem of resource shortage. Therefore, in order to realize the sustainable development of human beings, it is urgent to develop clean renewable energy. Hydrogen is a kind of energy with high combustion value, high efficiency and cleanliness. However, the production of hydrogen energy at present still mainly relies on the reforming of coal and natural gas, which will inevitably exacerbate the consumption of non-renewable energy and cause environmental pollution problems. Therefore, using water, biomass and other renewable resources as raw materials to produce hydrogen by solar energy is one of the ideal ways to fundamentally solve the problems of energy and environmental pollution.
[0003] Generally speaking, high-efficiency photocatalytic hydrogen evolution catalysts should have adjustable photo-induced charge separation structure characteristics, suitable electron energy band structure for light capture and appropriate photocatalytic kinetics. However, the photocatalytic materials studied at present still face the problems of poor performance, easy corrosion, high toxicity and the like, and therefore it is crucial to explore more efficient, stable and non-toxic photocatalysts. Among many excellent sulfide semiconductors, double metal sulfide ZnIn2S4 is widely used in the field of photocatalytic decomposition of water to produce hydrogen due to its unique physicochemical properties, such as structural stability, adjustable band gap, suitable energy band structure, widely available synthesis raw materials and easy synthesis. However, in the photocatalytic reaction, ZnIn2S4 still has the shortcomings of fast recombination of photo-induced charge carriers and insufficient light capture capacity. In order to overcome these shortcomings, scientists have proposed various strategies for ZnIn2S4, such as noble metal deposition, heterostructure construction, ion doping, defect engineering and cocatalyst modification, to further prolong the lifetime of electron-hole pairs and promote the separation of charge carriers.
[0004] As the most common cocatalysts, noble metals (such as Pt, Pd, and Au) can significantly improve the photocatalytic activity of semiconductors. Because the Fermi level of noble metals is typically lower than the conduction band (CB) potential of most semiconductor photocatalysts, photogenerated electrons are efficiently transferred through the interface, thereby suppressing charge carrier recombination. Unfortunately, the scarcity and high price of noble metal Pd cocatalysts hinder their widespread application. Therefore, there is an urgent need to construct a non-noble metal catalyst that is abundant in Earth's reserves, which can not only improve the performance of photocatalytic hydrogen evolution but also significantly reduce its overall cost, enabling its industrial application.
[0005] Transition metal compounds, including transition metal phosphides, sulfides, selenides, carbides, and oxides, have attracted considerable attention due to their abundant abundance in the Earth's crust, excellent photoelectric properties, and superior catalytic performance in various aspects, making them a widely studied subject in the field of photocatalysis. Through related research and development, transition metal compounds and their complexes hold promise as promising photocatalysts.
[0006] This study combines a transition metal sulfide / oxide with good conductivity and excellent stability with the bimetallic sulfide ZnIn2S4 to obtain a composite catalyst for photocatalytic hydrogen evolution, enabling safe and efficient hydrogen production, which has profound significance for future energy and industrial development. Summary of the Invention
[0007] This invention proposes a composite material prepared by combining a transition metal sulfide / oxide with the bimetallic sulfide ZnIn2S4, and applies it to photocatalytic water splitting for hydrogen production. This composite material alleviates the problem of charge carrier generation in ZnIn2S4 alone while enhancing its visible light absorption, thus improving both catalytic performance and stability, providing a new approach for related research in the field of photocatalysis.
[0008] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:
[0009] A transition metal sulfide / oxide modified bimetallic sulfide composite material—MoS2 / MoO 3-x @ZnIn2S4, MoS2 / MoO was prepared in one step by calcining a mixture of ammonium molybdate and thiourea under a nitrogen atmosphere. 3-x The complex was then added to an ethanol solution containing indium chloride tetrahydrate, zinc chloride, and thioacetamide, and MoS2 / MoO was prepared by a solvothermal method. 3-x @ZnIn2S4, this catalyst exhibits good photocatalytic activity.
