阅读说明：本技术 氧化铋/四氧化三铁/石墨烯三组分复合材料制备方法 (Preparation method of bismuth oxide/ferroferric oxide/graphene three-component composite material ) 是由 王芳 尚海滨 于 2019-09-25 设计创作，主要内容包括：本发明提供了一种氧化铋/四氧化三铁/石墨烯三组分异质结复合材料制备方法,包括：配制氧化铋溶液；加入同等量的硫酸铁溶液和硫酸亚铁溶液至氧化铋溶液中,搅拌后,形成第一混合溶液；加入氧化石墨烯至第一混合溶液中,超声震荡至溶液均匀分散,记作第二混合溶液；将第二混合溶液倒入反应釜中进行反应,经冷却、洗涤、干燥后,生成氧化铋/四氧化三铁/石墨烯三组分异质结复合材料。通过本发明的技术方案,有效增加了复合材料的比表面积,由于石墨烯的结构有利于电子对的迁移,从而提升了复合材料的光催化效率,具有较好的降解性能,同时也具有比较高的稳定性,催化剂的回收利用率更高,在光催化领域具有更加广泛的应用前景。(The invention provides a preparation method of a bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material, which comprises the following steps: preparing a bismuth oxide solution; adding the same amount of ferric sulfate solution and ferrous sulfate solution into the bismuth oxide solution, and stirring to form a first mixed solution; adding graphene oxide into the first mixed solution, and performing ultrasonic oscillation until the solution is uniformly dispersed, and recording the solution as a second mixed solution; and pouring the second mixed solution into a reaction kettle for reaction, and cooling, washing and drying to obtain the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material. According to the technical scheme, the specific surface area of the composite material is effectively increased, and the structure of the graphene is favorable for the migration of electron pairs, so that the photocatalytic efficiency of the composite material is improved, the composite material has good degradation performance and high stability, the catalyst is higher in recycling rate, and the composite material has a wider application prospect in the field of photocatalysis.)

1. A preparation method of a bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material is characterized by comprising the following steps:

preparing a bismuth oxide solution;

adding an equivalent amount of ferric sulfate solution and ferrous sulfate solution into the bismuth oxide solution, and stirring to form a first mixed solution;

adding graphene oxide into the first mixed solution, and performing ultrasonic oscillation until the solution is uniformly dispersed, and recording the solution as a second mixed solution;

and pouring the second mixed solution into a reaction kettle for reaction, and cooling, washing and drying to obtain the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material.

2. The preparation method of the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material according to claim 1, wherein the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material is prepared by mixing bismuth oxide, ferroferric oxide and graphene,

the mass ratio of the bismuth oxide to the ferroferric oxide to the graphene is 66-88%: 2% -4%: 10 to 30 percent.

3. The preparation method of the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material according to claim 2, wherein the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material is prepared by mixing bismuth oxide, ferroferric oxide and graphene,

the mass ratio of the bismuth oxide to the ferroferric oxide to the graphene is 82%: 3%: 15 percent.

4. The preparation method of the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material according to any one of claims 1 to 3, wherein the second mixed solution is poured into a reaction kettle for reaction, and after cooling, washing and drying, the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material is generated, and the preparation method specifically comprises the following steps:

pouring the second mixed solution into a reaction kettle, and placing the reaction kettle at a constant temperature of 160 ℃ for reaction for 12 hours;

after the reaction is finished, taking out the product in the reaction kettle, cooling, and washing with deionized water and absolute ethyl alcohol for multiple times;

and drying the washed product at a constant temperature of 80 ℃ for 6 hours to generate the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material.

5. The preparation method of the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material according to any one of claims 1 to 3, wherein the preparing of the bismuth oxide solution comprises:

bismuth nitrate was dissolved in a solution containing ethylene glycol and ethanol with stirring.

6. The preparation method of the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material according to claim 5, wherein the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material is prepared by mixing bismuth oxide, ferroferric oxide and graphene,

the molar/volume ratio of the bismuth nitrate to the solution of ethylene glycol and ethanol is 2: 40;

the volume ratio of the ethylene glycol to the ethanol in the solution of the ethylene glycol and the ethanol is 8: 32.

7. The preparation method of the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material according to claim 6, wherein the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material is prepared by mixing bismuth oxide, ferroferric oxide and graphene,

when the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material is applied to tetracycline degradation, the applicable pH value is 4.0-7.2.

8. The preparation method of the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material according to claim 7, wherein the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material is prepared by mixing bismuth oxide, ferroferric oxide and graphene,

when the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material is applied to tetracycline degradation, the applicable pH value is 7.0.

