阅读说明：本技术 一种具有光解水产氧助催化功能二硫化钴微球的制备方法 (Preparation method of cobalt disulfide microspheres with photocatalytic aquatic oxygen catalysis promoting function ) 是由 张明文 苏淑芬 蓝其玉 程锦添 陈益宾 杨金杯 于 2019-11-07 设计创作，主要内容包括：本发明涉及一种具有光解水产氧助催化功能二硫化钴微球的制备方法,包括以下步骤：1)将钴源加入去离子水中,制成钴离子透明溶液；2)加入含氨基有机物作为表面活性剂到透明溶液中,混合均匀；3)继续加入硫源至步骤2)的溶液中,混合均匀得到前驱物溶液；4)将步骤3)制备的前驱物溶液移入水热反应釜中,将水热反应釜置于程序升温鼓风干燥箱中,选择温控模式进行水热反应；5)水热反应后打开水热反应釜,收集溶液中的沉淀物质,将沉淀物质通过离心或抽滤的方式,在干燥箱中进行干燥即得黑色的具有立方相结构的CoS<Sub>2</Sub>材料。本发明合成工艺流程简单,普适性良好,重复性高,而且合成所需的都是常见、简单的设备,适合批量生产。(The invention relates to a preparation method of cobalt disulfide microspheres with photocatalytic aquatic oxygen assisted catalysis function, which comprises the following steps: 1) adding a cobalt source into deionized water to prepare a cobalt ion transparent solution; 2) adding amino-containing organic substances as a tableAdding the surfactant into the transparent solution, and uniformly mixing; 3) continuously adding a sulfur source into the solution obtained in the step 2), and uniformly mixing to obtain a precursor solution; 4) transferring the precursor solution prepared in the step 3) into a hydrothermal reaction kettle, placing the hydrothermal reaction kettle in a temperature programmed blowing dry box, and selecting a temperature control mode to carry out hydrothermal reaction; 5) opening the hydrothermal reaction kettle after the hydrothermal reaction, collecting the precipitate in the solution, and drying the precipitate in a drying box in a centrifugal or suction filtration mode to obtain black CoS with a cubic phase structure 2 A material. The synthesis process has the advantages of simple flow, good universality and high repeatability, and common and simple equipment is required for synthesis, so that the method is suitable for batch production.)

1. A preparation method of cobalt disulfide microspheres with photocatalytic aquatic oxygen catalysis promoting function is characterized by comprising the following steps:

1) adding a cobalt source into deionized water to prepare a cobalt ion with the concentration of 0.005-0.5 mol.L^-1The transparent solution of (1);

2) adding an amino-containing organic matter serving as a surfactant into the transparent solution obtained in the step 1), and uniformly mixing to enable the molar concentration ratio of the amino-containing organic matter to cobalt ions in the mixed solution to be 2-40: 1;

3) continuously adding a sulfur source into the solution obtained in the step 2), and uniformly mixing to obtain a precursor solution, wherein the molar concentration ratio of sulfur of the sulfur source compound to cobalt ions in the precursor solution is 2-20: 1;

4) transferring the precursor solution prepared in the step 3) into a hydrothermal reaction kettle, wherein the filling degree of the precursor solution is 40% -80%, placing the hydrothermal reaction kettle in a temperature programmed blowing drying oven, and selecting a temperature control mode to carry out hydrothermal reaction;

5) opening the hydrothermal reaction kettle after the hydrothermal reaction, collecting the precipitate in the solution, washing the precipitate by using deionized water and an ethanol solvent in a centrifugal or suction filtration mode, and drying the washed precipitate in a drying box to obtain black CoS with a cubic phase structure₂A material.

2. The method for preparing cobalt disulfide microspheres with oxygen-assisted catalysis function by photolysis water according to claim 1, wherein the cobalt source in step 1) is one of the following inorganic cobalt salts, namely CoCl₂·6H₂O、Co(NO₃)₂·6H₂O、CoSO₄·7H₂O、Co(OAc)₂·4H₂O。

3. The method for preparing cobalt disulfide microspheres with photocatalytic water generation oxygen-assisted catalysis function according to claim 1, wherein the amino-containing organic substance in step 2) is one or a combination of any two of ethylenediamine, ammonia water and diethylenetriamine; when any two are combined, the two are mixed in any ratio.

