Preparation method of NiSSe loaded sulfur-indium-zinc nanosheet film serving as hydrogen evolution photo-thermal catalyst

Abstract

The invention provides a preparation method and application of a NiSSe-loaded sulfur-indium-zinc (ZnIn2S4) nanosheet film serving as a hydrogen evolution photo-thermal catalyst, a NiS-loaded ZnIn2S4 composite material is prepared through photo-deposition, Se is doped through an anion exchange method to obtain a NiSSe-loaded ZnIn2S4 nanosheet film composite material, the photocatalytic hydrolysis hydrogen production rate of the catalyst under simulated sunlight irradiation reaches 256.78 mmol / m < 2 > / h, and the photocatalytic hydrolysis hydrogen production rate of the catalyst under simulated sunlight irradiation reaches 256.78 mmol / m < 2 > / h. The apparent quantum efficiency reaches 16.9% under the irradiation of 420 nm monochromatic wavelength. According to the method, the good conductivity and photo-thermal conversion efficiency of NiSSe are exerted, forward proceeding of the water decomposition reaction can be promoted, meanwhile, compared with a traditional powder material, the film material growing on the FTO is easier to increase the material temperature, recycling is easy, and the requirements for energy conservation and environment protection of industrial production are better met.

Description

Technical Field

[0001] The present invention belongs to the technical field of photothermal catalytic hydrogen production, and particularly relates to a preparation method of a NiSSe-loaded zinc indium sulfide nanosheet thin film composite material as a photothermal catalyst. Background Art

[0002] Compared with traditional photocatalysts, photothermal catalysts improve the utilization rate of sunlight. They use photothermal materials to absorb solar photons to generate heat, especially in the infrared light band, which significantly increases the local temperature of the material and promotes the flow of high-energy hot electrons on the surface. It has been proven that increasing the temperature of the photocatalytic system through the photothermal effect can promote the efficiency of the photocatalytic reaction and better meet the needs of modern industry to save costs. At present, the research on photothermal catalysts mostly uses powder catalysts that are easy to prepare. However, during the photothermal catalytic process, the powder catalysts are directly dispersed in water, and the nanoscale local heat generated at the catalyst-water interface will inevitably be lost to the water, greatly reducing the photothermal catalytic reaction temperature and resulting in a decrease in the photocatalytic hydrogen production efficiency. At the same time, powder materials are difficult to recycle and cannot be efficiently recycled. Therefore, designing a photothermal catalyst that can efficiently utilize the photothermal effect and is easy to recycle has become an urgent problem to be solved. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to propose a preparation method and application of a NiSSe-loaded ZnIn2S4 nanosheet thin film composite material. By restricting the heat transfer during the photothermal catalytic process with the NiSSe / ZnIn2S4 thin film composite material, the material temperature is increased to promote the forward progress of the reaction, the migration of photogenerated electrons is promoted, and more surface active sites are provided to promote the water decomposition reaction. At the same time, the thin film material is easier to recycle, meeting the requirements of industrial production.

[0004] To achieve the above object, the technical solution of the present invention is realized as follows:

[0005] A preparation method of a NiSSe-loaded ZnIn2S4 nanosheet thin film composite material as a hydrogen evolution photothermal catalyst. First, ZnIn2S4 nanosheets are grown on an FTO substrate by a hydrothermal method, then NiS is loaded on the surface of ZnIn2S4 by a photodeposition reduction method to obtain NiS / ZnIn2S4, and then Se ions are doped into the NiS / ZnIn2S4 material by an anion exchange method. The specific steps are as follows:

[0006] (1) Preparation of ZnIn2S4:

[0007] Using zinc nitrate hexahydrate as the zinc source, indium chloride anhydrous as the indium source, thioacetamide as the sulfur source, and ultrapure water as the solvent, prepare solution A and stir it thoroughly in a water bath. Place the treated fluorine-doped tin oxide glass substrate into a 50 ml polytetrafluoroethylene inner container with the FTO side facing down, then slowly pour the prepared solution A into it. Put the inner container into a stainless steel autoclave and seal it. Place the autoclave in a drying oven, heat it, and then let it cool naturally to room temperature. Take out the FTO substrate, rinse it thoroughly with deionized water, and perform annealing treatment to obtain a yellow ZnIn2S4 nanosheet film;

[0008] (2) Preparation of NiS / ZnIn2S4:

[0009] Prepare a mixed solution B containing nickel chloride, thiourea, ethanol, and ultrapure water. Place the ZnIn2S4 nanosheet film obtained in step (1) inside a sealed photoreactor, pour the above-mentioned mixed solution B into the sealed photoreactor, exhaust the air by passing argon gas, and then seal the container. Use a xenon lamp as a simulated sunlight source for irradiation to in-situ grow NiS on the ZnIn2S4 nanosheets to obtain NiS / ZnIn2S4.