Technical Field

The invention relates to the technical field of sewage treatment, and particularly relates to a preparation method of a bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material.

Background

In modern society with faster and faster economic development, the problem of environmental pollution is one of the most serious problems that need to be solved, and the problem of environmental pollution not only destroys ecological balance, but also seriously harms human health. The pollution problem is also becoming more serious with increasing waste water discharge, where most of the waste water is industrial waste water from plants. Therefore, researchers have been working on how to alleviate these contaminations, and the research of multifunctional materials that can effectively reduce the contaminations is an important means to solve the problem.

A large number of experiments and researches prove that the photocatalytic degradation technology is mature and widely applied in the field of sewage treatment, in the process, a plurality of photocatalytic materials with high-efficiency degradation capability are researched, and the bismuth-based oxide is favored by researchers. Meanwhile, most researchers conducted studies on composite materials due to the defectiveness of the one-component catalyst. However, existing composite materials are still not ideal for sewage treatment applications.

Therefore, how to simplify the preparation process of the composite material, improve the stability and repeatability of the composite material, and improve the use effect of the composite material in sewage treatment becomes an urgent problem to be solved.

Disclosure of Invention

The present invention is directed to solving at least one of the problems of the prior art or the related art.

Therefore, the invention aims to provide a preparation method of a bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material.

In order to achieve the purpose, the technical scheme of the invention provides a preparation method of a bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material, which comprises the following steps: preparing a bismuth oxide solution; adding the same amount of ferric sulfate solution and ferrous sulfate solution into the bismuth oxide solution, and stirring to form a first mixed solution; adding graphene oxide into the first mixed solution, and performing ultrasonic oscillation until the solution is uniformly dispersed, and recording the solution as a second mixed solution; and pouring the second mixed solution into a reaction kettle for reaction, and cooling, washing and drying to obtain the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material.

According to the technical scheme, bismuth oxide is used as a main photocatalytic degradation material, graphene is used as a carrier, ferroferric oxide increases the magnetism of the composite material, and the three-component heterojunction composite material is obtained. Meanwhile, the magnetism of the material can be improved by compounding the graphene and the magnetic material, and the ferroferric oxide serving as a carrier can be attached to the surface of the catalyst, so that the catalyst can be better recycled under the action of external magnetic force, and can be reused.

Preparing a bismuth oxide solution, adding ferroferric oxide and graphene oxide, and performing ultrasonic oscillation to obtain a three-component composite material, wherein the three-component composite material has a certain degradation function on tetracycline, and is high in recovery rate and utilization rate, and the forbidden bandwidth of the three-component heterojunction composite material is small compared with that of a single-component material as determined by ultraviolet-visible diffuse reflection analysis; through fluorescence analysis tests, compared with a single-component material, the band gap energy of the three-component heterozygotic junction composite material is obviously reduced; through X-ray diffraction pattern analysis, ferroferric oxide and graphene are only deposited on the surface of bismuth oxide, but do not enter the interior of crystal lattices and influence the growth of the bismuth oxide, and the three-component heterogenous junction composite material has better dispersion degree and larger surface area; according to specific surface area analysis, compared with a single-component material, the specific surface area and the pore volume of the three-component heterojunction composite material are large, so that the three-component heterojunction composite material is prepared by adding ferroferric oxide and graphene oxide, the forbidden bandwidth is reduced, the band gap energy is reduced, the catalytic reaction surface area is increased, and the specific surface area and the pore volume are increased, so that the catalytic effect is improved, and compared with the single-component material, the degradation efficiency of the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material on tetracycline is improved by more than 15%. And through stability test, after the composite material is centrifuged to remove tetracycline supernatant, new tetracycline with the same concentration is added again for degradation twice, and the result shows that the first degradation rate reaches 99.5%, and the degradation rate reaches 92.6% after one circulation, so that the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material has good stability and can be recycled.

The method has the advantages of simple steps and reasonable process design, effectively increases the specific surface area of the composite material, enhances the magnetism, ensures that the recovery and utilization rate of the catalyst is higher, and has wider application prospect in the field of photocatalysis.

In the above technical scheme, preferably, the mass ratio of bismuth oxide, ferroferric oxide and graphene is 66% to 88%: 2% -4%: 10 to 30 percent.

In the technical scheme, the mass ratio of bismuth oxide, ferroferric oxide and graphene is 66-88%: 2% -4%: 10-30%, and the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material prepared according to the mass ratio is high in tetracycline degradation efficiency through experimental verification.