[0010] The MoS2 / MoO 3-x Preparation method of ZnIn2S4:
[0011] Ammonium molybdate and thiourea were weighed out in a mortar and pestle at a molar ratio of 1:21 and ground continuously until a fine and uniform powder was formed. The ground and mixed raw materials were placed in a magnetic boat and heated to 380℃ in a tube furnace under nitrogen purging and held at that temperature for 2 hours to obtain the MoS2 / MoO sample. 3-x Then, the obtained MoS2 / MoO2 3-x The solution was added to 20 mL of ethanol solution containing indium chloride tetrahydrate, zinc chloride, and thioacetamide, and ultrasonically dispersed for 30 minutes. The mixture was then placed in a 50 mL polytetrafluoroethylene liner, heated to 120 °C and maintained for 2 hours. The precipitate was collected by centrifugation, washed several times with ethanol and deionized water, and dried in a vacuum drying oven at 60 °C for 6 hours. The resulting product was MoS2 / MoO. 3-x @ZnIn2S4.
[0012] The advantages of this invention are:
[0013] (1) This invention uses relatively inexpensive transition metal materials as raw materials to prepare a bimetallic sulfide composite material modified with transition metal sulfides / oxides, and by changing the MoS2 / MoO2 ratio... 3-x The content of MoS2 / MoO was found to be obtained when the loading was 10 mg. 3-x @ZnIn2S4 exhibits the highest photocatalytic hydrogen production rate (8649 μmol g). -1 h -1 It has excellent photocatalytic hydrogen evolution performance.
[0014] (2) The raw materials used in this invention are relatively inexpensive and readily available, the equipment and process conditions are simple, the operation is easy, the safety is high, the industrial application value is high, and there is great application potential. Attached Figure Description
[0015] Figure 1 It is the MoS2 / MoO in Example 2 3-x XRD pattern of the material.
[0016] Figure 2 It is MoS2 and MoS2 / MoO in Example 2 3-x XRD patterns of ZnIn2S4 and ZnIn2S4 material in Example 5.
[0017] Figure 3 Is MoS2 / MoO 3-x Scanning electron microscope image.
[0018] Figure 4 This is a scanning electron microscope image of the ZnIn2S4 material in Example 5.
[0019] Figure 5 It is a different MoS2 / MoO 3-x MoS2 / MoO prepared by content 3-x Photocatalytic hydrogen production rate of @ZnIn2S4.
[0020] Figure 6 It is MoS2@ZnIn2S4, MoO 3-x @ZnIn2S4、MoS2 / MoO 3-x Comparison of photocatalytic hydrogen production rates between ZnIn2S4 and pure ZnIn2S4.
[0021] Figure 7 It is MoS2 and MoS2 / MoO in Example 2 3-x @ZnIn2S4 and the UV-Vis diffuse reflectance spectra of ZnIn2S4 materials in Example 5. Detailed Implementation
[0022] To more clearly illustrate the purpose, synthesis method, and advantages of this invention, the invention is further explained in detail with reference to the following examples. It should be understood that the examples described herein are for illustrative purposes only and are not intended to limit the invention itself.
[0023] Example 1
[0024] Weigh 0.62 g of ammonium molybdate and 0.40 g of thiourea into a mortar and grind them continuously until a fine and uniform powder is formed. Place the ground material in a magnetic boat and heat it to 380 °C in a tube furnace under nitrogen purging, then hold the temperature for 2 hours to obtain the MoS2 / MoO sample. 3-x .
[0025] Weigh 0.30 g of indium chloride tetrahydrate, 0.07 g of zinc chloride, and 0.15 g of thioacetamide and add them to 20 mL of ethanol solution, stirring constantly until a homogeneous solution is obtained. Then add 5 mg of the MoS2 / MoO2 solution prepared above. 3-x The mixture was ultrasonically dispersed for 30 minutes. Then, the mixture was transferred to a 50 mL polytetrafluoroethylene liner, heated to 120 °C and maintained for 2 hours. The precipitate was collected by centrifugation, washed with ethanol and deionized water, and dried in a vacuum drying oven at 60 °C for 6 hours to obtain 5MoS2 / MoO2. 3-x @ZnIn2S4.
