阅读说明：本技术 一种硫化银/磷化钴复合光催化剂及其制备方法 (Silver sulfide/cobalt phosphide composite photocatalyst and preparation method thereof ) 是由 廖铁仙 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种硫化银/磷化钴复合光催化剂及其制备方法,该复合光催化剂是先通过水热法合成Co<Sub>2</Sub>P,然后将得到的Co<Sub>2</Sub>P添加到含有锌源化合物和硫源化合物的乙二胺和水的混合溶液,进行第二次水热反应,得到ZnS/Co<Sub>2</Sub>P,然后将其添加到硝酸银溶液中,在一定的温度下进行反应得到Ag<Sub>2</Sub>S/Co<Sub>2</Sub>P,通过上述方法制备的Ag<Sub>2</Sub>S/Co<Sub>2</Sub>P复合光催化剂材料,其与Ag<Sub>2</Sub>S光催化剂相比,可明显提高其光催化性能,而且对废水中的有机污染物具有很好的降解能力。(The invention discloses a silver sulfide/cobalt phosphide composite photocatalyst and a preparation method thereof 2 P, then the obtained Co 2 Adding P into the mixed solution of ethylenediamine and water containing zinc source compound and sulfur source compound, and performing a second hydrothermal reaction to obtain ZnS/Co 2 P, then adding the silver nitrate into silver nitrate solution, and reacting at a certain temperature to obtain Ag 2 S/Co 2 P, Ag prepared by the above method 2 S/Co 2 P composite photocatalyst material, and Ag 2 Compared with S photocatalyst, the photocatalyst can obviously improve the photocatalytic performance and has the function of treating organic pollutants in wastewaterGood degradation capability.)

1. A preparation method of a silver sulfide/cobalt phosphide composite photocatalyst is characterized by comprising the following steps: the method comprises the following steps:

(1): dissolving a cobalt source compound, a phosphorus source compound and a surfactant in a certain amount of deionized water in sequence, and stirring to uniformly mix the cobalt source compound, the phosphorus source compound and the surfactant;

(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 2-5 h at 180-240 ℃, naturally cooling to room temperature, washing and drying the obtained product to obtain a final product Co₂P；

(3) Dissolving a zinc source compound and a sulfur source compound in a mixed solution of ethylenediamine and water, and dissolving the Co obtained in the step (2)₂Adding P into the mixed solution, and performing hydrothermal reaction at the temperature of 150-₂A P composite material;

(4) ZnS/Co obtained in the step (3)₂Uniformly mixing the P composite material with a silver nitrate solution, reacting for 4-5 h at 80-110 ℃, filtering, washing and drying to obtain Ag₂S/Co₂P composite photocatalyst.

2. The method of claim 1, wherein: in the step (1), the cobalt source compound is selected from one or more of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate; the phosphorus source compound is selected from one or more of sodium hypophosphite, sodium hydrogen phosphate, disodium hydrogen phosphate and ammonium hydrogen phosphate; the surfactant is one or more selected from PVP, sodium dodecyl benzene sulfonate and polyethylene glycol-400.

3. The production method according to claim 1 or 2, characterized in that: the molar ratio of the cobalt source compound to the phosphorus source compound in the step (1) is 1: 13-18, and the addition ratio of the cobalt source compound to the surfactant is 1 mmol: 0.05 to 0.2 g.

4. The production method according to claim 1 or 2, characterized in that: in the step (2), the detergent is ethanol and/or deionized water, the washing times are 2-3 times, and the drying is performed at 50-70 ℃ for 10-14 h.

5. The method of claim 1, wherein: in the step (3), the volume ratio of the ethylenediamine to the water is 13-16: 1; the zinc source compound is selected from one or more of zinc acetate, zinc chloride and zinc nitrate, the sulfur source compound is thiourea, and the molar ratio of the zinc source compound to the sulfur source compound is 1: 2.

6. The method of claim 1, wherein: in the step (4), the molar ratio of the ZnS to the silver nitrate is 1: 1-2; the Ag is₂S and the Co₂The molar ratio of P is 1: 1-3.

7. The method of claim 1, wherein: the washing is centrifugal washing by dilute hydrochloric acid and deionized water respectively, and the drying is drying for 10-14 h at 50-70 ℃.

8. The silver sulfide/cobalt phosphide composite photocatalyst prepared by the preparation method according to any one of claims 1 to 7, which is characterized in that: the Co₂P is microspherical, in Co₂Ag with nano-sheet structure on surface of P microsphere₂S。

9. The use of the silver sulfide/cobalt phosphide composite photocatalyst as defined in claim 8, wherein: the silver sulfide/cobalt phosphide composite photocatalyst is used for photocatalytic degradation of organic pollutants in organic wastewater.

10. Use according to claim 9, characterized in that: the organic pollutant is rhodamine B or methyl orange.

Technical Field

The invention relates to the field of photocatalytic materials, in particular to a silver sulfide/cobalt phosphide composite photocatalyst and a preparation method thereof.

Background

The increasingly prominent energy crisis and industrialization bring about serious environmental pollution problems, which have important influence on the development of social economy, and the search for the research and development of new equipment, new technology and new production process is an urgent task for solving the current problems. The green, high-efficiency and secondary pollution-free photocatalysis technology becomes one of important means for solving energy and environmental problems for human beings, and has very important practical significance.