In any one of the above technical solutions, preferably, the mass ratio of bismuth oxide, ferroferric oxide, and graphene is 82%: 3%: 15 percent.

In the technical scheme, the mass ratio of bismuth oxide, ferroferric oxide and graphene is 82%: 3%: 15 percent, and experiments prove that the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material prepared according to the mass ratio has higher degradation efficiency on tetracycline, and can reach more than 90 percent.

In any of the above technical solutions, preferably, the second mixed solution is poured into a reaction kettle to react, and after cooling, washing and drying, a bismuth oxide/ferroferric oxide/graphene three-component hetero-junction composite material is generated, which specifically includes: pouring the second mixed solution into a reaction kettle, and placing the reaction kettle at the constant temperature of 160 ℃ for reaction for 12 hours; after the reaction is finished, taking out the product in the reaction kettle, cooling, and washing with deionized water and absolute ethyl alcohol for multiple times; and drying the washed product at the constant temperature of 80 ℃ for 6 hours to generate the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material.

In the technical scheme, the preparation process of the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material is further refined, the steps are simple, the process design is reasonable, and the repeatability for preparing the bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material is strong.

In any of the above embodiments, preferably, the preparing of the bismuth oxide solution includes: bismuth nitrate was dissolved in a solution containing ethylene glycol and ethanol with stirring.

In the technical scheme, the bismuth oxide solution is prepared by taking bismuth nitrate as a raw material, the raw material is easy to obtain, the cost is relatively low, the preparation process is simple, and the operability is strong.

In any of the above solutions, preferably, the molar/volume ratio of the solution of bismuth nitrate, ethylene glycol and ethanol is 2: 40; the volume ratio of the ethylene glycol to the ethanol in the solution of the ethylene glycol and the ethanol is 8: 32.

In any one of the above technical schemes, preferably, the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material has a pH value of 4.0-7.2 when being applied to tetracycline degradation.

In the technical scheme, when the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material is applied to tetracycline degradation, the pH value is adjusted to 4.0-7.2, and the degradation effect is good.

In any one of the above technical solutions, preferably, the applicable pH value of the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material is 7.0 when the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material is applied to tetracycline degradation.

In the technical scheme, when the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material is applied to tetracycline degradation, the pH value is adjusted to 7.0, and the degradation effect is better.

According to the technical scheme, the bismuth oxide solution is prepared firstly, then the ferroferric oxide and the graphene oxide are added, and the three-component composite material is obtained through ultrasonic vibration, the steps are simple, the process design is reasonable, the composite material can present a porous spherical structure due to the doping of the ferroferric oxide and the graphene oxide, the specific surface area of the composite material is effectively increased, the photocatalytic efficiency of the composite material is improved due to the fact that the structure of the graphene is favorable for the migration of electron pairs, and tests prove that the degradation rate of the tetracycline is as high as 97.65% under the optimal mass ratio, meanwhile, after three times of degradation and recycling, the degradation rate of the tetracycline for the first time can reach 99.5%, the degradation rate of the tetracycline for the second time is 92.6%, and the degradation rate of the tetracycline for the last time reaches 85%, so that the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material has good degradation performance, meanwhile, the catalyst has higher stability, higher recovery and utilization rate of the catalyst and wider application prospect in the field of photocatalysis.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Drawings

The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:

FIG. 1 shows a graph of the effect of bismuth oxide/ferroferric oxide materials containing different amounts of ferroferric oxide on tetracycline degradation performance;

FIG. 2 is a graph showing the effect of three different materials on tetracycline degradation;

figure 3 shows a graph of the forbidden band widths for three different materials;

FIG. 4 shows fluorescence spectra of three different materials at an excitation wavelength of 365 nm;

FIG. 5 shows adsorption/desorption isotherms for three different materials;

FIG. 6 is a graph showing the influence of different amounts of graphene on the tetracycline degradation performance of a bismuth oxide/ferroferric oxide/graphene three-component heterogeneous composite material prepared from different amounts of graphene;

fig. 7 shows a stability performance curve diagram of a bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material.

Detailed Description

The invention discloses a preparation method of a bismuth oxide/ferroferric oxide/graphene three-component heterojunction composite material, and a person skilled in the art can use the content of the composite material for reference and appropriately improve process parameters to realize the preparation. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.

Reagents and instruments adopted in the preparation method of the bismuth oxide/ferroferric oxide/graphene three-component heterogenous junction composite material provided by the invention can be purchased in the market, and the reagents and the instruments are specifically shown in the following tables 1 and 2:

TABLE 1 reagents

TABLE 2 Instrument

The invention is further illustrated by the following examples: