阅读说明：本技术 一种硫化铟锌/石墨相氮化碳复合材料及其制备和应用 (Indium zinc sulfide/graphite phase carbon nitride composite material and preparation and application thereof ) 是由 胡俊蝶 邵媛媛 李长明 于 2021-07-20 设计创作，主要内容包括：本发明属于新能源材料技术领域,具体涉及一种硫化铟锌/石墨相氮化碳复合材料及其制备和应用,应用于原位生产双氧水以进行杀菌,特别是污水杀菌,所述硫化铟锌/石墨相氮化碳复合材料的制备方法,包括以下步骤：将石墨相氮化碳纳米片分散到含有硫化铟锌前驱体的溶剂中,加热反应制得所述硫化铟锌/石墨相氮化碳复合材料。本发明的制备方法简单,原料易得；制得的硫化铟锌/石墨相氮化碳复合材料,是一种性能优良的光催化剂,其光催化产过氧化氢的效率高,稳定性好,且具有良好的杀菌消毒效果,有利于光催化剂的回收和重复利用。(The invention belongs to the technical field of new energy materials, and particularly relates to an indium zinc sulfide/graphite phase carbon nitride composite material, and a preparation method and an application thereof, wherein the indium zinc sulfide/graphite phase carbon nitride composite material is applied to in-situ production of hydrogen peroxide for sterilization, particularly for sterilization of sewage, and the preparation method of the indium zinc sulfide/graphite phase carbon nitride composite material comprises the following steps: dispersing graphite phase carbon nitride nanosheets into a solvent containing an indium zinc sulfide precursor, and heating for reaction to obtain the indium zinc sulfide/graphite phase carbon nitride composite material. The preparation method is simple, and the raw materials are easy to obtain; the prepared indium zinc sulfide/graphite phase carbon nitride composite material is a photocatalyst with excellent performance, has high efficiency of producing hydrogen peroxide by photocatalysis, good stability and good sterilization and disinfection effects, and is beneficial to the recovery and reutilization of the photocatalyst.)

1. A preparation method of an indium zinc sulfide/graphite phase carbon nitride composite material is characterized by comprising the following steps: dispersing graphite phase carbon nitride nanosheets into a solvent containing an indium zinc sulfide precursor, and heating for reaction to obtain the indium zinc sulfide/graphite phase carbon nitride composite material.

2. The method of preparing an indium zinc sulfide/graphite phase carbon nitride composite material according to claim 1, wherein the mass ratio of indium zinc sulfide to graphite phase carbon nitride in the indium zinc sulfide/graphite phase carbon nitride composite material is from 0.1 to 1.5: 1.

3. the method of claim 1, wherein the graphite phase carbon nitride nanosheets are obtained by calcining a carbonitride compound as a precursor.

4. The method of making an indium zinc sulfide/graphite phase carbon nitride composite as claimed in claim 3, wherein the method of making the graphite phase carbon nitride nanoplatelets is as follows:

a. calcining the carbon-nitrogen compound at the temperature of 200-550 ℃ for 1-5 hours to obtain a block;

b. grinding the cake to a powder;

c. and calcining the powder at the temperature of 200-550 ℃ for 1-3 hours to obtain the graphite-phase carbon nitride nanosheet.

5. The method of making an indium zinc sulfide/graphite phase carbon nitride composite material according to claim 3 or 4, wherein the carbon nitride compound is one or more of dicyandiamide, urea, thiourea, cyanamide and melamine.

6. The method of claim 1 wherein the indium zinc sulfide/graphite phase carbon nitride composite is prepared by combining zinc chloride, indium chloride and thioacetamide as indium zinc sulfide precursors and water and glycerol as a solvent.

7. The method of claim 1, wherein the heating is hydrothermal, the heating temperature is 60-120 ℃, and the heating time is 1.5-3 hours.

8. An indium zinc sulfide/graphite phase carbon nitride composite material produced by the production method as set forth in any one of claims 1 to 7.

9. Use of the indium zinc sulfide/graphite phase carbon nitride composite of claim 8 in the photocatalytic preparation of hydrogen peroxide.

10. Use of the indium zinc sulfide/graphite phase carbon nitride composite material of claim 8 in photocatalytic sterilization.

Technical Field

The invention belongs to the technical field of new energy materials, and particularly relates to an indium zinc sulfide/graphite phase carbon nitride composite material, and preparation and application thereof.

Background

Despite the highly developed medical technology, bacterial infections in sewage remain one of the major health threats facing humans, resulting in the death of millions of patients each year. Due to the influence of bacterial drug resistance, the environment-friendly photoelectric material is expected to become a replacement strategy of antibiotics. Among them, the photocatalytic technology has attracted attention of many researchers due to its advantages of low toxicity, mildness, low cost, high efficiency, etc.

Hydrogen peroxide (H)₂O₂) As an environment-friendly oxidant, the compound is widely applied to the fields of organic synthesis, wastewater treatment, medical disinfection and the like. At the same time H₂O₂Only water and oxygen are generated during medical disinfection, and secondary infection is not generated. Due to the fact that H is under normal temperature and normal pressure₂O₂The liquid fuel cell has the advantages of being soluble in water, capable of being used for sterilization and disinfection, convenient to store and transport and the like, and has attracted wide attention as a fuel cell energy carrier for replacing hydrogen. Currently, the anthraquinone process is mainly used in industrial production for large-scale production of H₂O₂But is a synthesis process with non-green characteristics due to high energy consumption resulting from multi-step hydrogenation and oxidation reactions. In addition, there are catalysts for the use of noble metals and their alloys₂(g) And O₂(g) Direct synthesis of H₂O₂But due to the presence of H₂/O₂The gas of the mixture is explosive and therefore dangerous. Scientists have therefore sought an efficient, green, economical H₂O₂The synthesis method, wherein the semiconductor photocatalysis, has the advantages of cleanness, one-step synthesis, environmental friendliness and the like, so that people pay attention to the synthesis method. However, so far, large-scale synthesis of H using solar energy has been carried out₂O₂It is also quite challenging.

In the photocatalytic preparation of H₂O₂In the field, graphite phase carbon nitride materials with better photocatalytic activity stand out, however, graphite phase carbon nitride materials have their ownHas more defects, such as narrow absorption range and weak absorption intensity of visible light, high recombination rate of photogenerated electrons and holes, low carrier mobility and the like, and greatly limits the preparation of H under the action of visible light₂O₂The performance of (c). In recent years, it has been found that the above-mentioned disadvantages can be overcome by the construction of heterojunctions. Reduction of CO in photocatalysis by indium-zinc sulfide₂And hydrogen production, and has attracted people's attention due to its better conductivity and stronger visible light absorption. Therefore, indium zinc sulfide grows in situ on the surface of the graphite-phase carbon nitride photocatalyst to promote H generation₂O₂The efficiency of the sterilization and disinfection is the key point of research.

Disclosure of Invention

The invention aims to provide an indium zinc sulfide/graphite phase carbon nitride composite material and a preparation method thereof, the indium zinc sulfide/graphite phase carbon nitride composite material is used for sterilizing hydrogen peroxide in situ under sunlight irradiation, particularly for sterilizing sewage, has higher hydrogen peroxide production efficiency and sterilization capability, and has the advantages of greenness, economy and the like.

According to the technical scheme of the invention, the preparation method of the indium zinc sulfide/graphite phase carbon nitride composite material comprises the following steps: dispersing graphite phase carbon nitride nanosheets into a solvent containing an indium zinc sulfide precursor, and heating for reaction to obtain the indium zinc sulfide/graphite phase carbon nitride composite material.

According to the invention, the indium zinc sulfide nanosheets grow on the surfaces of the graphite phase carbon nitride nanosheets, so that the surface area is increased, the morphology structure of the compound is regulated and controlled by controlling the addition amount of the indium zinc sulfide, the addition amount of the indium zinc sulfide is large, the attached nanosheets are dense, the addition amount of the indium zinc sulfide is small, and the small nanosheets on the surface are sparse.

Further, the mass ratio of the indium zinc sulfide to the graphite-phase carbon nitride is 0.1-1.5: 1.

further, the graphite-phase carbon nitride nanosheet is prepared by taking a carbon nitride compound as a precursor and calcining the precursor.

Further, the preparation method of the graphite phase carbon nitride nanosheet comprises the following steps:

a. calcining the carbon-nitrogen compound at the temperature of 200-550 ℃ for 1-5 hours to obtain a block;

b. grinding the cake to a powder;

c. and calcining the powder at the temperature of 200-550 ℃ for 1-3 hours to obtain the graphite-phase carbon nitride nanosheet.

Further, the carbon nitrogen compound is one or more of dicyandiamide, urea, thiourea, cyanamide, melamine and the like.

Further, the indium zinc sulfide precursor is zinc chloride, indium chloride and thioacetamide, and the solvent is a mixed solution of water and glycerol with the pH value of 1-5.

