阅读说明：本技术 二硒化镍/硫铟锌复合光催化剂及其制备方法和应用 (Nickel diselenide/sulfur indium zinc composite photocatalyst and preparation method and application thereof ) 是由 黄彩进 赖利娟 于 2021-03-11 设计创作，主要内容包括：本发明公开了一种0D/2D NiSe-2/ZnIn-2S-4复合光催化剂及其制备方法和其在可见光催化分解水产氢方面的应用。该复合光催化剂以二维ZnIn-2S-4纳米片组装的花状微球为主体,在其表面均匀的负载零维NiSe-2纳米颗粒而构成。本发明构建了NiSe-2纳米颗粒与ZnIn-2S-4纳米片间紧密的界面接触,充分暴露了反应位点且利于光生电子#空穴对的有效分离。且NiSe-2纳米粒子具有良好的导电性及高功函特性,有利于电荷的快速转移。与单纯ZnIn-2S-4的相比,本方法制备的复合光催化剂在可见光下光催化活性明显提高并具有良好的稳定性。本发明制备方法简单,条件温和,原料来源丰富,成本低,环境友好,易于大规模推广。(The invention discloses 0D/2D NiSe 2 /ZnIn 2 S 4 A composite photocatalyst, a preparation method thereof and application thereof in hydrogen production by visible light catalytic decomposition of water. The composite photocatalyst is two-dimensional ZnIn 2 S 4 The flower-shaped microspheres assembled by the nano sheets are taken as main bodies, and zero-dimensional NiSe is uniformly loaded on the surfaces of the flower-shaped microspheres 2 Nanoparticles. The invention constructs NiSe 2 Nanoparticles and ZnIn 2 S 4 The close interfacial contact between the nano sheets fully exposes reaction sites and facilitates the effective separation of hole pairs of the photo-generated electrons ‒. And NiSe 2 The nano particles have good conductivity and high work function characteristic, and are favorable for quick charge transferAnd (6) moving. And pure ZnIn 2 S 4 Compared with the prior art, the composite photocatalyst prepared by the method has the advantages that the photocatalytic activity is obviously improved under visible light, and the composite photocatalyst has good stability. The preparation method is simple, mild in condition, rich in raw material source, low in cost, environment-friendly and easy to popularize on a large scale.)

1. 0D/2D NiSe₂/ZnIn₂S₄The composite photocatalyst is characterized in that: the composite photocatalyst is two-dimensional ZnIn₂S₄Nano-sheet assembled flower-shaped microsphere loaded NiSe₂Nanoparticles.

2. The 0D/2D NiSe of claim 1₂/ZnIn₂S₄The composite photocatalyst is characterized in that: the ZnIn₂S₄The diameter of the microsphere is 300 ‒ 500 nm; the NiSe₂The particle size of the nano-particles is 30 ‒ 50 nm.

3. The 0D/2D NiSe of claim 1 or 2₂/ZnIn₂S₄The composite photocatalyst is characterized in that: the NiSe₂And ZnIn₂S₄Is 0.3 ‒ 10: 100.

4. The 0D/2D NiSe of claim 1, 1 ‒ 3₂/ZnIn₂S₄The preparation method of the composite photocatalyst is characterized by comprising the following steps: the method comprises the following steps:

(1) hydrothermal method for preparing zero-dimensional NiSe₂Nanoparticles

1) Dissolving selenium powder and sodium hydroxide in deionized water, uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, and reacting at a constant temperature of 180 ℃ for 12 hours to obtain NaHSe solution;

2) dissolving nickel nitrate hexahydrate, sodium citrate and hexamethylene tetramine in deionized water, uniformly stirring, transferring the mixed solution into a high-pressure reaction kettle, reacting at a constant temperature of 120 ℃ for 12 hours, cooling, adding NaHSe solution, transferring the mixed solution into the high-pressure reaction kettle, reacting at a constant temperature of 140 ℃ for 12 hours, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, and drying to obtain zero-dimensional NiSe₂A nanoparticle;

(2) solvothermal method for preparing 0D/2D NiSe₂/ZnIn₂S₄Composite photocatalyst

The zero-dimensional NiSe obtained in the step (1)₂Dispersing the nanoparticles in absolute ethyl alcohol and performing ultrasonic treatment for 30 min, dissolving zinc chloride, indium chloride and thioacetamide as a zinc source, an indium source and a sulfur source in the ethanol solution respectively, stirring uniformly, transferring to a high-pressure reaction kettle, keeping the temperature at 120 ℃ for 2 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, and drying to obtain 0D/2D NiSe₂/ZnIn₂S₄A composite photocatalyst is provided.