[0026] Application Example 1
[0027] The photocatalytic hydrogen production performance was tested in a closed Labsoler6 photocatalytic system. A 300W xenon lamp with a filter to control the incident light wavelength λ≥420nm was used as a stable light source. The amount of hydrogen produced was collected and analyzed using a GB-9890 gas chromatograph. The specific operating steps are as follows: 20mg of the prepared catalyst material was weighed and dispersed in 80mL of a mixed solution containing triethanolamine (10vol%) as a sacrificial agent, and then subjected to appropriate ultrasonic treatment to form a relatively homogeneous dispersion. The reaction solution was then poured into the reactor and connected to the device. Magnetic stirring was performed continuously, and the system was evacuated during stirring. Then, 20mL of high-purity Ar was injected using a syringe. Throughout the reaction, the system temperature was kept constant at 25℃ using a circulating water cooling system. The amount of hydrogen produced was collected every half hour after the reaction started. The average rate over two hours was measured to be 5952 μmol g. - 1 h -1 .
[0028] Example 2
[0029] Weigh 0.62 g of ammonium molybdate and 0.40 g of thiourea into a mortar and grind them continuously until a fine and uniform powder is formed. Place the ground material in a magnetic boat and heat it to 380 °C in a tube furnace under nitrogen purging, then hold the temperature for 2 hours to obtain the MoS2 / MoO sample. 3-x .
[0030] Weigh 0.30 g of indium chloride tetrahydrate, 0.07 g of zinc chloride, and 0.15 g of thioacetamide and add them to 20 mL of ethanol solution, stirring constantly until a homogeneous solution is obtained. Then add 10 mg of the MoS2 / MoO2 prepared above. 3-x The mixture was ultrasonically dispersed for 30 minutes. Then, the mixture was transferred to a 50 mL polytetrafluoroethylene liner, heated to 120 °C and maintained for 2 hours. The precipitate was collected by centrifugation, washed with ethanol and deionized water, and dried in a vacuum drying oven at 60 °C for 6 hours to obtain 10MoS2 / MoO2. 3-x @ZnIn2S4.
[0031] Application Example 2
[0032] The photocatalytic hydrogen production performance was tested in a closed Labsoler6 photocatalytic system. A 300W xenon lamp with a filter to control the incident light wavelength λ≥420nm was used as a stable light source. The amount of hydrogen produced was collected and analyzed using a GB-9890 gas chromatograph. The specific operating steps are as follows: 20mg of the prepared catalyst material was weighed and dispersed in 80mL of a mixed solution containing triethanolamine (10vol%) as a sacrificial agent, and then subjected to appropriate ultrasonic treatment to form a relatively homogeneous dispersion. The reaction solution was then poured into the reactor and connected to the device. Magnetic stirring was performed continuously, and the system was evacuated during stirring. Then, 20mL of high-purity Ar was injected using a syringe. Throughout the reaction, the system temperature was kept constant at 25℃ using a circulating water cooling system. The amount of hydrogen produced was collected every half hour after the reaction started. The average rate over two hours was measured to be 8649 μmol g. - 1 h -1 .
[0033] Example 3
[0034] Weigh 0.62 g of ammonium molybdate and 0.40 g of thiourea into a mortar and grind them continuously until a fine and uniform powder is formed. Place the ground material in a magnetic boat and heat it to 380 °C in a tube furnace under nitrogen purging, then hold the temperature for 2 hours to obtain the MoS2 / MoO sample. 3-x .
[0035] Weigh 0.30 g of indium chloride tetrahydrate, 0.07 g of zinc chloride, and 0.15 g of thioacetamide and add them to 20 mL of ethanol solution, stirring constantly until a homogeneous solution is obtained. Then add 12.5 mg of the MoS2 / MoO2 prepared above. 3-x The mixture was ultrasonically dispersed for 30 minutes. Then, the mixture was transferred to a 50 mL polytetrafluoroethylene liner, heated to 120 °C and maintained for 2 hours. The precipitate was collected by centrifugation, washed with ethanol and deionized water, and dried in a vacuum drying oven at 60 °C for 6 hours to obtain 12.5 MoS2 / MoO2. 3-x @ZnIn2S4.
