High-stability silver oxide-graphene composite material and preparation method and application thereof
阅读说明：本技术 一种高稳定性氧化银-石墨烯复合材料及其制备方法和应用 (High-stability silver oxide-graphene composite material and preparation method and application thereof ) 是由 常海欣 李刚辉 郭辉 于 2019-10-30 设计创作，主要内容包括：本发明公开了一种高稳定性氧化银-石墨烯复合材料及其制备方法和应用,属于复合材料技术领域。本发明的氧化银-石墨烯复合材料,包括氧化银和石墨烯,所述氧化银与石墨烯的质量比为10～20：100；其中：所述石墨烯是由电化学法制得,具体步骤如下：将成对石墨电极插入由硫酸钠和水组成的电解液中,然后对成对石墨电极通电进行电解,获得石墨烯电解液；再将所述石墨烯电解液进行后处理获得。本发明制备的复合材料能有效地抑制光腐蚀现象的发生,在模拟太阳光的照射下能有效降解有机染料废水中的孔雀石绿,具有较强的光催化活性以及较高的光化学稳定性,便于回收再生循环使用,且其制备工艺简单,在环境污水治理方面具有极大的应用价值。(The invention discloses a high-stability silver oxide-graphene composite material and a preparation method and application thereof, and belongs to the technical field of composite materials. The silver oxide-graphene composite material comprises silver oxide and graphene, wherein the mass ratio of the silver oxide to the graphene is 10-20: 100, respectively; wherein: the graphene is prepared by an electrochemical method, and the specific steps are as follows: inserting the paired graphite electrodes into an electrolyte composed of sodium sulfate and water, and then electrifying the paired graphite electrodes for electrolysis to obtain a graphene electrolyte; and carrying out post-treatment on the graphene electrolyte to obtain the graphene electrolyte. The composite material prepared by the invention can effectively inhibit the occurrence of the photo-corrosion phenomenon, can effectively degrade malachite green in organic dye wastewater under the irradiation of simulated sunlight, has stronger photocatalytic activity and higher photochemical stability, is convenient to recycle, regenerate and reuse, has simple preparation process, and has great application value in the aspect of environmental sewage treatment.)
1. A high-stability silver oxide-graphene composite material is characterized in that: the composite material comprises silver oxide and graphene, wherein: the mass ratio of the silver oxide to the graphene is 10-20: 100.
2. the high stability silver oxide-graphene composite material according to claim 1, wherein: the graphene is prepared by an electrochemical method, and the specific steps are as follows:
inserting the paired graphite electrodes into an electrolyte composed of sodium sulfate and water, and then electrifying the paired graphite electrodes for electrolysis to obtain a graphene electrolyte; and carrying out post-treatment on the graphene electrolyte to obtain the graphene.
3. The method for preparing the high-stability silver oxide-graphene composite material according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
step 1: preparing a silver nitrate aqueous solution: dissolving silver nitrate in deionized water according to the proportion, stirring uniformly, and preparing AgNO3An aqueous solution;
step 2: preparing a graphene dispersion liquid: mixing graphene powder, a dispersing agent and a solvent according to a ratio, and then ultrasonically dispersing the obtained mixed solution uniformly to obtain a graphene dispersion liquid;
and step 3: adding AgNO prepared in the step 1 into the graphene dispersion liquid obtained in the step 23Uniformly mixing the aqueous solution, adding an alkaline solution, adjusting the pH value of the obtained mixed solution to 8-10, and then heating to 80-120 ℃ for constant-temperature reaction for 1-2 h; and after the reaction is finished, cooling to room temperature, centrifuging, washing, filtering and drying in vacuum to obtain the high-stability silver oxide-graphene composite material.
4. The method for preparing the high-stability silver oxide-graphene composite material according to claim 3, wherein: step 1 AgNO3The concentration of the aqueous solution is 50 to 500 mM/L.
5. The method for preparing the high-stability silver oxide-graphene composite material according to claim 3, wherein: the graphene in the step 2 is prepared by an electrochemical method, and the specific steps are as follows:
inserting the paired graphite electrodes into an electrolyte composed of sodium sulfate and water, and then electrifying the paired graphite electrodes for electrolysis to obtain a graphene electrolyte; and carrying out post-treatment on the graphene electrolyte to obtain the graphene.
6. The method for preparing the high-stability silver oxide-graphene composite material according to claim 3, wherein: and 2, the dispersing agent is any one of polyvinylpyrrolidone or polyethylene glycol.
7. The method for preparing the high-stability silver oxide-graphene composite material according to claim 3, wherein: the solvent in the step 2 is an organic solvent or a mixed solvent composed of the organic solvent and water, wherein: the organic solvent is any one of methanol, ethanol, propylene glycol and isopropanol.
8. The method for preparing the high-stability silver oxide-graphene composite material according to claim 3, wherein: and 2, the concentration of graphene in the graphene dispersion liquid in the step 2 is 0.002-0.004 g/mL.
9. The method for preparing the high-stability silver oxide-graphene composite material according to claim 3, wherein: and 3, the alkaline solution is any one of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution or ammonia water.
10. The use of the high-stability silver oxide-graphene composite material according to claim 1 or 2 or the high-stability silver oxide-graphene composite material prepared by the method according to any one of claims 3 to 9 in visible light catalytic degradation of malachite green, an organic dye.
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a high-stability silver oxide-graphene composite material as well as a preparation method and application thereof.