Ag₂S is taken as a typical narrow-forbidden-band-width semiconductor material, silver sulfide has special response to illumination conditions, silver sulfide quantum dots also show special near-infrared luminescence characteristics, and the semiconductor material has low toxicity and good biocompatibilityHas the characteristics of good application prospect in practical application. But the single use of Ag is found in practical application₂S is not very high in photocatalytic performance, researchers compound S with other photocatalysts and form heterojunction with silver sulfide and other photocatalysts to improve the photocatalytic performance of S, such as Ag₂S/Ag₃VO₄，Ag₃PO₄/Ag₂S/g-C₃N₄And the like to further improve the performance of the photocatalyst. However, the photocatalytic activity is not improved significantly, so that further improvement of Ag is urgently required₂The composite photocatalyst of the S photocatalyst improves the degradation capability on organic pollutants and further expands the types of the photocatalysts.

Disclosure of Invention

The technical problem to be solved by the present invention is to provide an Ag alloy for overcoming the above-mentioned shortcomings in the prior art₂S/Co₂P composite photocatalyst and preparation method thereof, and Ag₂S/Co₂P composite photocatalyst and Ag₂Compared with S photocatalyst, the photocatalyst can obviously improve the photocatalytic performance and has good degradation capability on organic pollutants in wastewater.

The invention adopts the following technical scheme:

ag₂S/Co₂The preparation method of the P composite photocatalyst comprises the following steps:

(1): dissolving a cobalt source compound, a phosphorus source compound and a surfactant in a certain amount of deionized water in sequence, and stirring to uniformly mix the cobalt source compound, the phosphorus source compound and the surfactant;

(2) transferring the solution obtained in the step 1) into a polytetrafluoroethylene reaction kettle, reacting for 2-5 h at 180-240 ℃, naturally cooling to room temperature, washing and drying the obtained product to obtain a final product Co₂P；

(3) Dissolving a zinc source compound and a sulfur source compound in a mixed solution of ethylenediamine and water, and dissolving the Co obtained in the step (2)₂Adding P into the mixed solution, and performing hydrothermal reaction at the temperature of 150-₂A P composite material;

(4) ZnS/Co obtained in the step (3)₂Uniformly mixing the P composite material with a silver nitrate solution, reacting for 4-5 h at 80-110 ℃, filtering, washing and drying to obtain Ag₂S/Co₂P composite photocatalyst.

Preferably, in the step (1), the cobalt source compound is selected from one or more of cobalt chloride, cobalt sulfate, cobalt nitrate and cobalt acetate; the phosphorus source compound is selected from one or more of sodium hypophosphite, sodium hydrogen phosphate, disodium hydrogen phosphate and ammonium hydrogen phosphate; the surfactant is one or more selected from PVP, sodium dodecyl benzene sulfonate and polyethylene glycol-400.

Preferably, in the step (1), the molar ratio of the cobalt source compound to the phosphorus source compound is 1: 13-18, and the addition amount ratio of the cobalt source compound to the surfactant is 1 mmol: 0.05 to 0.2 g.

Preferably, in the step (2), the detergent is ethanol and/or deionized water, the washing times are 2-3 times, and the drying is performed at 50-70 ℃ for 10-14 h.

Preferably, in the step (3), the volume ratio of the ethylenediamine to the water is 13-16: 1; the zinc source compound is selected from one or more of zinc acetate, zinc chloride and zinc nitrate, the sulfur source compound is thiourea, and the molar ratio of the zinc source compound to the sulfur source compound is 1: 2.

Preferably, in the step (4), the molar ratio of the ZnS to the silver nitrate is 1: 1-2; the Ag is₂S and the Co₂The molar ratio of P is 1: 1-3.

Preferably, the washing is centrifugal washing with dilute hydrochloric acid and deionized water respectively, and the drying is drying at 50-70 ℃ for 10-14 h.

The other technical scheme of the invention is that the Ag prepared based on the preparation method₂S/Co₂P composite photocatalyst, said Co₂P is microspherical, in Co₂Ag with sheet structure on P microsphere surface₂S。

Another technical scheme of the invention is based on the Ag₂S/Co₂Application of P composite photocatalyst and photocatalystAg as described above₂S/Co₂The P composite photocatalyst is used for photocatalytic degradation of organic pollutants in organic wastewater.

Preferably, the organic pollutant is rhodamine B or methyl orange.

The Ag provided by the invention is adopted₂S/Co₂The P composite photocatalyst and the preparation method thereof have the following technical effects:

(1) the application firstly prepares Co by a hydrothermal method₂P microspheres, then Co is added₂P is dispersed in a mixed solution of ethylenediamine containing a zinc source and a sulfur source and water, and then subjected to hydrothermal reaction in Co₂ZnS nanosheets grow on the surfaces of the P microspheres, and then Ag is formed through ion replacement of Ag and Zn₂S nanosheet loaded to Co₂The specific surface area of the composite material is increased by the method, so that the contact area of the composite material and the composite material is increased, and the Ag is increased₂The photocatalytic performance of the S photocatalyst.

(2) By Ag₂S and Co₂P is compounded, a heterojunction structure is formed between the P and the P, the separation efficiency of photoproduction electrons and photoproduction holes is accelerated, and the photocatalysis performance is improved.

(3) The preparation method is simple, easy to control and beneficial to industrial production.

In conclusion, the Ag prepared by the invention₂S/Co₂The P composite photocatalyst has excellent photocatalytic performance, has good degradation capability on organic pollutants in wastewater, and is an ideal material.

Drawings

FIG. 1 is an activity diagram of photodegradation of rhodamine B in example 1 and comparative examples 1-2

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally shown may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.