[0010] (3) Preparation of NiSSe / ZnIn2S4:

[0011] Dissolve selenium powder and sodium borohydride in ultrapure water, and heat and stir to obtain an aqueous selenium ion solution. Then immerse the NiS / ZnIn2S4 film prepared in step (2) in the aqueous selenium ion solution and let it stand for 1 h. Finally, rinse it three times with deionized water and ethanol respectively to obtain NiSSe / ZnIn2S4.

[0012] Furthermore, in step (1), the mass-volume ratio of zinc nitrate hexahydrate, indium chloride anhydrous, thioacetamide, and the solvent ultrapure water is 0.1189 g:0.1769 g:0.1202 g:30 mL. Stir at room temperature for 30 min, keep it at 140 °C - 160 °C for 6 - 12 h, and the annealing process is to keep it at 200 °C for 30 min under nitrogen protection.

[0013] Furthermore, in step (2), the mass-volume ratio of nickel chloride, thiourea, ultrapure water, and ethanol is 0.24 mg:1.425 mg:10.9 mL:8 mL.

[0014] Furthermore, in step (3), the mass ratio of selenium powder to sodium borohydride is 5 mg:50 mg, and stir in a water bath at 50 °C - 60 °C for 1 h to obtain an aqueous selenium ion solution.

[0015] The present invention also provides a NiSSe-loaded ZnIn2S4 nanosheet film composite material prepared according to the above method.

[0016] The present invention also provides an application of the NiSSe-loaded ZnIn2S4 nanosheet thin film composite material prepared by the above-mentioned preparation method in photocatalytic water splitting for hydrogen production.

[0017] Compared with the prior art, the NiSSe-loaded ZnIn2S4 nanosheet thin film composite material, its preparation method, and application of the present invention have the following advantages:

[0018] The photocatalytic hydrolysis hydrogen production rate of the NiSSe-loaded ZnIn2S4 nanosheet thin film composite material of the present invention under simulated sunlight irradiation reaches 256.78 mmol / m 2 / h, and its apparent quantum efficiency reaches 16.9% under the irradiation of a single 420 nm wavelength. The preparation method has a simple process, low cost, and does not require precious metals. The in-situ growth of NiSSe on the ZnIn2S4 nanosheets is beneficial to electron transfer, and the uniform distribution does not affect the morphology of ZnIn2S4. The composite material has good water splitting hydrogen production ability and photothermal conversion efficiency as a photothermal catalyst. The loaded NiSSe is both a cocatalyst for promoting electron transfer and a photothermal material for increasing the reaction temperature, forming thermally assisted photocatalysis. The thin film sample prepared by the present invention can increase the ambient temperature during the reaction process to promote the forward progress of the water splitting reaction, and the sample is convenient to separate and conducive to reuse. Description of the Drawings

[0019] Figure 1 Among them, a is the SEM plan view of the NiSSe-loaded ZnIn2S4 nanosheets; b is the SEM cross-sectional view of the NiSSe-loaded ZnIn2S4 nanosheets;

[0020] Figure 2 is the SEM-EDS element mapping diagram of the NiSSe-loaded ZnIn2S4 nanosheets;

[0021] Figure 3 Among them, a is the hydrogen production performance test diagram of the ZnIn2S4 nanosheet thin film, the NiS-loaded ZnIn2S4 nanosheet thin film, and the NiSSe-loaded ZnIn2S4 nanosheet thin film under simulated sunlight irradiation; b is the hydrogen production rate test diagram of the ZnIn2S4 nanosheet thin film, the NiS-loaded ZnIn2S4 nanosheet thin film, and the NiSSe-loaded ZnIn2S4 nanosheet thin film under simulated sunlight irradiation; c is the photocatalytic hydrogen production cycle stability test of the NiSSe-loaded ZnIn2S4 nanosheet thin film; d is the apparent quantum efficiency diagram of the NiSSe-loaded ZnIn2S4 nanosheet thin film;