Background
In recent years, with the continuous development of society and the continuous progress of science and technology, the quality of life of people is greatly improved, and the two problems of energy resource shortage and environmental deterioration are more and more severe. Different from the traditional method, the photocatalysis technology completely degrades organic pollutants in water and air by utilizing solar energy, does not generate secondary pollution, is simple to operate, and is considered to be one of the most promising technologies in wastewater treatment, particularly industrial wastewater treatment.
The single silver compound photocatalytic material has high light response performance, but has poor photochemical stability due to a photo-corrosion phenomenon, which severely limits the application and development of the material. Graphene is a two-dimensional carbon nanomaterial consisting of carbon atoms in sp2 hybridized orbitals to form a hexagonal honeycomb lattice. The graphene has excellent optical, electrical and mechanical properties, and has important application prospects in the aspects of materials science, micro-nano processing, energy, photocatalysis and the like. These characteristics make graphene better able to facilitate the transfer between photogenerated electrons and holes. Currently, research work on silver oxide-graphene composite materials is very rare.
The present application has been made for the above reasons.
Disclosure of Invention
In view of the problems or defects in the prior art, the present invention aims to provide a preparation method of a high-stability silver oxide-graphene composite material, and a product prepared by the method and an application of the composite material. According to the invention, the silver oxide and the graphene are compounded, so that the occurrence of a photo-corrosion phenomenon can be effectively inhibited, and the composite photocatalytic material with high activity and high stability is prepared.
In order to achieve the above purpose of the present invention, the technical solution adopted by the present invention is as follows:
a high stability silver oxide-graphene composite comprising silver oxide and graphene, wherein: the mass ratio of the silver oxide to the graphene is 10-20: 100.
further, according to the technical scheme, the graphene is prepared by an electrochemical method, and the method comprises the following specific steps:
inserting the paired graphite electrodes into an electrolyte composed of sodium sulfate and water, and then electrifying the paired graphite electrodes for electrolysis to obtain a graphene electrolyte; and carrying out post-treatment on the graphene electrolyte to obtain the graphene.
The second object of the present invention is to provide a method for preparing the above high-stability silver oxide-graphene composite material, the method comprising the steps of:
step 1: silver nitrate (AgNO)3) Preparing an aqueous solution: dissolving silver nitrate in deionized water according to the proportion, stirring uniformly, and preparing AgNO3An aqueous solution;
step 2: preparing a graphene dispersion liquid: mixing graphene powder, a dispersing agent and a solvent according to a ratio, and then ultrasonically dispersing the obtained mixed solution uniformly to obtain a graphene dispersion liquid;
and step 3: adding AgNO prepared in the step 1 into the graphene dispersion liquid obtained in the
Further, the AgNO in the step 1 of the technical scheme is3The concentration of the aqueous solution is 50 to 500mM/L, preferably 200 mM/L.
Further, in the above technical scheme, the graphene in
inserting the paired graphite electrodes into an electrolyte composed of sodium sulfate and water, and then electrifying the paired graphite electrodes for electrolysis to obtain a graphene electrolyte; and carrying out post-treatment on the graphene electrolyte to obtain the graphene.
Further, in the above technical solution, the dispersant in
Further, in the above technical solution, the solvent in
Preferably, in the above technical solution, the volume ratio of the organic solvent to the water in the mixed solvent is 5: 1.
further, according to the technical scheme, the concentration of graphene in the graphene dispersion liquid in the
Further, in the above technical solution, the alkaline solution in
Further, according to the technical scheme, the washing is carried out by alternately washing with deionized water and absolute ethyl alcohol until the pH value of the washing liquid is 7-7.5.
The silver oxide in the
The second purpose of the invention is to provide an application of the high-stability silver oxide-graphene composite material prepared by the method, which can be used for visible light catalytic degradation of organic dye malachite green.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a preparation method and application of a high-stability silver oxide-graphene composite material, aiming at the problem of poor photochemical stability of a single silver compound photocatalytic material in the prior art.
(2) According to the invention, the graphene is prepared by an electrochemical method preferably, compared with a common chemical oxidation-reduction method, a strong oxidant, a strong reducing agent and a toxic reagent are not needed, the cost is low, the method is clean and environment-friendly, the internal structure of the graphene can be ensured to the greatest extent, and a large number of defects are not generated, so that the conductivity of the graphene is not influenced; secondly, due to the fact that the graphene with high conductivity can transfer electrons separated by photoexcitation in time, the recombination efficiency of photo-generated electrons and cavities is reduced, the occurrence of a photo-corrosion phenomenon can be effectively inhibited, the photo-catalytic activity and the stability of the graphene are greatly improved through the synergistic effect of silver oxide and the graphene, malachite green in organic dye wastewater can be effectively degraded under the irradiation of simulated sunlight, the graphene has high photo-catalytic activity and high photochemical stability, recycling and recycling are facilitated, the preparation process is simple, and the graphene has great application value in the aspect of environmental sewage treatment.
Drawings
FIG. 1 is a comparison graph of performances of a silver oxide-graphene composite material obtained in examples 1 to 3 of the present invention in photocatalytic degradation of an organic dye, malachite green, under simulated sunlight.
Fig. 2 is a diagram showing the photocatalytic degradation effect of the organic dye malachite green in 3 experiments with a single silver oxide material cycle.
FIG. 3 is a diagram showing the photocatalytic degradation effect of the product zinc ferrite obtained in example 3 of the present invention in 8 experiments on the organic dye malachite green.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.