5. The 0D/2D NiSe of claim 4₂/ZnIn₂S₄The preparation method of the composite photocatalyst is characterized by comprising the following steps: in the step (1), the molar ratio of nickel nitrate hexahydrate, sodium citrate and hexamethylene tetramine is 1: 1: 2.5.

6. The 0D/2D NiSe of claim 4₂/ZnIn₂S₄The preparation method of the composite photocatalyst is characterized by comprising the following steps: the zero-dimensional NiSe added in the step (2)₂The mass range of the nano particles is 1.26-42 mg.

7. The 0D/2D NiSe of claim 4₂/ZnIn₂S₄The preparation method of the composite photocatalyst is characterized by comprising the following steps: in the step (2), the molar ratio of zinc chloride to indium chloride to thioacetamide is 1: 2: 4.

8. The 0D/2D NiSe of claim 1₂/ZnIn₂S₄The application of the composite photocatalytic photocatalyst is characterized in that: the method is used for hydrogen production by photocatalytic decomposition of water with visible light.

Technical Field

The invention belongs to the technical field of photocatalytic materials, and particularly relates to 0D/2D NiSe₂/ZnIn₂S₄A composite photocatalyst, a preparation method thereof and application thereof in hydrogen production by visible light catalytic decomposition of water.

Background

The excessive use of fossil fuels causes a great deal of environmental pollution problems, and the search for clean energy is very important. The hydrogen energy has the advantages of high energy density, environmental friendliness, recyclability and the like, and is an important substitute for future fossil fuels. Therefore, the semiconductor photocatalysis technology is used for converting solar energy into hydrogen energy, and has great significance for relieving the current energy shortage and environmental pollution conditions.

The sulfur indium zinc is an important semiconductor photocatalytic material with an energy positive response under visible light, and has a controllable energy band structure (2.06 ‒ 2.85 eV). Over the past decades, zinc indium sulfide has been widely used in dye degradation, carbon dioxide reduction, photocatalytic water splitting to produce hydrogen, and the like. However, the photocatalytic performance of the sulfur indium zinc material is greatly limited by the defects of rapid recombination of photogenerated electron and hole pairs, poor carrier mobility and the like. Currently, many strategies have been adopted to improve the photocatalytic performance of zinc indium sulfide, such as: noble metals (Pt, Au) and sulfur indium zinc are compounded, so that the photocatalytic performance is improved. However, noble metals are expensive, greatly limiting their widespread use. Therefore, it is important to find cheaper materials to compound with zinc indium sulfide and improve the photocatalytic performance.

Disclosure of Invention

The invention aims to provide 0D/2D NiSe with more efficient photocatalytic performance₂/ZnIn₂S₄A composite photocatalyst, a preparation method thereof and application thereof in hydrogen production by visible light catalytic decomposition of water. The invention constructs NiSe₂Nanoparticles and ZnIn₂S₄The close interface contact among the nano sheets fully exposes reaction sites, is beneficial to the effective separation of a photogenerated electron ‒ hole pair, shows excellent activity in the visible light catalytic decomposition of water to produce hydrogen andand (4) stability.

In order to achieve the purpose, the invention adopts the following technical scheme:

0D/2D NiSe₂/ZnIn₂S₄A composite photocatalyst which is prepared from two-dimensional ZnIn₂S₄The nano-sheet assembled flower-shaped microspheres are used as a carrier, and the surface of the nano-sheet assembled flower-shaped microspheres is uniformly loaded with zero-dimensional NiSe₂Nanoparticles; wherein, the zero-dimensional nano-particle NiSe₂And two-dimensional ZnIn₂S₄The mass ratio of the nanosheets was 0.3% ‒ 10%.

The two-dimensional ZnIn₂S₄The diameter of the flower-shaped microsphere assembled by the nano-sheets is 300-500 nm; the zero-dimensional NiSe₂The particle size of the nanoparticles was 30 ‒ 50 nm.