4. The method for preparing cobalt disulfide microspheres with photocatalytic water yielding oxygen assisted catalysis function according to claim 1, wherein the sulfur source in step 3) is one of carbon disulfide, thiourea and cysteine.

5. The method for preparing cobalt disulfide microspheres with photocatalytic water yielding oxygen assisted catalysis function according to claim 1, wherein the temperature control mode in step 4) is as follows: the heating rate is 1-6 ℃ per minute^-1Keeping the temperature at 160-210 ℃ for 5-48 h.

6. The method for preparing cobalt disulfide microspheres with photocatalytic aquatic oxygen catalysis promoting function according to claim 1, wherein CoS₂When the material is loaded on the photocatalyst, the rate of the photolysis water to generate oxygen half reaction can be effectively promoted.

7. The method for preparing cobalt disulfide microspheres with photocatalytic water yielding oxygen assisted catalysis function according to claim 1, wherein the drying temperature in step 5) is 60 ℃.

Technical Field

The invention relates to the technical field of photocatalysis, in particular to a preparation method and a production method of cobalt disulfide microspheres with photocatalytic water oxygen generation catalysis promoting function.

Background

The photocatalysis technology is to utilize solar energy to excite a semiconductor photocatalyst, the generated holes can oxidize water to obtain oxygen, and the excited electrons reduce water or carbon dioxide to obtain chemical fuels such as hydrogen, methanol and the like. Therefore, the technology has wide application prospect in the aspects of solving energy crisis and environmental pollution.

Currently, one of the key problems of this technology is the oxidation half-reaction of water. It is a half-reaction in which both water decomposition and carbon dioxide reduction occur. This process involves multiple processes such as cleavage of O-H, 4 electron transfer, and O-O linkage. Therefore, the reaction is a large climbing process, and the overpotential is large. Several oxygen-producing semiconductor photocatalysts, such as graphite-like phase carbon nitride, Ta₃N₅，BiVO₄，WO₃Etc., and the efficiency of the reaction for producing oxygen half-reaction still needs to be improved. The main problems are that the valence band positions of the compounds are not deep enough, the oxidation capability is not enough, the recombination of photogenerated electrons and holes is easy to occur, and the photogenerated holes are easy to autooxidize, so that the oxidation selectivity is poor. The above problems can be effectively solved by supporting a suitable cocatalyst. The cocatalyst can reduce the oxygen generation overpotential, increase the active sites on the surface of the catalyst, promote the separation and directional migration of current carriers, and prevent the autoxidation behavior of cavities, thereby improving the efficiency and stability of water oxygen photolysisAnd (4) sex.

At present, more photolysis water oxygen generation promoter systems are compounds of Ru and Ir, and the efficiency of the oxygen generation promoter is higher. However, both Ru and Ir belong to noble metals, which is not favorable for popularization and application. In recent years, transition metal systems of the fourth cycle, such as compounds of Mn, Fe, Co, Ni, etc., have been developed in succession for the production of oxygen promoters. Among these transition metal compounds, Co-based materials have received much attention because of their characteristics of being inexpensive and readily available, being environmentally friendly, having a special electronic structure, being low in the overpotential for oxygen generation in a neutral environment, and the like. Co-Pi, cube Co, Co are developed₃O₄And the like. However, the oxygen-generating promoter efficiency of these materials still remains to be further improved. Therefore, there is a need to provide a new photocatalytic water yielding oxygen promoter that achieves high photocatalytic efficiency when used in conjunction with a semiconductor photocatalyst. The defects of the technology are that when the compounds of Ru and Ir are used as oxygen production promoters, the materials are expensive and are not beneficial to popularization and use; and 2, the photocatalytic efficiency of the photocatalytic water generation and oxygen generation of other transition metal system materials is still to be improved.

Disclosure of Invention

Technical problem to be solved

In order to solve the problems in the prior art, the invention provides a preparation method of cobalt disulfide microspheres with photocatalytic water generation oxygen-assisted catalysis function, and the photocatalytic water generation oxygen-assisted catalysis performance is excellent. When the photocatalyst is compounded with a conventional semiconductor photocatalyst, the oxygen production rate of photocatalytic water can be effectively improved.