Specifically, in the indium zinc sulfide precursor, the molar ratio of zinc chloride, indium chloride and thioacetamide is 1: 1.5-2.5: 3-5, preferably 1: 2: 4; in the solvent, the volume ratio of water to glycerin is 8-12: 3, preferably 10: 3.

furthermore, the heating is carried out by a hydrothermal method, the heating temperature is 60-120 ℃, and the heating time is 1.5-3 h.

Specifically, the preparation method of the indium zinc sulfide/graphite phase carbon nitride composite material can be as follows: putting a precursor of indium zinc sulfide into a solution with pH value of 1-5 (preferably 2.5), adding graphite phase carbon nitride nanosheets, ultrasonically dispersing, and heating in an oil bath at 60-120 ℃ for 1.5-3 h; centrifuging the heated solution, washing the centrifuged precipitate with water and ethanol for multiple times (3-6), and vacuum drying at 50-70 deg.C to obtain solution of indium zinc sulfide/graphite phase carbon nitride composite material.

The step can successfully modify the indium zinc sulfide nanosheets to the surface of the graphite phase carbon nitride nanosheets, and find the indium zinc sulfide/graphite phase carbon nitride nanosheets which are uniformly distributed, so that a perfect heterojunction structure is formed, and the step plays a vital role in improving the efficiency of photocatalytic hydrogen peroxide production.

According to the method, a carbon nitrogen compound (such as dicyandiamide) is used as a raw material, the graphite phase carbon nitride nanosheet is prepared through secondary calcination, and then the indium zinc sulfide nanosheet is modified to the surface of the graphite phase carbon nitride nanosheet through a hydrothermal method to form a perfect heterojunction structure. The introduction of indium zinc sulfide enables the composite material to have strong absorption capacity to visible light, and the composite material has a proper band gap and good conductivity, so that the photocatalytic performance can be greatly improved.

The second aspect of the invention provides the indium zinc sulfide/graphite phase carbon nitride composite material prepared by the preparation method. The composite material has strong absorption capacity to visible light due to excellent visible light response and high carrier mobility, and shows high hydrogen peroxide production efficiency and sterilization capacity.

The third aspect of the invention provides an application of the indium zinc sulfide/graphite phase carbon nitride composite material in photocatalytic preparation of hydrogen peroxide and photocatalytic sterilization, and the photocatalytic sterilization is specifically to photocatalytic in-situ preparation of hydrogen peroxide for sterilization, especially for sterilization and purification of sewage.

Compared with the prior art, the technical scheme of the invention has the following advantages:

1. the preparation method of the indium zinc sulfide/graphite phase carbon nitride composite material is simple, the raw materials are easy to obtain, the operation is simple and convenient, and the method is very key to industrial application.

2. According to the invention, the surface area of the indium zinc sulfide/graphite phase carbon nitride structure can be increased by controlling the structure, so that the efficiency of producing hydrogen peroxide by photocatalysis is improved; the introduction of indium zinc sulfide can greatly improve the electron transmission efficiency, increase the absorption range of visible light, improve the utilization rate of graphite-phase carbon nitride to the visible light, and further improve the efficiency of producing hydrogen peroxide by photocatalysis.

3. The indium zinc sulfide/graphite phase carbon nitride composite material is a photocatalyst with excellent performance, has high efficiency of producing hydrogen peroxide by photocatalysis, good stability and good sterilization and disinfection effects, and is beneficial to the recovery and reutilization of the photocatalyst.

Drawings

FIG. 1 is a Scanning Electron Micrograph (SEM) of graphite phase carbon nitride;

FIG. 2 is a Transmission Electron Micrograph (TEM) of graphite-phase carbon nitride;

FIG. 3 is a scanning electron micrograph of indium zinc sulfide;

FIG. 4 is a transmission electron micrograph of indium zinc sulfide;

FIG. 5 is a scanning electron micrograph of an indium zinc sulfide/graphite phase carbon nitride composite;

FIGS. 6 and 7 are transmission electron micrographs of a zinc indium sulfide/graphite phase carbon nitride composite;

FIG. 8 is a graph showing the effect of photocatalytic generation of hydrogen peroxide;

FIG. 9 is a graph showing the effect of the cycle of photocatalytic generation of hydrogen peroxide;

FIG. 10 is a graph showing the effect of the photocatalytic material in killing Escherichia coli.

Detailed Description

The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.

