阅读说明：本技术 一种温和条件下制备BiOCl超薄纳米片的方法及其应用 (Method for preparing BiOCl ultrathin nanosheets under mild conditions and application thereof ) 是由 冯德鑫 张显龙 咸漠 于 2019-09-30 设计创作，主要内容包括：本发明公开了一种温和条件下制备BiOCl超薄纳米片的方法及其应用,属于纳米材料合成领域。本发明解决现有制备BiOCl工艺存在制造成本高,反应工艺复杂,难以扩大化生产等问题。本发明制备方法如下：将硝酸铋加入到有机醇中,搅拌0.5-2h,溶解均匀后,向其中加入二氯甲烷和水,继续搅拌0.5-2h后,将混合溶液转移至具有聚四氟乙烯内衬的高压反应釜中,反应温度70-120℃,反应2-12h即可得到BiOCl超薄纳米片,本发明具有制备过程简单,制备温度低,反应条件温和,易于工业化生产等优点。本发明BiOCl用作光催化剂。(the invention discloses a method for preparing BiOCl ultrathin nanosheets under mild conditions and application thereof, and belongs to the field of synthesis of nanomaterials. The invention solves the problems of high manufacturing cost, complex reaction process, difficult expanded production and the like of the existing BiOCl preparation process. The preparation method comprises the following steps: adding bismuth nitrate into organic alcohol, stirring for 0.5-2h, adding dichloromethane and water after uniform dissolution, continuously stirring for 0.5-2h, transferring the mixed solution into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting for 2-12h at 70-120 ℃ to obtain the BiOCl ultrathin nanosheet. The BiOCl of the invention is used as a photocatalyst.)

1. A method for preparing BiOCl ultrathin nanosheets under mild conditions is characterized in that the method for preparing BiOCl ultrathin nanosheets is realized through the following steps:

Step one, adding pentahydrate bismuth nitrate into organic alcohol, and stirring for 0.5-2 h;

secondly, adding a chlorine source and water, and stirring for 0.5-2 h;

and step three, transferring the obtained product to a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 2-12h at 70-120 ℃, filtering and separating out solids, respectively washing the obtained solid compound for 3 times by using water and ethanol, and drying the solid compound in an oven at 50-80 ℃ to obtain the BiOCl ultrathin nanosheets.

2. the method for preparing BiOCl ultrathin nanosheets under mild conditions as recited in claim 1, wherein: and the chlorine source in the second step is dichloromethane.

3. The method for preparing BiOCl ultrathin nanosheets under mild conditions as recited in claim 1, wherein: in the first step, the organic alcohol is one or a combination of methanol, ethanol, propanol, isopropanol and ethylene glycol.

4. The method for preparing BiOCl ultrathin nanosheets under mild conditions as recited in claim 1, wherein: the dosage ratio of the bismuth nitrate to the organic alcohol in the first step is as follows: (0.1-1) mmol: 1 mL.

5. The method for preparing BiOCl ultrathin nanosheets under mild conditions as recited in claim 1, wherein: in the second step, the volume ratio of the organic alcohol to the dichloromethane to the water is 4: (1-4): (1-8).

6. the method for preparing BiOCl ultrathin nanosheets under mild conditions as recited in claim 1, wherein: and step three, the reaction temperature is 80-100 ℃, and the reaction time is 4-10 h.

7. BiOCl ultrathin nanoplates synthesized according to the method of any one of claims 1-6 are used as photocatalysts.

8. use of BiOCl ultrathin nanoplates as in claim 7, characterised in that BiOCl ultrathin nanoplates photocatalytically degrade industrial dyes.

Technical Field

The invention belongs to the technical field of preparation of nano materials, and particularly provides a preparation method and application of BiOCl ultrathin nanosheets.

Background

with the rapid development of industrial technology, the environmental pollution problem is more and more prominent, and the human life is seriously influenced and threatened. The photocatalysis technology is a green advanced oxidation technology and has wide research and application in the field of environmental pollution. The development of efficient, stable and low-cost photocatalyst has been a research hotspot in the field of photocatalyst research.