[0036] Application Example 3
[0037] The photocatalytic hydrogen production performance was tested in a closed Labsoler6 photocatalytic system. A 300W xenon lamp with a filter to control the incident light wavelength λ≥420nm was used as a stable light source. The amount of hydrogen produced was collected and analyzed using a GB-9890 gas chromatograph. The specific operating steps are as follows: 20mg of the prepared catalyst material was weighed and dispersed in 80mL of a mixed solution containing triethanolamine (10vol%) as a sacrificial agent, and then subjected to appropriate ultrasonic treatment to form a relatively homogeneous dispersion. The reaction solution was then poured into the reactor and connected to the device. Magnetic stirring was performed continuously, and the system was evacuated during stirring. Then, 20mL of high-purity Ar was injected using a syringe. Throughout the reaction, the system temperature was kept constant at 25℃ using a circulating water cooling system. The amount of hydrogen produced was collected every half hour after the reaction started. The average rate over two hours was measured to be 7669 μmol g. - 1 h -1 .
[0038] Example 4
[0039] Weigh 0.62 g of ammonium molybdate and 0.40 g of thiourea into a mortar and grind them continuously until a fine and uniform powder is formed. Place the ground material in a magnetic boat and heat it to 380 °C in a tube furnace under nitrogen purging, then hold the temperature for 2 hours to obtain the MoS2 / MoO sample. 3-x .
[0040] Weigh 0.30 g of indium chloride tetrahydrate, 0.07 g of zinc chloride, and 0.15 g of thioacetamide and add them to 20 mL of ethanol solution, stirring constantly until a homogeneous solution is obtained. Then add 20 mg of the MoS2 / MoO2 prepared above. 3-x The mixture was ultrasonically dispersed for 30 minutes. Then, the mixture was transferred to a 50 mL polytetrafluoroethylene liner, heated to 120 °C and maintained for 2 hours. The precipitate was collected by centrifugation, washed with ethanol and deionized water, and dried in a vacuum drying oven at 60 °C for 6 hours to obtain 20MoS2 / MoO2. 3-x @ZnIn2S4.
[0041] Application Example 4
[0042] The photocatalytic hydrogen production performance was tested in a closed Labsoler6 photocatalytic system. A 300W xenon lamp with a filter to control the incident light wavelength λ≥420nm was used as a stable light source. The amount of hydrogen produced was collected and analyzed using a GB-9890 gas chromatograph. The specific operating steps are as follows: 20mg of the prepared catalyst material was weighed and dispersed in 80mL of a mixed solution containing triethanolamine (10vol%) as a sacrificial agent, and then subjected to appropriate ultrasonic treatment to form a relatively homogeneous dispersion. The reaction solution was then poured into the reactor and connected to the device. Magnetic stirring was performed continuously, and the system was evacuated during stirring. Then, 20mL of high-purity Ar was injected using a syringe. Throughout the reaction, the system temperature was kept constant at 25℃ using a circulating water cooling system. The amount of hydrogen produced was collected every half hour after the reaction started. The average rate over two hours was measured to be 5137 μmol g. - 1 h -1 .
[0043] Example 5
[0044] 0.12 g of ammonium molybdate and 1.08 g of thiourea were weighed and placed in a mortar, and ground continuously until a fine and uniform powder was formed. The ground material was placed in a magnetic boat and heated to 380 °C in a tube furnace under nitrogen purging and held at that temperature for 2 h to obtain the sample MoS2. Then, 0.30 g of indium chloride tetrahydrate, 0.07 g of zinc chloride, and 0.15 g of thioacetamide were weighed and added to 20 mL of ethanol solution, and stirred continuously until a homogeneous solution was obtained. Finally, 10 mg of the MoS2 / MoO2 prepared above was added. 3-x The mixture was ultrasonically dispersed for 30 minutes. Then, the mixture was transferred to a 50 mL polytetrafluoroethylene liner, heated to 120 °C and maintained for 2 h, centrifuged to collect the precipitate, washed with ethanol and deionized water, and dried in a vacuum drying oven at 60 °C for 6 h to obtain MoS2@ZnIn2S4, which was used as a control sample.
[0045] Weigh 0.5g of ammonium molybdate into a mortar and grind it continuously until a fine and uniform powder is formed. Place the ground material in a magnetic boat and heat it to 380℃ in a tube furnace under nitrogen purging, then hold the temperature for 2 hours to obtain the sample MoO. 3-x Next, weigh out 0.30 g of indium chloride tetrahydrate, 0.07 g of zinc chloride, and 0.15 g of thioacetamide and add them to 20 mL of ethanol solution, stirring constantly until a homogeneous solution is obtained. Then add 10 mg of the MoS2 / MoO2 prepared above. 3-x The mixture was ultrasonically dispersed for 30 minutes. Then, the mixture was transferred to a 50 mL polytetrafluoroethylene liner, heated to 120 °C and maintained for 2 hours. The precipitate was collected by centrifugation, washed with ethanol and deionized water, and dried in a vacuum drying oven at 60 °C for 6 hours to obtain MoO. 3-x@ZnIn2S4, used as a control sample.