(II) technical scheme

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

a preparation method of cobalt disulfide microspheres with photocatalytic aquatic oxygen catalysis promoting function comprises the following steps:

1) adding a cobalt source into deionized water to prepare a cobalt ion with the concentration of 0.005-0.5 mol.L^-1The transparent solution of (1);

2) adding an amino-containing organic matter serving as a surfactant into the transparent solution obtained in the step 1), and uniformly mixing to enable the molar concentration ratio of the amino-containing organic matter to cobalt ions in the mixed solution to be 2-40: 1;

3) continuously adding a sulfur source into the solution obtained in the step 2), and uniformly mixing to obtain a precursor solution, wherein the molar concentration ratio of sulfur of the sulfur source compound to cobalt ions in the precursor solution is 2-20: 1;

4) transferring the precursor solution prepared in the step 3) into a hydrothermal reaction kettle, wherein the filling degree of the precursor solution is 40% -80%, placing the hydrothermal reaction kettle in a temperature programmed blowing drying oven, and selecting a temperature control mode to carry out hydrothermal reaction;

5) opening the hydrothermal reaction kettle after the hydrothermal reaction, collecting precipitate in the solution, washing the precipitate by using deionized water and an ethanol solvent in a centrifugal or suction filtration mode, drying the washed precipitate in a drying box at the drying temperature of 60 ℃ to obtain black CoS with a cubic phase structure₂A material.

Further, the cobalt source in the step 1) is CoCl which is one of the following inorganic cobalt salts₂·6H₂O、Co(NO₃)₂·6H₂O、CoSO₄·7H₂O、Co(OAc)₂·4H₂O。

Further, the amino-containing organic matter in the step 2) is one or any two of ethylenediamine, ammonia water and diethylenetriamine; when any two are combined, the two are mixed in any ratio.

Further, the sulfur source in step 3) is one of carbon disulfide, thiourea and cysteine.

Further, the conditions of the temperature control mode in the step 4) are as follows: the heating rate is 1-6 ℃ per minute^-1Keeping the temperature at 160-210 ℃ for 5-48 h.

Further, CoS₂When the material is loaded on the photocatalyst, the rate of the photolysis water to generate oxygen half reaction can be effectively promoted.

Further, the material is not limited to applications in the field of photocatalytic water generation and oxygen-assisted catalysis.

(III) advantageous effects

The invention has the beneficial effects that: the method adopts a self-induced assembly strategy, utilizes a cobalt salt compound as a cobalt source, a sulfur-containing compound as a sulfur source and an amino-containing organic matter as a surfactant, and obtains the cobalt disulfide microsphere photolysis water oxygen cocatalyst material by hydrothermal reaction, cleaning, centrifugation and normal-pressure drying under a water solvent.

In the invention, the related process flow is simple, expensive raw materials are not needed, and the cobalt disulfide material can be produced in batch in a short time; the microcosmic appearance of the obtained cobalt disulfide is a microsphere structure formed by freely assembling nanosheets with small sizes; the multi-stage micro-nano mesoporous structure is very beneficial to the mass transfer effect in the catalytic reaction, and can fully expose the active sites on the surface of the catalyst.

The prepared cobalt disulfide microspheres can be directly and quickly loaded on the surface of a photocatalyst in a suspension containing the semiconductor photocatalyst by an electrostatic adsorption method, and the photolysis water-oxygen generation reaction performance of the composite material can be remarkably improved.

The invention can better overcome the defects of the prior art shown in the background part, and the prepared cobalt disulfide microsphere is a photocatalytic aquatic oxygen generation promoter with great potential and has wide application prospect.

Drawings

Figure 1 is an XRD pattern of cobalt disulphide according to one embodiment 2 of the present invention;

figure 2 is an SEM image of cobalt disulfide according to example 2 of the present invention;

fig. 3 is a graph showing the performance of the photolytic water-to-oxygen half-reaction measured after cobalt disulfide is loaded on the surface of graphite-like carbon nitride nanosheets according to one embodiment 2 of the present invention;

figure 4 is a graph of the photolytic oxygen half-reaction performance of cobalt disulfide supported on different semiconductor photocatalysts according to example 2 of the present invention.

Detailed Description

For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.