[0022] Figure 4 is the photocatalytic hydrogen production performance diagram of the NiSSe-loaded ZnIn2S4 nanosheet thin film at different temperatures;

[0023] Figure 5Temperature-time change curves of ZnIn2S4 nanosheet thin films, NiS-loaded ZnIn2S4 nanosheet thin films, and NiSSe-loaded ZnIn2S4 nanosheet thin films under light illumination;

[0024] Figure 6 Photothermal imaging diagrams of ZnIn2S4 nanosheet thin films, NiS-loaded ZnIn2S4 nanosheet thin films, and NiSSe-loaded ZnIn2S4 nanosheet thin films under simulated sunlight irradiation in the reaction solution. Detailed implementation manners

[0025] To more clearly elaborate the technical solutions, features, technical means, and specific purposes and effects achieved by the present invention, the following further detailed description of the present invention will be given in conjunction with the accompanying drawings and specific embodiments.

[0026] Transition metal sulfide cocatalysts have a good energy band structure with a suitable band gap and good light absorption ability in the visible and near-infrared light ranges. Among them, nickel sulfide (NiS) has a suitable d-electron configuration, making the Gibbs free energy (ΔGH*) value of surface hydrogen proton adsorption and desorption close to zero. Its metallic nature also endows it with excellent electrical conductivity, making it very suitable as a cocatalyst for photocatalytic hydrogen production. Moreover, since nickel sulfide belongs to a narrow-bandgap semiconductor, it has good light absorption ability and photothermal conversion efficiency, meeting the characteristics that an ideal photocatalyst for a photothermal-assisted system should possess, and enabling it to play a good role in the photothermal catalytic process. However, pure NiS has a high electron-hole recombination rate and is prone to photocorrosion, which limits its application.

[0027] To improve the performance of NiS, the heteroatom doping method is used to optimize the active sites of the original anions and cations, reduce the Gibbs free energy of surface hydrogen proton adsorption and desorption, and promote carrier transfer. The Se element is an efficient non-metallic dopant that can increase the conductivity of the material, adjust the electronic state of the metal center, and optimize the Gibbs free energy of hydrogen proton adsorption. Therefore, it is used to prepare NiSSe materials for participating in the photothermal catalytic reaction. ZnIn2S4, as a typical ternary sulfide, is suitable as a support for the photodeposition growth of NiSSe. At the same time, the photocatalytic activity of ZnIn2S4 is sensitive to temperature, and its activity increases with the increase of temperature.

[0028] The thermally assisted photocatalytic system combines the advantages of photocatalysis and thermocatalysis, which is an ideal strategy to extend the electron lifetime and achieve efficient energy conversion. Compared with single photocatalysis, the photothermal-assisted photocatalytic system improves the utilization rate of sunlight by adding photothermal materials, causing an increase in the local temperature on the catalyst surface, and accelerating the thermodynamic and kinetic transfer processes of the reaction by increasing the entropy of the chemical reaction (ΔS > 0), thereby enhancing the reaction rate. At the same time, the water splitting hydrogen production reaction is a challenging endothermic reaction with a high energy barrier. Providing a high-temperature environment can increase the average kinetic energy of reactant molecules, accelerate the collision frequency and energy between reactant molecules, and effectively promote the progress of the photocatalytic water splitting hydrogen production reaction.

[0029] Experimental materials and instruments

[0030] Experimental raw materials: Zinc nitrate hexahydrate (Sinopharm Chemical Reagent Co., Ltd.), Indium chloride (Shanghai Macklin Biochemical Co., Ltd.), Thioacetamide (Aladdin Reagent Co., Ltd. China), Thiourea (Tianjin Jiangtian Chemical Technology Co., Ltd.), Nickel chloride (Shanghai Huacheng Industry Development Co., Ltd.), Ultra-pure water (resistivity 18.4 MΩ·cm -1 ) collected from the Thermo Scientific GenPure UV-TOC ultra-pure water system.

[0031] Experimental instruments: GC-2014C gas chromatograph (Shimadzu), 300W xenon lamp (Zolix Sirius 300P), oven, electronic balance, other glass instruments, etc.