[0046] Weigh 0.30 g of indium chloride tetrahydrate, 0.07 g of zinc chloride, and 0.15 g of thioacetamide and add them to 20 mL of ethanol solution, stirring continuously until a homogeneous solution is obtained. Then, transfer the mixture to a 50 mL polytetrafluoroethylene-lined container, heat to 120 °C and maintain for 2 h, centrifuge to collect the precipitate, wash with ethanol and deionized water, and dry in a vacuum drying oven at 60 °C for 6 h to obtain ZnIn2S4, which was used as a control sample.
[0047] Application Example 5
[0048] The photocatalytic hydrogen production performance was tested in a closed Labsoler6 photocatalytic system. A 300W xenon lamp with a filter to control the incident light wavelength λ≥420nm was used as a stable light source. The amount of hydrogen produced was collected and analyzed using a GB-9890 gas chromatograph. The specific operating steps are as follows: 20mg of the prepared catalyst material was weighed and dispersed in 80mL of a mixed solution containing triethanolamine (10vol%) as a sacrificial agent, and then subjected to appropriate ultrasonic treatment to form a relatively homogeneous dispersion. The reaction solution was then poured into a reactor and connected to the device. Continuous magnetic stirring was performed, and the system was evacuated during stirring. Then, 20mL of high-purity Ar was injected using a syringe. Throughout the reaction, the system temperature was kept constant at 25℃ using a circulating water cooling system. The amount of hydrogen produced was collected every half hour after the reaction started. The production of MoS2@ZnIn2S4 and MoO was also tested. 3-x The average rates of ZnIn2S4 and ZnIn2S4 over four hours were 3965 μmol g. -1 h -1 2720 μmol g -1 h -1 and 778 μmol g -1 h -1 .
[0049] Figure 1 MoS2 / MoO obtained by high-temperature calcination 3-x The X-ray diffraction pattern of MoS2 / MoO is shown in the figure. 3-x The diffraction peaks at 26.0°, 37.0°, 53.6°, and 66.8° point well to the standard card for MoS2 (PDF#37-1492). Furthermore, the diffraction peaks at 14.4°, 33.4°, and 60.4° belong to MoO2 (PDF#62-0671). These results indicate that the prepared MoS2 / MoO2... 3-x It is composed of MoS2 and MoO 3-x Composite materials.
[0050] Figure 2 for MoS2 / MoO 3-x MoS2 / MoO 3-x X-ray diffraction patterns of ZnIn2S4 and ZnIn2S4. MoS2 / MoO 3-x MoS2 / MoO2 was observed simultaneously at the ZnIn2S4 peak position. 3-x The diffraction peaks of ZnIn2S4 indicate the successful composite of these two materials.
[0051] Figure 3 MoS2 / MoO obtained by calcination 3-x The scanning electron microscope (SEM) image shows that the composite material exhibits an aggregated morphology of particles and flakes of different sizes.
[0052] Figure 4 The image shows a scanning electron microscope (SEM) image of the prepared pure ZnIn2S4. The SEM image shows that the material exhibits a flower-like microsphere morphology formed by the aggregation of two-dimensional nanosheets.
[0053] Figure 5 For different MoS2 / MoO 3-x MoS2 / MoO prepared by content 3-x The photocatalytic hydrogen production rate of @ZnIn2S4 can be seen from the comparison. The added MoS2 / MoO2... 3-x 10MoS2 / MoO2 prepared with a mass of 10 mg 3-x @ZnIn2S4 exhibits the highest reaction rate and the best catalytic hydrogen evolution performance.