The 0D/2D NiSe of the invention₂/ZnIn₂S₄The preparation method of the composite photocatalyst specifically comprises the following steps:

(1) hydrothermal method for preparing zero-dimensional NiSe₂Nanoparticles

0.228 g of selenium powder and 2.857 g of sodium hydroxide are dissolved in 25 mL of deionized water and stirred uniformly, then the mixed solution is transferred to a high-pressure reaction kettle to react for 12 hours at a constant temperature of 180 ℃, and the obtained solution is NaHSe solution.

Dissolving nickel nitrate hexahydrate, sodium citrate and hexamethylene tetramine in 40 mL of deionized water according to the molar ratio of 1: 1: 2.5, stirring for 30 min, and transferring the mixed solution into a high-pressure reaction kettle to react for 12 h at the constant temperature of 120 ℃. After cooling, adding NaHSe solution, transferring the mixed solution into a high-pressure reaction kettle, reacting at the constant temperature of 140 ℃ for 12 hours, naturally cooling to room temperature, washing the obtained precipitate for multiple times by deionized water, and drying to obtain zero-dimensional NiSe₂And (3) nanoparticles.

(2) Solvothermal method for preparing 0D/2D NiSe₂/ZnIn₂S₄Composite photocatalyst

Weighing the zero-dimensional NiSe obtained in the step (1)₂Dispersing the nanoparticles in absolute ethanol and performing ultrasonic treatment for 30 min, dissolving zinc chloride, indium chloride and thioacetamide in the ethanol solution as zinc source, indium source and sulfur source respectively at a molar ratio of 1: 2: 4, stirringStirring, transferring to high pressure reactor, keeping constant temperature at 120 deg.C for 2 hr, naturally cooling to room temperature, washing the obtained precipitate with deionized water for several times, and drying to obtain 0D/2D NiSe₂/ZnIn₂S₄A composite photocatalyst is provided.

The zero-dimensional NiSe added in the step (2) is₂The mass range of the nano particles is 1.26-42 mg.

0D/2D NiSe mentioned in the step (2) above₂/ZnIn₂S₄NiSe in composite photocatalyst₂Nanoparticles and ZnIn₂S₄The mass ratio of the nano sheets is 0.3-10%.

The 0D/2D NiSe₂/ZnIn₂S₄The composite photocatalyst can be applied to photocatalytic hydrogen production under visible light.

The invention has the following remarkable advantages:

(1) the invention provides 0D/2D NiSe₂/ZnIn₂S₄The preparation method of the composite photocatalyst has the advantages of simple steps, easy operation, no use of a template agent and a surfactant, avoidance of transitional consumption of chemical raw materials and energy, strong controllability, mild conditions and contribution to large-scale popularization.

(2) The invention firstly uses NiSe₂Nanoparticles and ZnIn₂S₄The flower-shaped microspheres assembled by the nanosheets are compounded, a composite photocatalytic system with close interface contact is constructed, a Schottky junction is formed, and rapid transfer of electrons is facilitated; NiSe-loaded substrate₂After the nano particles are formed, more active sites are exposed in the catalyst, no noble metal is involved, the production cost is greatly saved, and the catalyst is based on ZnIn₂S₄The heterojunction design and the application thereof in photocatalytic hydrogen production provide some new ideas.

(3) 0D/2D NiSe prepared by the invention₂/ZnIn₂S₄The composite photocatalyst is applied to hydrogen production by photolysis of water under visible light, can effectively convert solar energy into chemical energy, and has high stability and high practical value.

(4) 0 prepared by the inventionD/2D NiSe₂/ZnIn₂S₄The composite photocatalyst has better visible light photocatalytic hydrogen production performance, and is compared with ZnIn singly loaded with nickel atoms or selenium atoms₂S₄ Composite photocatalyst, 0D/2D NiSe₂/ZnIn₂S₄The composite photocatalyst has better stability under visible light.