[0032] Example 1

[0033] A preparation method of a NiSSe-loaded ZnIn2S4 nanosheet thin film composite material provided by the present invention is as follows:

[0034] (1) Preparation of ZnIn2S4:

[0035] ZnIn2S4 nanosheets attached to a fluorine-doped tin oxide glass rigid substrate were prepared by a hydrothermal method; the specific operation steps were as follows: Using zinc nitrate hexahydrate as the zinc source with a dosage of 0.1189 g, indium chloride anhydrous as the indium source with a dosage of 0.1769 g, thioacetamide as the sulfur source with a dosage of 0.1202 g, and 30 mL of ultra-pure water as the solvent to prepare a solution and stir well in a water bath. Place the treated fluorine-doped tin oxide glass substrate into a 50 ml polytetrafluoroethylene inner liner, with the FTO side facing down, then slowly pour the prepared solution, seal the inner liner in a stainless steel high-pressure reaction kettle, transfer the reaction kettle into a drying oven, heat up to 140 °C, keep warm for 6 h, cool down naturally, take out the FTO substrate, thoroughly rinse it with deionized water, and keep it warm at 200 °C for 30 min under nitrogen protection to obtain a ZnIn2S4 nanosheet thin film for the next experiment.

[0036] (2) Preparation of NiS / ZnIn2S4:

[0037] Take 0.24 mg of nickel chloride and 1.425 mg of thiourea, and prepare a NiS growth precursor solution by adding 10.9 ml of ultrapure water and 8 ml of absolute ethanol. Transfer it to a quartz reactor, place a ZnIn2S4 nanosheet film at the bottom, purge with argon for 30 min to exhaust air, irradiate with a 300 W xenon lamp for 30 min, and in-situ grow NiS on the ZnIn2S4 nanosheets to obtain a NiS-loaded ZnIn2S4 thin film composite.

[0038] (3) Preparation of NiSSe / ZnIn2S4:

[0039] Weigh 5 mg of Se powder and 50 mg of NaBH4, dissolve them in 50 mL of deionized water, and stir at 50 °C for 1 hour to obtain an Se 2- aqueous solution. Then immerse the NiS / ZnIn2S4 thin film prepared according to the above conditions in the Se 2- aqueous solution and let it stand for 1 h. Finally, rinse it three times with deionized water and ethanol respectively to obtain a NiSSe-loaded ZnIn2S4 thin film composite.

[0040] Example 2

[0041] A preparation method of a NiSSe-loaded ZnIn2S4 nanosheet thin film composite provided by the present invention is as follows:

[0042] (1) Preparation of ZnIn2S4:

[0043] Prepare ZnIn2S4 nanosheets attached to a fluorine-doped tin oxide glass rigid substrate by hydrothermal method; the specific operation steps are as follows: use zinc nitrate hexahydrate as the zinc source with a dosage of 0.1189 g, anhydrous indium chloride as the indium source with a dosage of 0.1769 g, thioacetamide as the sulfur source with a dosage of 0.1202 g, and 30 mL of ultrapure water as the solvent to prepare a solution and stir it well in a water bath. Place the treated fluorine-doped tin oxide glass substrate into a 50 ml polytetrafluoroethylene inner liner, with the FTO side facing down, then slowly pour the prepared solution into it, put the inner liner into a stainless steel autoclave and seal it, transfer the autoclave into an oven, heat it to 160 °C, keep it warm for 12 h, cool it naturally, take out the FTO substrate, rinse it thoroughly with deionized water, and keep it warm at 200 °C for 30 min under nitrogen protection to obtain a ZnIn2S4 nanosheet thin film for the next experiment.

[0044] (2) Preparation of NiS / ZnIn2S4:

[0045] Take 0.24 mg of nickel chloride, 1.425 mg of thiourea, 10.9 ml of ultrapure water, and 8 ml of anhydrous ethanol to prepare NiS growth precursor solution, transfer it to a quartz reactor, place a ZnIn2S4 nanosheet film on the bottom, pass argon gas for 30 minutes to exhaust the air, use a 300 W xenon lamp to irradiate for 30 minutes, and in situ grow NiS on the ZnIn2S4 nanosheets to obtain a NiS-loaded ZnIn2S4 thin film composite material.