BiOCl is a novel layered semiconductor compound having a tetragonal crystal structure consisting of [ Bi2O2 ]]And double-layer Cl atoms are stacked in a staggered way, so that the photocatalyst has the advantages of no toxicity, chemical stability and the like, has a good photocatalytic activity due to the inherent layered structure and electronic characteristics, and has wide application prospect and competitiveness. Generally, the performance of the two-dimensional nano material is closely related to the thickness of the two-dimensional nano material, and the thinner the thickness of the two-dimensional nano material is, more active sites are exposed for reaction, so that the conductivity of the two-dimensional nano material is increased, and the photocatalytic activity of the two-dimensional nano material can be obviously improved. Wu et al synthesize BiOCl ultrathin nanosheets (Crystal. grown Des.2018,18,5479-5491) with the thickness of 2.5-12nm by adjusting the addition amounts of polyvinylpyrrolidone and polyethyleneimine in an ethylene glycol solution of bismuth nitrate pentahydrate; zhang et al found the thickness of BiOCl nanosheet and H in the reaction system⁺The concentration is closely related with the H in the reaction system⁺the thickness of the BiOCl nanosheets is reduced from 250nm to 15 nm (ACS Sustainable chem. Eng.2017,5, 4619-4629).

Although various methods have been developed to prepare the BiOCl ultrathin nanosheet, in order to control the thickness of the BiOCl nanomaterial, the pH value of a reaction system needs to be controlled, or a surfactant which is difficult to clean is added, and a high-temperature reaction is needed, so that the problems of high manufacturing cost, complex reaction process, difficulty in expanded production and the like exist. Therefore, the development of a method for preparing the BiOCl ultrathin nanosheet, which is simple in operation, low in manufacturing cost and mild in reaction condition, is very important.

disclosure of Invention

the invention solves the technical problems of high manufacturing cost, complex reaction process, difficult expanded production and the like of the existing BiOCl preparation process; the invention provides a method for preparing BiOCl ultrathin nanosheets under mild conditions and application thereof, and has the advantages of simple operation, low reaction temperature, low production cost, short production period, easiness in large-scale industrial production and the like.

the method for preparing the BiOCl ultrathin nanosheet under the mild condition is carried out according to the following steps:

Step one, adding pentahydrate bismuth nitrate into organic alcohol, and stirring for 0.5-2 h;

Secondly, adding a chlorine source and water, and stirring for 0.5-2 h;

and step three, transferring the obtained product to a high-pressure reaction kettle with a polytetrafluoroethylene lining, reacting for 2-12h at 70-120 ℃, filtering and separating out solids, respectively washing the obtained solid compound for 3 times by using water and absolute ethyl alcohol, and drying the solid compound in an oven at 50-80 ℃ to obtain the BiOCl ultrathin nanosheet.

further, the chlorine source in the second step is dichloromethane.

Further limiting, in the step one, the organic alcohol is one or a combination of several of methanol, ethanol, propanol, isopropanol and ethylene glycol in any ratio.

Further limiting, the dosage ratio of the bismuth nitrate to the organic alcohol in the first step is as follows: (0.1-1) mmol: 1mL of

Further limiting, in the second step, the volume ratio of the organic alcohol, the dichloromethane and the water is 4: (1-4): (1-8).

Further limiting, the reaction temperature of the third step is 80-100 ℃, and the reaction time is 4-10 h.

the BiOCl ultrathin nanosheet synthesized by the method is used as a photocatalyst and can be used for photocatalytic industrial dyes.

According to the invention, a clear and transparent precursor is synthesized by a solvothermal method, and then the BiOCl ultrathin nanosheet is prepared by adding water and quickly hydrolyzing, wherein the hydrolysis process can be completed within a few seconds.

the BiOCl synthesized by the invention has the following two beneficial effects when used as a photocatalyst to degrade industrial dye under visible light:

The ultrathin BiOCl nanosheet prepared by the method is simple in process, short in synthesis period, low in energy consumption, easy in obtaining of raw materials, and excellent in degradation effect when industrial dyes are degraded under visible light photocatalysis.

the invention firstly proposes that organic dichloromethane is used as a chlorine source to synthesize the BiOCl ultrathin nanosheets, and compared with the traditional technology using an inorganic chlorine source, the organic dichloromethane not only is used as the chlorine source, but also plays a key role in regulating and controlling the morphology. The invention explores a new trend of synthesizing BiOCl from an organic chlorine source.

drawings

FIG. 1 is an X-ray powder diffraction test chart of a BiOCl ultrathin nanosheet;

FIG. 2 is a scanning electron microscope image of BiOCl ultrathin nanosheets;

FIG. 3 is a performance representation of rhodamine B degradation of BiOCl ultrathin nanosheets under visible light irradiation.

Detailed Description