阅读说明：本技术 一种铜网原位生长三维硫化铜的光催化材料、制备方法及应用 (Photocatalytic material for in-situ growth of three-dimensional copper sulfide on copper mesh, preparation method and application ) 是由 杨艳玲 和茹梅 陈志刚 朱建峰 锁国权 冯雷 叶晓慧 张荔 侯小江 孙瑜 毕雅欣 于 2020-03-25 设计创作，主要内容包括：一种铜网原位生长三维硫化铜的光催化材料、制备方法及应用,所述材料是以一定的电流恒定输出,以石墨为阴极、铜网为阳极、溶液A为电解液阳极氧化,去离子水反复冲洗阳极氧化后的铜网并氮气吹干,得到产物A；将产物A置于氩气中退火得到产物B；直接将产物B作为光催化薄膜材料。催化剂直接原位生长于载体上是的催化剂易于收集清洗与反复使用。该方法制备简便,受外界影响因素少,可大面积均匀制备且使得光催化剂易于回收利用,制备所得的光催化剂太阳光利用率高。本发明所得硫化铜薄膜可用于光催化降解亚甲蓝。(A copper mesh in-situ growth three-dimensional copper sulfide photocatalytic material, a preparation method and application thereof are disclosed, wherein the material is prepared by carrying out anodic oxidation on graphite serving as a cathode, a copper mesh serving as an anode and a solution A serving as an electrolyte with a constant output current, repeatedly washing the copper mesh subjected to anodic oxidation by deionized water, and drying the copper mesh by nitrogen to obtain a product A; placing the product A in argon gas for annealing to obtain a product B; directly taking the product B as a photocatalytic film material. The catalyst directly grows on the carrier in situ is easy to collect, clean and repeatedly use. The method is simple and convenient to prepare, is less influenced by external factors, can be used for large-area uniform preparation, enables the photocatalyst to be easily recycled, and enables the prepared photocatalyst to have high sunlight utilization rate. The copper sulfide film obtained by the invention can be used for photocatalytic degradation of methylene blue.)

1. A preparation method of a photocatalytic material for in-situ growth of three-dimensional copper sulfide on a copper mesh is characterized by comprising the following steps:

immersing the cleaned copper mesh base material in a solution containing Na₂In the electrolyte of S, taking the bottom of a copper mesh as an anode, introducing 5-30 mA current to carry out anodic oxidation reaction, and attaching a black active substance to the bottom surface of the copper mesh to obtain a product A; and annealing the product at 120-200 ℃ in an inert atmosphere to obtain a copper mesh photocatalytic material product B attached with copper sulfide.

2. The method of claim 1, wherein the sodium sulfide provides a sulfur source for the electrolyte; the bottom of the copper net is an anode and provides a copper ion source; na (Na)₂The concentration of the S electrolyte is 0.5-1.5M.

3. The method according to claim 1, wherein the anodic oxidation reaction is performed for 5-30 min under a constant output of 5-30 mA current.

4. The method of claim 1, wherein the inert atmosphere is argon.

5. The method according to claim 1, characterized in that the specific steps comprise:

the method comprises the following steps: cutting a copper mesh into a certain size, sequentially putting the copper mesh into absolute ethyl alcohol, acetone and deionized water for ultrasonic treatment, and soaking the copper mesh in dilute hydrochloric acid with a certain concentration to obtain a plurality of polished copper meshes;

step two: mixing a certain molar amount of Na₂S▪9H₂Dissolving O in 200 ml deionized water to obtain a solution A;

step three: adjusting a triple-constant electrophoresis apparatus, outputting the product with a certain constant current, taking graphite as a cathode, a copper net as an anode and a solution A as electrolyte, anodizing for a certain time, repeatedly washing the anodized copper net with deionized water, and drying the anodized copper net with nitrogen to obtain a product A with black active substances attached to the copper net;

step four: and placing the product A in argon gas, and annealing at a certain temperature for a certain time to obtain a product B of the silver particle modified copper sulfide nanosheet.

