阅读说明：本技术 一种在硫化镉上光沉积磷化镍助催化剂的制备方法 (Preparation method of nickel phosphide cocatalyst by performing photo-deposition on cadmium sulfide ) 是由 任守田 盖琪晓 于 2019-11-26 设计创作，主要内容包括：本发明公开了一种在硫化镉上光沉积磷化镍助催化剂的制备方法,包括以下步骤：将氯化镉和硫粉充分溶解于二亚乙基三胺中,并在高压反应釜中80℃加热48小时,待自然冷却后清洗,即得硫化镉纳米片；将硫化镉纳米片配置成硫化镉溶液,并向含有氯化镍和次亚磷酸钠的水溶液中加入硫化镉溶液,待将溶液中的氧气抽取后利用模拟太阳光光源照射,得到硫化镉/磷化镍可见光催化剂。本发明采用光化学还原法在硫化镉纳米片表面负载磷化镍助催化剂,并且利用光照时间调节磷化镍沉积量,具有制备方法简单、快速、效率高和成本低等优点。该硫化镉/磷化镍光催化剂在可见光激发下的制氢效率达到28.7mmolg<Sup>-1</Sup>h<Sup>-1</Sup>,是硫化镉活性的3.9倍。(The invention discloses a method for preparing a nickel phosphide cocatalyst by performing photo-deposition on cadmium sulfide, which comprises the following steps: fully dissolving cadmium chloride and sulfur powder in diethylenetriamine, heating for 48 hours at 80 ℃ in a high-pressure reaction kettle, and cleaning after naturally cooling to obtain cadmium sulfide nanosheets; preparing cadmium sulfide nanosheets into a cadmium sulfide solution, adding the cadmium sulfide solution into an aqueous solution containing nickel chloride and sodium hypophosphite, and irradiating by using a simulated sunlight light source after oxygen in the solution is extracted to obtain the cadmium sulfide/nickel phosphide visible-light-driven photocatalyst. The invention adopts a photochemical reduction method to load a nickel phosphide catalyst promoter on the surface of cadmium sulfide nanosheets, and adjusts the nickel phosphide by utilizing the illumination timeThe deposition amount has the advantages of simple and rapid preparation method, high efficiency, low cost and the like. The hydrogen production efficiency of the cadmium sulfide/nickel phosphide photocatalyst under the excitation of visible light reaches 28.7 mmoleg ‑1 h ‑1 And is 3.9 times of the activity of cadmium sulfide.)

1. A method for preparing nickel phosphide catalyst promoter by photo-deposition on cadmium sulfide is characterized in that: the method comprises the following steps:

(1) preparing cadmium sulfide nanosheets: fully dissolving cadmium chloride and sulfur powder in diethylenetriamine, heating in a high-pressure reaction kettle at 80 ℃ for 48 hours, naturally cooling, cleaning, and drying to obtain cadmium sulfide nanosheets;

(2) preparing cadmium sulfide nanosheet/nickel phosphide: preparing the cadmium sulfide nanosheets in the step (1) into a cadmium sulfide solution, adding the cadmium sulfide solution into an aqueous solution containing nickel chloride and sodium hypophosphite, transferring the mixed solution into a reactor, and irradiating by using a simulated sunlight light source after oxygen in the solution is extracted to obtain the cadmium sulfide/nickel phosphide visible-light-driven photocatalyst.

2. The process of claim 1, wherein the nickel phosphide promoter is prepared by a process comprising: 0.183g of cadmium chloride, 0.16g of sulfur powder, 30ml of diethylenetriamine, 50ml of deionized water, 0.019g of nickel chloride and 0.059g of sodium hypophosphite.

3. The process of claim 1, wherein the nickel phosphide promoter is prepared by a process comprising: the high-pressure reaction kettle in the step (1) is an autoclave with a polytetrafluoroethylene inner container of 50 ml.

4. The process of claim 1, wherein the nickel phosphide promoter is prepared by a process comprising: the drying temperature in the step (1) is 60 ℃.

5. The process of claim 1, wherein the nickel phosphide promoter is prepared by a process comprising: the reactor in the step (2) is a reactor of a full-automatic photocatalytic activity online evaluation system, and the model of the full-automatic photocatalytic activity online evaluation system is CEL-SPH2N-S9, CEAULIGHT.

6. The process of claim 1, wherein the nickel phosphide promoter is prepared by a process comprising: the simulated sunlight light source in the step (2) is a 300-watt xenon lamp, and the irradiation time is 5-30 minutes.

Technical Field

The invention belongs to the technical field of preparation and application of visible light catalytic materials, and particularly relates to a preparation method of a nickel phosphide cocatalyst through photo-deposition on cadmium sulfide.

Background

In recent years, the application of a large amount of fossil fuels causes global energy shortage and environmental pollution, and urgent needs are made for the development of clean energy. The photocatalytic hydrogen production technology utilizes a semiconductor material to absorb electron hole pairs generated by sunlight so as to decompose water molecules into hydrogen and oxygen, thereby perfectly solving the problems of energy shortage and environmental pollution. Cadmium sulfide is the most effective visible light catalyst in the photocatalytic hydrogen production technology, but the problems of serious carrier recombination, light corrosion and the like exist, and therefore a small amount of cocatalyst needs to be loaded on the surface of cadmium sulfide to rapidly separate photon-generated electrons from holes. Platinum is currently the most efficient promoter, but its high cost and low yield prevent its large-scale use. Recently, transition metal phosphide is proved to have high hydrogen production catalytic activity, but the preparation method is complex and the experimental conditions are harsh, so that the development of a simple and effective method for controllably loading the transition metal phosphide on the cadmium sulfide photocatalyst has great significance.