Drawings

FIG. 1 shows ZnIn of the present invention₂S₄、 NiSe₂And 0D/2D NiSe obtained in examples 1 to 6₂/ZnIn₂S₄An X-ray diffraction pattern of the composite;

FIG. 2 shows ZnIn of the present invention₂S₄ (a)、NiSe₂ (b)、1.0 wt% NiSe₂/ZnIn₂S₄ (c)、10 wt% NiSe₂/ZnIn₂S₄ (d) Scanning Electron microscopy of the Material and 1.0 wt% NiSe₂/ZnIn₂S₄Transmission electron micrographs (e) and high resolution transmission electron micrographs (f);

FIG. 3 shows 1.0 wt% NiSe in the present invention₂/ZnIn₂S₄Selecting an element distribution diagram of the composite photocatalyst;

FIG. 4 shows ZnIn of the present invention₂S₄And 0D/2D NiSe₂/ZnIn₂S₄A comparison graph of the activity of the composite photocatalyst for photolyzing water to produce hydrogen;

FIG. 5 shows 1.0 wt% NiSe in the present invention₂/ZnIn₂S₄A long-time hydrogen production circulation experimental diagram of the composite photocatalyst.

Detailed Description

In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.

The preparation steps of the invention are as follows:

(1) hydrothermal method for preparing zero-dimensional NiSe₂Nanoparticles

0.228 g of selenium powder and 2.857 g of sodium hydroxide are dissolved in 25 mL of deionized water and stirred, the mixed solution is transferred to a high-pressure reaction kettle to react for 12 hours at a constant temperature of 180 ℃, and the obtained solution is NaHSe solution.

Dissolving nickel nitrate hexahydrate (0.1 mmol), sodium citrate (0.1 mmol) and hexamethylene tetramine (0.25 mmol) in 40 mL of deionized water, stirring for 30 min, and transferring the mixed solution to an autoclave for constant-temperature reaction at 120 ℃ for 12 h. After cooling, adding NaHSe solution, transferring the mixed solution into a high-pressure reaction kettle, reacting at the constant temperature of 140 ℃ for 12 hours, naturally cooling to room temperature, washing the obtained precipitate for multiple times by deionized water, and drying to obtain NiSe₂And (3) powder.

(2) Solvothermal method for preparing 0D/2D NiSe₂/ZnIn₂S₄Composite photocatalyst

Weighing the NiSe obtained in the step (1)₂Dispersing the powder in absolute ethyl alcohol and performing ultrasonic treatment for 30 min, dissolving zinc chloride, indium chloride and thioacetamide in the ethanol solution as a zinc source, an indium source and a sulfur source respectively according to a molar ratio of 1: 2: 4, uniformly stirring, transferring to a high-pressure reaction kettle, keeping the temperature at 120 ℃ for 2 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, and drying to obtain 0D/2D NiSe₂/ZnIn₂S₄A composite photocatalyst is provided.

NiSe added in the step (2)₂The mass range of the powder was 1.26 ‒ 42 mg.

Example 1

(1) Hydrothermal method for preparing zero-dimensional NiSe₂Nanoparticles

0.228 g of selenium powder and 2.857 g of sodium hydroxide are dissolved in 25 mL of deionized water and stirred, the mixed solution is transferred to a high-pressure reaction kettle to react for 12 hours at a constant temperature of 180 ℃, and the obtained solution is NaHSe solution.

Dissolving nickel nitrate hexahydrate (0.1 mmol), sodium citrate (0.1 mmol) and hexamethylene tetramine (0.25 mmol) in 40 mL of deionized water, stirring for 30 min, and transferring the mixed solution to an autoclave for constant-temperature reaction at 120 ℃ for 12 h. After cooling, adding NaHSe solution, transferring the mixed solution into a high-pressure reaction kettle, reacting for 12 hours at the constant temperature of 140 ℃, naturally cooling to room temperature, washing the obtained precipitate for multiple times by deionized water, drying,obtaining NiSe₂And (3) powder.

(2) Solvothermal method for preparing 0D/2D NiSe₂/ZnIn₂S₄Composite photocatalyst

Weighing 1.26 mg of NiSe obtained in the step (1)₂Dispersing the powder in absolute ethyl alcohol and performing ultrasonic treatment for 30 min, dissolving zinc chloride, indium chloride and thioacetamide respectively serving as a zinc source, an indium source and a sulfur source in the ethanol solution according to a molar ratio of 1: 2: 4, uniformly stirring, transferring the solution to a high-pressure reaction kettle, keeping the temperature at 120 ℃ for 2 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, and drying to obtain 0.3 wt% NiSe₂/ZnIn₂S₄A composite photocatalyst is provided.