6. A photocatalytic material prepared by the method according to any one of claims 1 to 5.

7. Use of the material according to claim 6 for the photocatalytic degradation of methylene blue.

Technical Field

The invention relates to the technical field of photocatalysis, in particular to a preparation method and application of three-dimensional copper sulfide by in-situ growth of a copper mesh.

Background

Energy and environment are two major problems faced by the present society, with the increasing shortage of energy and the continuous deterioration of environment, the global embarrassment of energy shortage and environmental deterioration, the development of new energy and the management of environment are in the forefront, so the development of environment-friendly energy and the management of pollutants are very important subjects. Hydrogen gas is a clean, sustainable new energy source that is one of the candidates for fossil fuel hot substitutes. The photocatalysis technology utilizes clean solar energy to degrade pollutants and produce clean energy hydrogen while cracking water. How to improve the photocatalytic performance is an effective way to solve the current problems of environmental pollution and energy shortage.

In recent years, copper sulfide is favored in the fields of lithium ion batteries, sensors, supercapacitors, photocatalytic hydrogen production and the like, which is mainly due to excellent physicochemical stability, besides, the copper sulfide has a narrow band gap width and a wide photoresponse range, compared with common oxide photocatalysts, the utilization rate of the copper sulfide to sunlight is higher, the conductivity of the copper sulfide is higher by several orders of magnitude than that of corresponding oxides, and the copper sulfide shows higher electron transmission speed in the electrochemical reaction process; copper sulfide is one of the more desirable photocatalysts.

Disclosure of Invention

In order to improve and simplify the repeated utilization rate of the photocatalyst, the invention aims to provide a preparation method of a photocatalytic material for in-situ growth of three-dimensional copper sulfide on a copper mesh.

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

a preparation method of a photocatalytic material for in-situ growth of three-dimensional copper sulfide on a copper mesh comprises the following steps:

the method comprises the following steps: cutting the copper mesh into a certain size, sequentially putting the copper mesh into absolute ethyl alcohol, acetone and deionized water for ultrasonic treatment, and soaking the copper mesh in dilute hydrochloric acid with a certain concentration. Obtaining a plurality of polished copper meshes;

step two: mixing a certain molar amount of Na₂S▪9H₂Dissolving O in 200 ml deionized water to obtain a solution A;

step three: adjusting a triple-constant electrophoresis apparatus, outputting the product with a certain constant current, taking graphite as a cathode, a copper net as an anode and a solution A as electrolyte, anodizing for a certain time, repeatedly washing the anodized copper net with deionized water, and drying the anodized copper net with nitrogen to obtain a product A with black active substances attached to the copper net;

step four: and placing the product A in argon gas, and annealing for a certain time at a certain temperature to obtain a product B attached with the copper sulfide nanosheet.

In the second step, the concentration range of the solvent A is 0.5-1.5M.

In the third step, the anodic oxidation current range is 5-25 mA, and the oxidation time range is 5-30 min.

In the fourth step, the annealing temperature is 120-200 ℃, and the reaction lasts for 2-4 h.

The copper sulfide film prepared by the invention is used for photocatalytic degradation of organic matters containing hydrogen peroxide.

The copper sheet in-situ grown copper sulfide film provided by the invention is in a nano scale, and the copper sulfide nanosheets grown on the copper sheet vertically and uniformly grow on the copper mesh bottom; copper sulfide materials grown in situ on the copper mesh are in a micron scale, copper sulfide grown on the copper mesh is in a sheet structure and smooth in surface, and sheets are mutually connected and vertically and uniformly grow on a copper mesh line.

The preparation method has the advantages of low requirement on preparation equipment, small influence from the outside, simple method, low cost and high controllability, and is suitable for large-scale industrial production.

Drawings

FIG. 1 (a) is a simple schematic diagram of an anodic oxidation apparatus, (B) optical photographs of a product B of example 1 (c and d) scanning electron micrographs before and after oxidation of a copper mesh.

FIG. 2 is a UV-VIS absorption spectrum of a copper sulfide degradation methylene blue degradation liquid in example 1.

Detailed Description

The present invention will be described in further detail below.