阅读说明：本技术 一种光催化材料BiOBr/ZnSn(OH)6@碳纤维布的制备方法 (Photocatalytic material BiOBr/ZnSn (OH)6Preparation method of @ carbon fiber cloth ) 是由 张志伟 宋爱君 鲁勖琳 于 2020-07-13 设计创作，主要内容包括：一种光催化材料BiOBr/ZnSn(OH)<Sub>6</Sub>@碳纤维布的制备方法,它涉及光催化材料的制备方法。本发明旨在解决现有的光催化材料回收困难的技术问题。本方法：将碳纤维布放入水、乙醇、丙酮的混合溶液中超声处理。将碳纤维布放入王水中浸泡24h,再洗涤干燥。将SnCl<Sub>4</Sub>·5H<Sub>2</Sub>O和ZnCl<Sub>2</Sub>配成溶液后,调节pH值；再将它们等体积混合,放入碳纤维布,静置6h,取出后洗涤干燥,制得ZnSn(OH)<Sub>6</Sub>@碳纤维布；将Bi(NO<Sub>3</Sub>)<Sub>3</Sub>·5H<Sub>2</Sub>O溶解,与含溴的盐溶液搅拌混合；将ZnSn(OH)<Sub>6</Sub>@碳纤维布放入水热反应釜内的混合液中进行反应,洗涤干燥后得BiOBr/ZnSn(OH)<Sub>6</Sub>@碳纤维布。它用于光催化领域。(Photocatalytic material BiOBr/ZnSn (OH) 6 A preparation method of @ carbon fiber cloth, which relates to a preparation method of a photocatalytic material. The invention aims to solve the technical problem that the existing photocatalytic material is difficult to recover. The method comprises the following steps: putting the carbon fiber cloth into a mixed solution of water, ethanol and acetone for ultrasonic treatment. Soaking carbon fiber cloth in the king waterAnd washing and drying for 24 h. SnCl 4 ·5H 2 O and ZnCl 2 After preparing a solution, adjusting the pH value; mixing them in equal volume, placing into carbon fiber cloth, standing for 6 hr, taking out, washing, and drying to obtain ZnSn (OH) 6 @ carbon fiber cloth; adding Bi (NO) 3 ) 3 ·5H 2 Dissolving O, and stirring and mixing with a bromine-containing salt solution; ZnSn (OH) 6 @ carbon fiber cloth is put into the mixed liquid in the hydrothermal reaction kettle for reaction, and BiOBr/ZnSn (OH) is obtained after washing and drying 6 @ carbon fiber cloth. It is used in the field of photocatalysis.)

1. Photocatalytic material BiOBr/ZnSn (OH)₆The preparation method of the @ carbon fiber cloth is characterized by comprising the following steps of:

s1: cutting carbon fiber cloth into small pieces, adding into mixed solution of water, ethanol and acetone, and performing ultrasonic treatment for 30 min; putting the carbon fiber cloth into the king water, and soaking for 24 hours; washing the carbon fiber cloth with deionized water, and drying for 4-5h at 50-60 ℃ for later use;

s2: SnCl₄·5H₂O and ZnCl₂Respectively dissolving with deionized water, dropwise adding an alkaline solution, and adjusting the pH value of the solution; mixing the above solutions in equal volume, placing into carbon fiber cloth, standing for 5-6h, taking out, washing with ethanol and deionized water for 3-4 times, drying at 50-60 deg.C for 5-6h to obtain ZnSn (OH)₆@ carbon fiber cloth;

s3: adding Bi (NO)₃)₃·5H₂Ultrasonically dissolving O in ethylene glycol; mixing a certain amount of bromine-containing salt solution with the bromine-containing salt solution, and stirring for 0.5-1h to obtain a mixed solution; ZnSn (OH)₆@ carbon fiber cloth is put into the mixed solution in the hydrothermal reaction kettle for reaction, the product is washed by ethanol and deionized water and dried for 4 to 5 hours at the temperature of between 50 and 60 ℃ to prepare BiOBr/ZnSn (OH)₎₆@ carbon fiber cloth.