[0046] (3) Preparation of NiSSe / ZnIn2S4:

[0047] Weigh 5 mg of Se powder and 50 mg of NaBH4 and dissolve them in 50 mL of deionized water. Stir at 50 °C for 1 hour to obtain Se 2- Then the NiS / ZnIn2S4 film prepared according to the above conditions is immersed in Se 2- The aqueous solution was allowed to stand for 1 hour and then rinsed with deionized water and ethanol three times respectively to obtain a NiSSe-loaded ZnIn2S4 thin film composite material.

[0048] Example 3

[0049] The present invention provides a method for preparing a NiSSe-loaded ZnIn2S4 nanosheet thin film composite material, and the specific steps are as follows:

[0050] (1) Preparation of ZnIn2S4:

[0051] The ZnIn2S4 nanosheets attached to the fluorine-doped tin oxide glass rigid substrate were prepared by hydrothermal method; the specific operation steps are as follows: 0.1189g of zinc nitrate hexahydrate as zinc source, 0.1769g of anhydrous indium chloride as indium source, 0.1202g of thioacetamide as sulfur source, 30mL of ultrapure water as solvent were prepared into a solution and stirred fully in a water bath. The treated fluorine-doped tin oxide glass substrate was placed in a 50ml polytetrafluoroethylene liner with the FTO side facing down, and then the prepared solution was slowly poured in, the liner was placed in a stainless steel high-pressure reactor and sealed, the reactor was moved into a drying oven, heated to 140℃, kept warm for 6h, cooled naturally, the FTO substrate was taken out and thoroughly rinsed with deionized water and kept warm at 200℃ for 30min under nitrogen protection, and the ZnIn2S4 nanosheet film was obtained for the next experiment.

[0052] (2) Preparation of NiS / ZnIn2S4:

[0053] Take 0.24 mg of nickel chloride, 1.425 mg of thiourea, 10.9 ml of ultrapure water, and 8 ml of anhydrous ethanol to prepare NiS growth precursor solution, transfer it to a quartz reactor, place a ZnIn2S4 nanosheet film on the bottom, pass argon gas for 30 minutes to exhaust the air, use a 300 W xenon lamp to irradiate for 30 minutes, and in situ grow NiS on the ZnIn2S4 nanosheets to obtain a NiS-loaded ZnIn2S4 thin film composite material.

[0054] (3) Preparation of NiSSe / ZnIn2S4:

[0055] Weigh 5 mg of Se powder and 50 mg of NaBH4 and dissolve them in 50 mL of deionized water. Stir at 55 °C for 1 hour to obtain Se 2- Then the NiS / ZnIn2S4 film prepared according to the above conditions is immersed in Se 2- The aqueous solution was allowed to stand for 1 hour and then rinsed with deionized water and ethanol three times respectively to obtain a NiSSe-loaded ZnIn2S4 thin film composite material.

[0056] Example 4

[0057] The present invention provides a method for preparing a NiSSe-loaded ZnIn2S4 nanosheet thin film composite material, and the specific steps are as follows:

[0058] (1) Preparation of ZnIn2S4:

[0059] The ZnIn2S4 nanosheets attached to the fluorine-doped tin oxide glass rigid substrate were prepared by hydrothermal method; the specific operation steps are as follows: 0.1189g of zinc nitrate hexahydrate as zinc source, 0.1769g of anhydrous indium chloride as indium source, 0.1202g of thioacetamide as sulfur source, 30mL of ultrapure water as solvent were prepared into a solution and stirred fully in a water bath. The treated fluorine-doped tin oxide glass substrate was placed in a 50ml polytetrafluoroethylene liner with the FTO side facing down, and then the prepared solution was slowly poured in, the liner was placed in a stainless steel high-pressure reactor and sealed, the reactor was moved into a drying oven, heated to 140℃, kept warm for 6h, cooled naturally, the FTO substrate was taken out and thoroughly rinsed with deionized water and kept warm at 200℃ for 30min under nitrogen protection, and the ZnIn2S4 nanosheet film was obtained for the next experiment.

[0060] (2) Preparation of NiS / ZnIn2S4:

[0061] Take 0.24 mg of nickel chloride and 1.425 mg of thiourea. Take 10.9 ml of ultrapure water and 8 ml of absolute ethanol to prepare a NiS growth precursor solution. Transfer it to a quartz reactor. Place a ZnIn2S4 nanosheet film at the bottom, purge with argon for 30 min to exhaust air, irradiate with a 300 W xenon lamp for 30 min, and in-situ grow NiS on the ZnIn2S4 nanosheets to obtain a NiS-loaded ZnIn2S4 thin film composite material.