Example 1: preparation of indium zinc sulfide nanosheet

20mL of water and 6mL of glycerol were charged into a round bottom flask, the pH of the solution was adjusted to 2.5 with hydrochloric acid, and the solution was ultrasonically dispersed to give a homogeneous solution. Subsequently, 27.2mg of zinc chloride, 117.2mg of indium chloride tetrahydrate and 60mg of thioacetamide were added to the above solution, stirred for 30min and heated at 80 ℃ for two hours. And centrifuging the product after reaction, washing the centrifuged precipitate for multiple times by using water and ethanol respectively, and drying in vacuum at 50-70 ℃ to obtain yellow indium zinc sulfide nanosheet powder.

Fig. 3 and fig. 4 are SEM and TEM images of indium zinc sulfide, respectively, and it can be seen from the images that pure indium zinc sulfide exhibits a structure of nanoflower.

Example 2: preparation of graphite phase carbon nitride nanosheet

10g of dicyandiamide is placed in a crucible with a cover and directly calcined in a muffle furnace, the heating rate is 2.3 ℃/min, the calcining temperature is 550 ℃, and the calcining time is 4 h. A dark yellow block g-C is obtained₃N₄And then ground to a dark yellow powder. A little dark yellow powder is put into a porcelain boat, the heating rate is 5 ℃/min, the heating is carried out to 550 ℃, and the calcination time is 2 h. Finally obtaining light yellow graphite phase nitridingCarbon nanosheet powder.

Fig. 1 and 2 are SEM and TEM images of graphite-phase carbon nitride, respectively, from which the prepared graphite-phase carbon nitride can be observed to have a lamellar structure.

Example 3: preparation of indium zinc sulfide/graphite phase carbon nitride composite material

20mL of water and 6mL of glycerol were poured into a round-bottom flask, the pH of the solution was adjusted to 2.5 with 0.5M hydrochloric acid, and the solution was sonicated for 3min to disperse the solution uniformly. Subsequently, 27.2mg of zinc chloride, 117.2mg of indium chloride tetrahydrate and 60mg of thioacetamide were added to the above suspension, stirred for 30min, and graphite-phase carbon nitride nanosheets (obtained in example 2) of different masses (indium zinc sulfide/graphite-phase carbon nitride mass ratios of 0.1: 1, 0.5: 1, 1.0: 1 and 1.5: 1, respectively) were added, stirred for 30min, and heated at 80 ℃ for two hours. After the reaction is finished, centrifugally separating the product, then respectively washing the product with water and ethanol for three times, and finally drying the product in a vacuum oven at 65 ℃ to obtain the indium zinc sulfide/graphite phase carbon nitride composite material.

Fig. 5 and fig. 6-7 are SEM and TEM images of the indium zinc sulfide/graphite phase carbon nitride composite material, respectively, from which it can be clearly and intuitively seen that the indium zinc sulfide nanosheets successfully decorated the surface of the graphite phase carbon nitride nanosheets, forming a perfect heterojunction structure.

Detection examples

20mg of the indium zinc sulfide/graphite phase carbon nitride composite material prepared in example 3, 45mL of deionized water and 5mL of isopropanol were uniformly mixed, placed in a photocatalytic reactor, stirred for 10min, introduced with condensed water, and turned on with a xenon lamp light source to start a photocatalytic reaction.

The isopropanol is added as a sacrificial agent, oxidation reaction is carried out at a cavity to generate acetone, recombination of electrons and the cavity is prevented, the efficiency of producing hydrogen peroxide through photocatalytic reaction is improved, and the sacrificial agent can also adopt ethanol, furfuryl alcohol, methanol and the like.

Fig. 8 and 9 are a graph showing the effect of photocatalytic hydrogen peroxide generation and the effect of hydrogen peroxide generation cycle of an indium zinc sulfide/graphite phase carbon nitride composite material, respectively. As can be seen from the figure, the efficiency of the indium zinc sulfide/graphite phase carbon nitride composite material for catalyzing and producing hydrogen peroxide is obviously superior to that of a pure graphite phase carbon nitride material and a pure indium zinc sulfide material, and the indium zinc sulfide/graphite phase carbon nitride composite material has good stability.

FIG. 10 is a diagram showing the effect of photocatalytic killing of Escherichia coli by using an indium zinc sulfide/graphite phase carbon nitride composite material. As can be seen from the figure, the indium zinc sulfide/graphite phase carbon nitride composite material can completely kill escherichia coli after being illuminated for 40min, and has good sterilization effect.

It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.