2. The photocatalytic material BiOBr/ZnSn (OH) as claimed in claim 1₎₆The preparation method of the @ carbon fiber cloth is characterized in that in the step S1, the volume ratio of water to ethanol to acetone is 1:1: 1.

3. The photocatalytic material BiOBr/ZnSn (OH) as set forth in claim 1₆The preparation method of the @ carbon fiber cloth is characterized in that in step S2, the alkaline solution is NaOH or KOH solution.

4. The photocatalytic material BiOBr/ZnSn (OH) as set forth in claim 1₆The preparation method of the @ carbon fiber cloth is characterized in that in step S2, the pH value of the alkaline solution is 11-13.

5. The photocatalytic material BiOBr/ZnSn (OH) as set forth in claim 1₆The preparation method of the @ carbon fiber cloth is characterized in that in step S3, the bromine-containing salt solution is NaBr or KBr solution.

6. The photocatalytic material BiOBr/ZnSn (OH) as set forth in claim 1₆The preparation method of the @ carbon fiber cloth is characterized in that in the step S3, the hydrothermal reaction temperature is 160-220 ℃, and the reaction is carried outThe reaction time is 10-24 h.

Technical Field

The invention relates to a photocatalytic material BiOBr/ZnSn (OH)₆A preparation method of the @ carbon fiber cloth.

Background

The problem of environmental pollution is a major problem at present, and the photocatalytic technology plays an important role in solving the problem. The semiconductor photocatalysis technology has the advantages of high efficiency, energy conservation, high feasibility, secondary pollution avoidance and the like, so the technology is concerned about pollution control and environment purification. In the field of photocatalysis, due to ZnSn (OH)₆The abundant surface hydroxyl group can easily form hydroxyl radical with strong oxidizing property with photoproduction cavity in the catalytic reaction, and ZnSn (OH)₆The special energy band structure determines that a photoproduction electron hole has stronger oxidation reduction capability, so the photoproduction electron hole has huge application potential in the aspects of treating environmental pollution and solving energy crisis, and simultaneously, the problems of low visible light utilization rate, easy recombination of the photoproduction electron and the hole and the like exist, and the problems always restrict ZnSn (OH)₆Application in life and industrial production. Much research is currently being devoted to ZnSn (OH)₆The modification is carried out, the photoresponse range of the material is expanded, and the separation rate of photo-generated electron-hole pairs is improved. For example, Pengynggang and Lu et al respectively combine GO, C and ZnSn (OH)₆The photocatalysis efficiency is effectively improved by increasing the specific surface area and the crystallinity of the material by compounding.

BiOBr is nearA new photocatalytic material that has gradually developed over a decade. The material has the advantages of low price, simple synthesis method and strong absorption in a visible light region. Meanwhile, the electron-hole pairs are easy to separate, so that the photocatalyst has high photocatalytic activity. Comprehensively considering the physical characteristics of the two materials, the BiOBr and the ZnSn (OH)₆Heterojunction can be formed by compounding, the photoresponse range of the material in a visible light region is widened, and the photocatalytic performance of the material is improved. However, the current powdered catalyst has the problems of poor dispersibility, easy agglomeration, difficult recycling and the like, and greatly limits the further application of the material.

Aiming at the problem, the invention provides a method for loading ZnSn (OH) by adopting carbon fiber cloth₆The proposal of the/BiOBr heterojunction composite material not only widens ZnSn (OH)₆The visible light response effectively improves the photocatalytic performance of the material and skillfully solves the problem that the powder photocatalytic material is difficult to recycle.

Disclosure of Invention

The invention aims to solve the technical problem of difficult recovery of the existing photocatalytic material, thereby providing a photocatalytic material BiOBr/ZnSn (OH)₆A preparation method of the @ carbon fiber cloth.