[0062] (3) Preparation of NiSSe / ZnIn2S4:

[0063] Weigh 5 mg of Se powder and 50 mg of NaBH4 and dissolve them in 50 mL of deionized water. Stir at 60 °C for 1 hour to obtain an Se 2- aqueous solution. Then immerse the NiS / ZnIn2S4 thin film prepared according to the above conditions in the Se 2- aqueous solution and let it stand for 1 h. Finally, rinse it three times with deionized water and ethanol respectively to obtain a NiSSe-loaded ZnIn2S4 thin film composite material.

[0064] As Figure 1 shown, the microscopic morphology of the NiSSe / ZnIn2S4 thin film is that ZnIn2S4 grows vertically on the FTO surface in the form of an ultrathin layered nanosheet array. The surface of the nanosheets is flat and the layer thickness is uniform. After loading NiSSe, the NiSSe / ZnIn2S4 thin film is still an ultrathin layered nanosheet array structure, and dense and fine nanoparticles appear on the surface of the nanosheets. These uniform and fine particles are NiSSe.

[0065] As Figure 2 shown, the SEM-EDS elemental mapping of the NiSSe / ZnIn2S4 thin film shows that Zn, In, S, Ni, and Se are all uniformly distributed on the sample, which proves that NiSSe is uniformly dispersed on ZnIn2S4.

[0066] Photocatalytic hydrolysis hydrogen production experiment:

[0067] Put the prepared NiS-loaded ZnIn2S4 thin film composite material into a quartz reactor, add 10 ml of benzyl alcohol aqueous solution (2 ml of benzyl alcohol and 8 ml of ultrapure water), transfer the reactor to the gas path, purge with argon for 30 min to exhaust the air in the reactor. Use a 300 W xenon lamp (Zolix Sirius 300P) as the simulated sunlight source, detect the H2 concentration using gas chromatography (Shimadzu, GC2014C), use a TCD detector, and high-purity Ar gas as the carrier gas.

[0068] Photocatalytic hydrolysis temperature-controlled hydrogen production experiment:

[0069] The temperature was controlled by providing a water bath heating to the reactor, and the experiments of photocatalytic water splitting at different temperatures were carried out.

[0070] Photothermal performance test:

[0071] The temperature of the sample during the reaction process was recorded by using a Fluke Ti10 thermal imager.

[0072] Figure 3 It is a comparison chart of the hydrogen production activity and the hydrogen production rate per hour of ZnIn2S4, NiS / ZnIn2S4 and NiSSe / ZnIn2S4 thin films under full-spectrum sunlight irradiation, placed in the surrounding environment (20 °C) without any temperature control, as well as the cyclic test and apparent quantum efficiency test of NiSSe / ZnIn2S4 thin film. The results show that the NiSSe / ZnIn2S4 sample has the highest hydrogen production activity, and the hydrogen production rate is 256.78 mmol / m 2 / h, and the photocatalytic hydrogen production amount reaches 770.74 mmol / m in 3 hours 2 . The hydrogen production rate of the NiSSe / ZnIn2S4 sample exceeds that of the ZnIn2S4 and NiS / ZnIn2S4 samples, indicating that the NiSSe / ZnIn2S4 sample obtained after Se doping is more conducive to improving the photocatalytic water splitting rate, and the photocatalytic hydrolysis hydrogen production performance of ZnIn2S4 with a single NiS load is significantly improved. The NiSSe / ZnIn2S4 sample has stable performance in the 3-cycle 9-hour light irradiation test, and the hydrogen production performance does not decrease significantly. The apparent quantum efficiency at a monochromatic wavelength of 420 nm reaches 16.9%.

[0073] Figure 4 It is the photocatalytic water splitting hydrogen production performance of NiSSe / ZnIn2S4 thin film under different temperature controls. It can be seen that the hydrogen production activity of the material increases with the increase of temperature, indicating that the increase of temperature promotes the forward progress of the hydrogen production reaction.

[0074] Figure 5 It is the curve of the material temperature changing with time of ZnIn2S4, NiS / ZnIn2S4 and NiSSe / ZnIn2S4 thin films under simulated sunlight irradiation. The surface of the NiSSe / ZnIn2S4 thin film can reach 124.3 °C under light irradiation, which is much higher than 94.2 °C of the NiS / ZnIn2S4 thin film and 68.2 °C of the ZnIn2S4 thin film.