Disclosure of Invention

The invention aims to provide a preparation method of a nickel phosphide promoter by photo-deposition on cadmium sulfide, so as to solve the problems in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a nickel phosphide cocatalyst by performing photo-deposition on cadmium sulfide has the structural key points that: the method comprises the following steps:

(1) preparing cadmium sulfide nanosheets: fully dissolving cadmium chloride and sulfur powder in diethylenetriamine, heating in a high-pressure reaction kettle at 80 ℃ for 48 hours, naturally cooling, cleaning, and drying to obtain cadmium sulfide nanosheets;

(2) preparing cadmium sulfide nanosheet/nickel phosphide: preparing the cadmium sulfide nanosheets in the step (1) into a cadmium sulfide solution, adding the cadmium sulfide solution into an aqueous solution containing nickel chloride and sodium hypophosphite, transferring the mixed solution into a reactor, and irradiating by using a simulated sunlight light source after oxygen in the solution is extracted to obtain the cadmium sulfide/nickel phosphide visible-light-driven photocatalyst.

Preferably, the cadmium chloride is 0.183g, the sulfur powder is 0.16g, the diethylenetriamine is 30ml, the deionized water is 50ml, the nickel chloride is 0.019g, and the sodium hypophosphite is 0.059 g.

Preferably, the high-pressure reaction kettle in the step (1) is an autoclave with a 50ml polytetrafluoroethylene inner container.

Preferably, the temperature for drying in step (1) is 60 ℃.

Preferably, the reactor in the step (2) is a reactor of a full-automatic online photocatalytic activity evaluation system, and the model of the full-automatic online photocatalytic activity evaluation system is CEL-SPH2N-S9, CEAULIGHT.

Preferably, the simulated sunlight light source in the step (2) is a 300-watt xenon lamp, and the irradiation time is 5-30 minutes.

Compared with the prior art, the invention has the beneficial effects that: the invention adopts a photochemical reduction method to load the nickel phosphide catalyst promoter on the surface of the cadmium sulfide nanosheet, and has the advantages of simple and rapid preparation method, high efficiency, low cost and the like. The method adopts a photochemical reduction method to realize the in-situ growth of the nickel phosphide on the cadmium sulfide and ensure that electrons generated on the cadmium sulfide are effectively transferred to the nickel phosphide, thereby inhibiting the recombination of photo-generated electron-hole pairs and improving the visible light catalytic activity of the nickel phosphide. The photocatalytic hydrogen production efficiency reaches 28.7 mmoleg^-1h^-1And is 3.9 times of the activity of cadmium sulfide.

Drawings

FIG. 1 is an XRD spectrum of cadmium sulfide and cadmium sulfide/nickel phosphide in accordance with the present invention;

FIG. 2 is a TEM image (a) and a HRTEM image (b) of a cadmium sulfide/nickel phosphide photocatalyst of the present invention;

FIG. 3 is a diagram of the hydrogen production effect of the cadmium sulfide/nickel phosphide photocatalyst of the present invention under the irradiation of visible light.

Detailed Description

The invention is further explained below with reference to the drawings, without limiting the scope of protection of the invention.

In the description of the present invention, it should be noted that the terms "upper", "lower", "left", "right", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.

A method for preparing nickel phosphide promoter by photo-deposition on cadmium sulfide comprises the following steps:

(1) preparing cadmium sulfide nanosheets: dissolving 0.183g of cadmium chloride and 0.16g of sulfur powder in 30ml of diethylenetriamine, uniformly stirring for 30 minutes, transferring the solution to a 50ml of autoclave with a polytetrafluoroethylene liner, heating the solution at 80 ℃ for 48 hours, naturally cooling the solution, fully washing the solution by using deionized water and ethanol, and drying the solution at 60 ℃ to obtain cadmium sulfide nanosheets;

(2) preparing cadmium sulfide nanosheet/nickel phosphide: preparing the cadmium sulfide nanosheets in the step (1) into a cadmium sulfide solution, adding the cadmium sulfide solution into an aqueous solution containing nickel chloride and sodium hypophosphite, transferring the mixed solution into a reactor, and irradiating by using a simulated sunlight light source after oxygen in the solution is extracted to obtain the cadmium sulfide/nickel phosphide visible-light-driven photocatalyst.

Ultrasonically dispersing 0.02g of cadmium sulfide nanosheets in the step (1) into 20ml of deionized water, respectively dispersing 0.019g of nickel chloride and 0.059g of sodium hypophosphite into 15ml of deionized water, mixing with a cadmium sulfide aqueous solution, transferring into a reactor of a full-automatic online photocatalytic activity evaluation system, evacuating air in the reactor by using a mechanical pump, and carrying out light deposition on nickel phosphide by using a 300 watt xenon lamp as a light source, wherein the illumination time is 5-30 minutes.

The cadmium sulfide/nickel phosphide photocatalyst prepared by the invention is applied to visible light catalytic hydrogen production, a full-automatic online evaluation system with photocatalytic activity is used for carrying out photocatalytic activity test, the hydrogen production amount is detected online, and the photocatalytic activity of the catalyst is evaluated according to the hydrogen production amount of the catalyst per unit mass in unit time. Wherein the test conditions are as follows: the dosage of the catalyst is 0.02g, 20 percent by volume of ethanol is used as a cavity sacrificial agent, the PH value of the solution is equal to 13, the reaction temperature is room temperature, and the light source is a xenon lamp.