Example 2

(1) Hydrothermal method for preparing zero-dimensional NiSe₂Nanoparticles

0.228 g of selenium powder and 2.857 g of sodium hydroxide are dissolved in 25 mL of deionized water and stirred, the mixed solution is transferred to a high-pressure reaction kettle to react for 12 hours at a constant temperature of 180 ℃, and the obtained solution is NaHSe solution.

Dissolving nickel nitrate hexahydrate (0.1 mmol), sodium citrate (0.1 mmol) and hexamethylene tetramine (0.25 mmol) in 40 mL of deionized water, stirring for 30 min, and transferring the mixed solution to an autoclave for constant-temperature reaction at 120 ℃ for 12 h. After cooling, adding NaHSe solution, transferring the mixed solution into a high-pressure reaction kettle, reacting at the constant temperature of 140 ℃ for 12 hours, naturally cooling to room temperature, washing the obtained precipitate for multiple times by deionized water, and drying to obtain NiSe₂And (3) powder.

(2) Solvothermal method for preparing 0D/2D NiSe₂/ZnIn₂S₄Composite photocatalyst

Weighing 2.1 mg of NiSe obtained in the step (1)₂Dispersing the powder in absolute ethyl alcohol and performing ultrasonic treatment for 30 min, dissolving zinc chloride, indium chloride and thioacetamide respectively serving as a zinc source, an indium source and a sulfur source in the ethanol solution according to a molar ratio of 1: 2: 4, uniformly stirring, transferring the solution to a high-pressure reaction kettle, keeping the temperature at 120 ℃ for 2 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, and drying to obtain 0.5 wt% 0D/2D NiSe₂/ZnIn₂S₄A composite photocatalyst is provided.

Example 3

(1) Hydrothermal method for preparing zero-dimensional NiSe₂Nanoparticles

0.228 g of selenium powder and 2.857 g of sodium hydroxide are dissolved in 25 mL of deionized water and stirred, the mixed solution is transferred to a high-pressure reaction kettle to react for 12 hours at a constant temperature of 180 ℃, and the obtained solution is NaHSe solution.

Dissolving nickel nitrate hexahydrate (0.1 mmol), sodium citrate (0.1 mmol) and hexamethylene tetramine (0.25 mmol) in 40 mL of deionized water, stirring for 30 min, and transferring the mixed solution to an autoclave for constant-temperature reaction at 120 ℃ for 12 h. After cooling, adding NaHSe solution, transferring the mixed solution into a high-pressure reaction kettle, reacting at the constant temperature of 140 ℃ for 12 hours, naturally cooling to room temperature, washing the obtained precipitate for multiple times by deionized water, and drying to obtain NiSe₂And (3) powder.

(2) Solvothermal method for preparing 0D/2D NiSe₂/ZnIn₂S₄Composite photocatalyst

Weighing 4.2 mg of NiSe obtained in the step (1)₂Dispersing the powder in absolute ethyl alcohol and performing ultrasonic treatment for 30 min, dissolving zinc chloride, indium chloride and thioacetamide respectively serving as a zinc source, an indium source and a sulfur source in the ethanol solution according to a molar ratio of 1: 2: 4, uniformly stirring, transferring the solution to a high-pressure reaction kettle, keeping the temperature at 120 ℃ for 2 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, and drying to obtain 1.0 wt% of 0D/2D NiSe₂/ZnIn₂S₄A composite photocatalyst is provided.

Example 4

(1) Hydrothermal method for preparing zero-dimensional NiSe₂Nanoparticles

0.228 g of selenium powder and 2.857 g of sodium hydroxide are dissolved in 25 mL of deionized water and stirred, the mixed solution is transferred to a high-pressure reaction kettle to react for 12 hours at a constant temperature of 180 ℃, and the obtained solution is NaHSe solution.

Dissolving nickel nitrate hexahydrate (0.1 mmol), sodium citrate (0.1 mmol) and hexamethylene tetramine (0.25 mmol) in 40 mL of deionized water, stirring for 30 min, transferring the mixed solution into a high-pressure reaction kettle, and reacting at constant temperature of 120 DEG CAnd the time is 12 hours. After cooling, adding NaHSe solution, transferring the mixed solution into a high-pressure reaction kettle, reacting at the constant temperature of 140 ℃ for 12 hours, naturally cooling to room temperature, washing the obtained precipitate for multiple times by deionized water, and drying to obtain NiSe₂And (3) powder.