[0075] Figure 6Thermal imaging photos of the reaction solution temperature of ZnIn2S4, NiS / ZnIn2S4, and NiSSe / ZnIn2S4 thin films under simulated sunlight illumination. The photothermal conversion efficiency of the NiSSe / ZnIn2S4 thin film is higher than that of the ZnIn2S4 and NiS / ZnIn2S4 thin films. Therefore, the highest solution temperature is 65.5 °C, and the absorbed sunlight is converted into heat to promote the improvement of catalytic activity.

[0076] Finally, it should be noted that the above embodiments are only used for the technical solutions of this invention patent and are not intended to limit it. Although the present invention patent has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments or perform equivalent replacements for the technical features therein. These modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this invention patent.

Claims

1. A preparation method of a composite material of nickel sulfoselenide (NiSSe) loaded with zinc indium sulfide (ZnIn2S4) nanosheet thin films as a hydrogen evolution photothermal catalyst, characterized in that, First, ZnIn2S4 nanosheets are grown on an FTO substrate by a hydrothermal method. Then, NiS is loaded on the surface of ZnIn2S4 by a photoreduction method using photodeposition to obtain NiS / ZnIn2S4. After that, Se ions are doped into the NiS / ZnIn2S4 material by an anion exchange method; the specific steps are as follows: (1) Preparation of ZnIn2S4: A solution A is prepared with zinc nitrate hexahydrate as the zinc source, indium chloride anhydrous as the indium source, thioacetamide as the sulfur source, and ultrapure water as the solvent, and is fully stirred in a water bath. The treated fluorine-doped tin oxide glass substrate is placed in a polytetrafluoroethylene inner liner with the FTO side facing down, and then the prepared solution A is slowly poured in. The inner liner is placed in a stainless steel autoclave and sealed. The autoclave is placed in an oven, heated, and then naturally cooled to room temperature. The FTO substrate is taken out, thoroughly rinsed with deionized water, and annealed to obtain a yellow ZnIn2S4 nanosheet thin film; (2) Preparation of NiS / ZnIn2S4: A mixed solution B containing nickel chloride, thiourea, ethanol, and ultrapure water is prepared. The ZnIn2S4 nanosheet thin film obtained in step (1) is placed inside a sealed photoreactor, and the above mixed solution B is poured into the sealed photoreactor. After purging the air with argon, the container is sealed, and a xenon lamp is used as a simulated sunlight source for irradiation to in-situ grow NiS on the ZnIn2S4 nanosheets to obtain NiS / ZnIn2S4; (3) Preparation of NiSSe / ZnIn2S4: Selenium powder and sodium borohydride are dissolved in ultrapure water and heated and stirred to obtain an aqueous selenium ion solution; then the NiS / ZnIn2S4 thin film prepared in step (2) is immersed in the aqueous selenium ion solution and left standing for 1 - 2 h; finally, it is rinsed with deionized water and ethanol respectively to obtain NiSSe / ZnIn2S4.

2. The preparation method according to claim 1, wherein In step (1), the mass-volume ratio of zinc nitrate hexahydrate, indium chloride anhydrous, thioacetamide, and the solvent ultrapure water is 0.1189 g:0.1769 g:0.1202 g:30 mL, stirred at room temperature, kept at 140 °C - 160 °C for 6 - 12 h, and the annealing process is to keep at 200 °C for 30 - 45 min under nitrogen protection.

3. The preparation method according to claim 1, wherein, In step (2), the mass-volume ratio of nickel chloride, thiourea, ultrapure water, and ethanol is 0.24 mg:1.425 mg:10.9 mL:8 mL.

4. The preparation method according to claim 1, characterized in that, In step (3), the mass ratio of selenium powder to sodium borohydride is 5 mg:50 mg, and an aqueous selenium ion solution is obtained by stirring in a water bath at 50 °C - 60 °C for 0.5 - 1 h.

5. A NiSSe-loaded ZnIn2S4 nanosheet thin film composite material prepared by the preparation method according to any one of claims 1 - 4.

6. Application of the NiSSe-loaded ZnIn2S4 nanosheet thin film composite material according to claim 5 in photocatalytic water splitting for hydrogen production.

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