The invention discloses a photocatalytic material BiOBr/ZnSn (OH)₆The preparation method of the @ carbon fiber cloth comprises the following steps:

s1: cutting carbon fiber cloth into small pieces, adding into mixed solution of water, ethanol, and acetone (or acetylacetone), and performing ultrasonic treatment for 30 min. Putting the carbon fiber cloth into the king water, and soaking for 24 hours; washing the carbon fiber cloth with deionized water, drying at 60 ℃ for 120min, and drying for later use;

s2: SnCl₄·5H₂O and ZnCl₂Respectively dissolving with deionized water, dropwise adding an alkaline solution, and adjusting the pH value of the solution; mixing the above solutions in equal volume, placing into carbon fiber cloth, standing for 5-6h, taking out, washing with ethanol and deionized water for 3-4 times, drying at 50-60 deg.C for 5-6h to obtain ZnSn (OH)₆@ carbon fiber cloth;

s3: adding Bi (NO)₃)₃·5H₂Ultrasonically dissolving O in ethylene glycol; dissolving a certain amount of bromine-containing saltMixing the solution with the water, and stirring for 0.5-1h to obtain a mixed solution; ZnSn (OH)₆@ carbon fiber cloth is put into the mixed solution in a hydrothermal reaction kettle for reaction, the product is washed by ethanol and deionized water and dried for 4 to 5 hours at the temperature of between 50 and 60 ℃ to prepare BiOBr/ZnSn (OH)₆@ carbon fiber cloth.

Preferably, the volume ratio of the water to the ethanol to the acetone in the step S1 is 1:1: 1;

preferably, the acetone in step S1 may be replaced by acetylacetone.

Preferably, the alkaline solution in step S2 is a NaOH or KOH solution;

preferably, the pH value of the solution in the step S2 is 11-13;

preferably, the bromine-containing salt solution in step S3 is NaBr or KBr solution

Preferably, the hydrothermal reaction temperature in the step S3 is 160-220 ℃, and the time is 10-24 h;

the invention takes carbon fiber cloth as a carrier, and BiOBr/ZnSn (OH) is loaded on the carrier₆And (4) granulating to prepare the composite photocatalytic material. Because the carbon fiber cloth has the advantages of low price, easy acquisition, large specific surface area, high mechanical strength, good adsorption performance, no pollution to the environment, good compatibility with a catalyst and the like, the invention selects the carbon fiber cloth as BiOBr/ZnSn (OH)₆A carrier of nano powder. BiOBr/ZnSn (OH)₆Firmly combined with the carbon fiber cloth, is not easy to fall off, not only avoids the agglomeration of the catalyst and realizes the recycling, but also can utilize the good adsorption performance of the carbon fiber cloth to adsorb degradation substances to the surface of a carrier and increase BiOBr/ZnSn (OH)₆Contact surface with degradation material to improve BiOBr/ZnSn (OH)₆The degradation efficiency of (a). The photocatalytic material prepared by the invention can achieve 99.96% of photocatalytic degradation effect on rhodamine B, and can be recycled.

The invention is further described with reference to the following figures and detailed description.

Drawings

FIG. 1 shows ZnSn (OH) in example 1₆@ scanning electron microscope photograph of carbon fiber cloth;

FIG. 2 is a scanning electron micrograph of BiOBr @ carbon fiber cloth in example 1;

FIG. 3 shows BiOBr @ ZnSn (OH) in example 1₆The XRD test result of the @ carbon fiber cloth;

FIG. 4 is BiOBr @ ZnSn (OH) in example 1₆@ carbon fiber cloth scanning electron microscope photograph;

FIG. 5 shows ZnSn (OH) in example 1₆@ carbon fiber cloth, BiOBr @ ZnSn (OH)₆@ carbon fiber cloth.

Detailed Description

The invention will be described more fully hereinafter with reference to the accompanying drawings. Those skilled in the art will be able to implement the invention based on these teachings.