(2) Solvothermal method for preparing 0D/2D NiSe₂/ZnIn₂S₄Composite photocatalyst

Weighing 8.4 mg of NiSe obtained in the step (1)₂Dispersing the powder in absolute ethyl alcohol and performing ultrasonic treatment for 30 min, dissolving zinc chloride, indium chloride and thioacetamide respectively serving as a zinc source, an indium source and a sulfur source in the ethanol solution according to a molar ratio of 1: 2: 4, uniformly stirring, transferring the solution to a high-pressure reaction kettle, keeping the temperature at 120 ℃ for 2 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, and drying to obtain 2.0 wt% of 0D/2D NiSe₂/ZnIn₂S₄A composite photocatalyst is provided.

Example 5

(1) Hydrothermal method for preparing zero-dimensional NiSe₂Nanoparticles

0.228 g of selenium powder and 2.857 g of sodium hydroxide are dissolved in 25 mL of deionized water and stirred, the mixed solution is transferred to a high-pressure reaction kettle to react for 12 hours at a constant temperature of 180 ℃, and the obtained solution is NaHSe solution.

Dissolving nickel nitrate hexahydrate (0.1 mmol), sodium citrate (0.1 mmol) and hexamethylene tetramine (0.25 mmol) in 40 mL of deionized water, stirring for 30 min, and transferring the mixed solution to an autoclave for constant-temperature reaction at 120 ℃ for 12 h. After cooling, adding NaHSe solution, transferring the mixed solution into a high-pressure reaction kettle, reacting at the constant temperature of 140 ℃ for 12 hours, naturally cooling to room temperature, washing the obtained precipitate for multiple times by deionized water, and drying to obtain NiSe₂And (3) powder.

(2) Solvothermal method for preparing 0D/2D NiSe₂/ZnIn₂S₄Composite photocatalyst

Weighing 21.2 mg of NiSe obtained in the step (1)₂Dispersing the powder in anhydrous ethanol, performing ultrasonic treatment for 30 min, and dissolving zinc chloride, indium chloride and thioacetamide in the ethanol respectively as zinc source, indium source and sulfur source at molar ratio of 1: 2: 4Stirring the solution uniformly, transferring the solution to a high-pressure reaction kettle, keeping the temperature of the high-pressure reaction kettle at 120 ℃ for 2 hours, naturally cooling the solution to room temperature, washing the obtained precipitate for multiple times by using deionized water, and drying the precipitate to obtain 5.0 wt% of 0D/2D NiSe₂/ZnIn₂S₄A composite photocatalyst is provided.

Example 6

(1) Hydrothermal method for preparing zero-dimensional NiSe₂Nanoparticles

0.228 g of selenium powder and 2.857 g of sodium hydroxide are dissolved in 25 mL of deionized water and stirred, the mixed solution is transferred to a high-pressure reaction kettle to react for 12 hours at a constant temperature of 180 ℃, and the obtained solution is NaHSe solution.

Dissolving nickel nitrate hexahydrate (0.1 mmol), sodium citrate (0.1 mmol) and hexamethylene tetramine (0.25 mmol) in 40 mL of deionized water, stirring for 30 min, and transferring the mixed solution to an autoclave for constant-temperature reaction at 120 ℃ for 12 h. After cooling, adding NaHSe solution, transferring the mixed solution into a high-pressure reaction kettle, reacting at the constant temperature of 140 ℃ for 12 hours, naturally cooling to room temperature, washing the obtained precipitate for multiple times by deionized water, and drying to obtain NiSe₂And (3) powder.

(2) Solvothermal method for preparing 0D/2D NiSe₂/ZnIn₂S₄Composite photocatalyst

Weighing 42 mg of NiSe obtained in the step (1)₂Dispersing the powder in absolute ethyl alcohol and performing ultrasonic treatment for 30 min, dissolving zinc chloride, indium chloride and thioacetamide respectively serving as a zinc source, an indium source and a sulfur source in the ethanol solution according to a molar ratio of 1: 2: 4, uniformly stirring, transferring the solution to a high-pressure reaction kettle, keeping the temperature at 120 ℃ for 2 h, naturally cooling to room temperature, washing the obtained precipitate with deionized water for multiple times, and drying to obtain 10 wt% of 0D/2D NiSe₂/ZnIn₂S₄A composite photocatalyst is provided.