[0054] Figure 6 For MoS2@ZnIn2S4, MoO 3-x @ZnIn2S4、MoS2 / MoO 3-x The photocatalytic hydrogen production rate graphs of ZnIn2S4 and pure ZnIn2S4 show that the composite MoS2 / MoO ... 3-x The hydrogen production rate of @ZnIn2S4 is higher than that of MoS2@ZnIn2S4 and MoO. 3-x @ZnIn2S4 exhibits a higher hydrogen production rate, significantly higher than that of unmodified ZnIn2S4. This leads to the conclusion that MoS2 / MoO... 3-x The introduction of [a specific ingredient] greatly influenced the photocatalytic hydrogen evolution process of ZnIn2S4, resulting in faster reaction kinetics.
[0055] Figure 7 for MoS2 / MoO 3-x @ZnIn2S4、MoS2 / MoO 3-xA comparison of the UV-Vis diffuse reflectance spectra of ZnIn2S4 and MoS2 / MoO shows that the absorption edge of ZnIn2S4 is around 500 nm, while that of MoS2 / MoO2 is much smaller. 3-x It exhibits strong absorption in the 380–800 nm range. Notably, the MoS2 / MoO supported... 3-x After that, MoS2 / MoO 3-x The ZnIn2S4 sample exhibits an absorption edge similar to ZnIn2S4, but its visible light capture capability is enhanced compared to ZnIn2S4, accompanied by a redshift of the absorption edge, indicating improved visible light utilization of the material.
[0056] Although the relevant content of this invention has been demonstrated through the above examples and methods, the scope of protection disclosed in this invention is not limited thereto. Modifications and alterations to this invention by those skilled in the art, after reading the above materials, should fall within the scope of protection of this invention.
Claims
1. A transition metal sulfide / oxide modified bimetallic sulfide composite material, its preparation method, and its application, characterized in that: MoS2 / MoO can be prepared in one step by calcination of a mixture of ammonium molybdate and thiourea. 3-x The composite was then added to an ethanol solution containing indium chloride tetrahydrate, zinc chloride, and thioacetamide, and the aforementioned transition metal hydroxide / oxide modified bimetallic sulfide composite material was prepared by a solvothermal method.
2. The method for preparing the transition metal sulfide / oxide modified bimetallic sulfide composite material according to claim 1, characterized in that: The specific preparation steps include: (1) Weigh out ammonium molybdate and thiourea separately, place them in a mortar, and grind them continuously until a fine and uniform powder is formed. Place the ground raw material in a magnetic boat, and then place it in a tube furnace for calcination under a nitrogen atmosphere to obtain MoS2 / MoO. 3-x (2) The MoS2 / MoO obtained above 3-x The solution was added to an ethanol solution containing indium chloride tetrahydrate, zinc chloride, and thioacetamide, and ultrasonically dispersed for 30 minutes to obtain a mixed solution. Finally, the prepared solution was placed in a polytetrafluoroethylene-lined reactor, solvothermal treated, and vacuum dried to obtain MoS2 / MoO2. 3-x @ZnIn2S4 composite material.
3. The method for preparing the transition metal sulfide / oxide modified bimetallic sulfide composite material according to claim 2, characterized in that: The molar ratio of ammonium molybdate and thiourea weighed in step (1) is 1:
21.
4. The method for preparing the transition metal sulfide / oxide modified bimetallic sulfide composite material according to claim 2, characterized in that: In step (1), the calcination temperature in the tube furnace is 380℃, the duration is 3h, and the inert gas used in the gas atmosphere is N2. The MoS2 / MoO2 composite can be directly obtained through a single calcination method.
5. The method for preparing the transition metal sulfide / oxide modified bimetallic sulfide composite material according to claim 2, characterized in that: In step (2), the molar ratio of zinc source, indium source and sulfur source is 1:2:4, and the volume of ethanol used is 20 mL.
6. The method for preparing the transition metal sulfide / oxide modified bimetallic sulfide composite material according to claim 2, characterized in that: Step (2) The solvothermal reaction is maintained at a temperature of 120°C for 2 hours.
7. The method for preparing the transition metal sulfide / oxide modified bimetallic sulfide composite material according to claim 2, characterized in that: Step (2) Vacuum drying temperature is 60℃, time is 6h.
8. A transition metal sulfide / oxide modified bimetallic sulfide composite material prepared by the method according to any one of claims 1-10.
9. The application of a transition metal sulfide / oxide modified bimetallic sulfide composite material prepared by the method according to any one of claims 1-10 in photocatalytic hydrogen evolution.