Comparative example 1

Dissolving zinc chloride, indium chloride and thioacetamide respectively serving as a zinc source, an indium source and a sulfur source in an ethanol solution according to a molar ratio of 1: 2: 4, uniformly stirring, transferring the mixture into a high-pressure reaction kettle, keeping the temperature of the high-pressure reaction kettle constant at 120 ℃ for 2 hours, naturally cooling the mixture to room temperature, washing the obtained precipitate for multiple times by using deionized water, and drying the washed precipitate to obtain pure ZnIn₂S₄The catalyst served as a control.

Application example 1

The obtained NiSe powder is 0.3 wt%, 0.5 wt%, 1.0 wt%, 2.0 wt%, 5.0 wt% and 10 wt%₂/ZnIn₂S₄The catalyst is sequentially used for decomposing water to produce hydrogen under visible light, and the method comprises the following specific steps: weighing 20 mg of sample, adding the sample into 100 mL of aqueous solution containing 10 mL of triethanolamine sacrificial agent, placing the solution into a photocatalytic hydrogen production system, and starting a xenon lamp light source to carry out photocatalytic hydrogen production after the system is vacuumized. The amount of photocatalytic hydrogen generation was determined by gas chromatography.

FIG. 1 shows ZnIn of the present invention₂S₄、 NiSe₂And 0D/2D NiSe₂/ZnIn₂S₄X-ray diffraction pattern (XRD) of the composite material. The ZnIn obtained can be seen from FIG. 1₂S₄、 NiSe₂And 0D/2D NiSe₂/ZnIn₂S₄The X-ray diffraction peak of the composite material is matched with the corresponding standard XRD card, which indicates the successful preparation of the catalyst.

FIG. 2 shows ZnIn of the present invention₂S₄ (a)、NiSe₂ (b)、1.0 wt% NiSe₂/ZnIn₂S₄ (c)、10 wt% NiSe₂/ZnIn₂S₄ (d) Scanning Electron microscopy of the Material and 1.0 wt% NiSe₂/ZnIn₂S₄Transmission electron microscopy images (e) and high resolution transmission electron microscopy images (f). FIG. 2a shows the ZnIn produced₂S₄The sample is in a flower-like microsphere shape, and the diameter of the sample is about 500 nm; FIG. 2b shows the NiSe produced₂The sample is in a nanoparticle shape, and the particle size is 30 ‒ 50 nm; scanning Electron microscopy and Transmission Electron microscopy (2 c ‒ 2 e) show NiSe₂The nano particles are successfully loaded in ZnIn₂S₄Nano-sheets; the 0.27 and 0.32 nm lattice fringes in the high resolution TEM (2 f) are due to NiSe, respectively₂(210) plane of (1) and ZnIn₂S₄The (102) crystal face of (i) further proves that NiSe is a crystal having a high crystal grain density₂/ZnIn₂S₄The successful preparation.

FIG. 3 shows 1.0 wt% NiSe in the present invention₂/ZnIn₂S₄Selective element of composite catalystAnd (5) distribution diagram. The uniform distribution of each element in the composite catalyst in the flower-shaped microsphere area is shown.

FIG. 4 shows ZnIn of the present invention₂S₄, NiSe₂, 0D/2D NiSe₂/ZnIn₂S₄A comparison graph of the activity of the composite photocatalyst in water photolysis and hydrogen production. As can be seen, 0D/2D NiSe₂/ZnIn₂S₄The activity of the composite photocatalyst is obviously improved compared with that of a pure sulfur indium zinc catalyst, and the highest hydrogen production rate is improved by about 3.3 times, which shows that the NiSe catalyst provided by the invention₂/ZnIn₂S₄The composite photocatalyst has high-efficiency photocatalytic hydrogen production activity.

FIG. 5 is 1.0 wt% NiSe₂/ZnIn₂S₄A long-time hydrogen production circulation experimental diagram of the composite photocatalyst. As can be seen from the figure, after five light reaction cycles (total 20 h), the activity of the composite catalyst is not obviously reduced, which indicates that the catalyst has better stability.

The preferred embodiments of the present invention described above are only for illustrating the present invention and are not to be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present application shall fall within the scope of the present invention.