阅读说明：本技术 一种基于共价键结合的光催化剂负载织物的制备方法 (Preparation method of photocatalyst-loaded fabric based on covalent bond combination ) 是由 刘保江 杨瑞祥 钟山 张漓杉 高品 晏凌峰 杨瑞颖 朱智甲 胡春艳 赵强强 朱晨 于 2019-09-09 设计创作，主要内容包括：本发明涉及一种基于共价键结合的光催化剂负载织物的制备方法,分别用硅烷偶联剂对光催化剂和棉织物进行改性反应制备。本发明中,光催化剂与棉织物是基于共价键连接的,从而使光催化剂与棉织物的结合比较牢固,具有高的循环稳定性能；同时制备方法简单,制备条件要求低,绿色环保,极大提高了光催化技术在污水处理中的应用。(The invention relates to a preparation method of a photocatalyst-loaded fabric based on covalent bond combination, which is prepared by respectively carrying out modification reaction on a photocatalyst and a cotton fabric by using a silane coupling agent. In the invention, the photocatalyst and the cotton fabric are connected based on covalent bonds, so that the combination of the photocatalyst and the cotton fabric is firmer and the photocatalyst has high cycle stability; meanwhile, the preparation method is simple, the requirement on preparation conditions is low, the preparation method is green and environment-friendly, and the application of the photocatalysis technology in sewage treatment is greatly improved.)

1. The photocatalytic functional fabric is characterized in that a photocatalyst modified by a silane coupling agent containing carbon-carbon double bonds and a fabric modified by a silane coupling agent containing sulfydryl are obtained by connecting through thiol-ene click chemical reaction.

2. The fabric of claim 1, wherein the photocatalyst isFe(III)/BiVO₄(ii) a The silane coupling agent containing carbon-carbon double bonds is KH 570; the mercapto silane coupling agent is KH 580.

3. A preparation method of a photocatalytic functional fabric comprises the following steps:

under the irradiation of ultraviolet light, the photocatalyst modified by the silane coupling agent containing carbon-carbon double bonds and the fabric modified by the silane coupling agent containing sulfydryl are connected in a reaction way.

4. The method according to claim 3, wherein the photocatalyst is Fe/BiVO₄Prepared by the following method: and dropwise adding the ammonium vanadate solution into the bismuth nitrate solution, adjusting the pH value to perform hydrothermal reaction, washing and drying to obtain bismuth vanadate, then dispersing the bismuth vanadate into the ferric nitrate solution, reacting, washing and drying to obtain the bismuth vanadate.

5. The method according to claim 3, wherein the photocatalyst modified by the silane coupling agent containing a carbon-carbon double bond is Fe (III)/BiVO₄a/KH 570 complex; the fabric modified by the silane coupling agent containing the mercapto group is KH 580/cotton.

6. The preparation method according to claim 3, wherein the photocatalyst modified by the silane coupling agent containing carbon-carbon double bonds is specifically: adding the silane coupling agent containing carbon-carbon double bonds into the aqueous solution of the photocatalyst, stirring in a water bath at 50-80 ℃, washing and drying.

7. The preparation method according to claim 3, wherein the mercapto group-containing silane coupling agent modified fabric is specifically: adding the fabric into an ethanol-deionized water solution; then, adding a silane coupling agent solution containing sulfydryl into the solution, adjusting the pH value to 2-6 by using acetic acid, and continuing stirring; finally, curing in an oven; the fabric is one or two of cotton fabric, hemp fabric, polyester fabric, viscose fabric, silk fabric, spandex fabric, nylon fabric and vinylon fabric.

8. The preparation method according to claim 3, wherein the reactive linkage is specifically: dispersing a photocatalyst modified by a silane coupling agent containing carbon-carbon double bonds in an ethanol-deionized water solution, adding 2, 2-dimethylolpropionic acid, then soaking the photocatalyst into a sulfydryl-containing silane coupling agent modified fabric, and stirring for 2-6 hours under the irradiation of 400-600W ultraviolet rays.

9. A photocatalytic functional fabric prepared by the method of claim 3.

10. Use of the photocatalytic functional fabric according to claim 1.

Technical Field

The invention belongs to the field of preparation of photocatalyst functional fabrics, and particularly relates to a preparation method of a photocatalyst loading fabric based on covalent bond combination.

Background

Water pollution has become an important factor that restricts the current socioeconomic development. Wherein organic pollutants and heavy metal ions are the main pollution sources. The traditional water pollution treatment method has certain problems such as secondary pollution, high energy consumption, poor system stability and the like. Therefore, the photocatalytic method with green environmental protection, low energy consumption and high stability has attracted extensive attention of researchers.

Among various semiconductors, bismuth vanadate is a photocatalyst having non-toxicity, high photostability and excellent photocatalytic performance; in addition, by doping with iron metal ions, the photocatalytic activity is greatly improved. However, in an aqueous solution, iron ion-doped bismuth vanadate powder has poor dispersibility and is easy to aggregate, so that the photocatalytic performance is reduced; more importantly, the photocatalyst powder is dispersed in the aqueous solution, so that the reprocessing is more difficult, the reusability is poor, and even secondary pollution is caused.

To address this problem, researchers have supported photocatalysts on suitable substrates. To date, many techniques have been developed such as suspension impregnation, sol-gel and electrospinning. In addition, many different types of substrates have been used, such as stainless steel, activated carbon, silica and carbon cloth. However, the photocatalyst-supported cotton fabric prepared by the suspension impregnation method has poor adhesion and is easily released since the substrate and the photocatalyst are connected only by van der waals force and hydrogen bond. Although the sol-gel method and the electrospinning method can solve the problems caused by poor connection, most of the catalysts cannot react with contaminants because they are surrounded by useless matrices.

CN 103194888A discloses a preparation method of a high-efficiency visible light catalytic function fabric, the prepared photocatalytic fabric catalyst and the fabric have the problems of relatively poor durability and poor cycle stability through intermolecular forces (hydrogen bonds and Van der Waals force).

Disclosure of Invention

The invention aims to solve the technical problems of providing a preparation method of a photocatalyst-loaded fabric based on covalent bond combination, overcoming the technical problems of poor adhesion and easy shedding of the photocatalyst in the prior art, and modifying the photocatalyst and the cotton fabric by using a silane coupling agent containing carbon-carbon double bonds and sulfydryl respectively; the photocatalyst was then attached to the cotton fabric by thiol-ene click chemistry.

The photocatalytic functional fabric is obtained by connecting a photocatalyst modified by a silane coupling agent containing carbon-carbon double bonds and a fabric modified by a silane coupling agent containing sulfydryl through a mercaptan-alkene click chemical reaction.

The photocatalyst is Fe (III)/BiVO₄(ii) a The silane coupling agent containing carbon-carbon double bonds is KH 570; the mercapto silane coupling agent is KH 580.

The invention relates to a preparation method of a photocatalytic functional fabric, which comprises the following steps: under the irradiation of ultraviolet light, the photocatalyst modified by the silane coupling agent containing carbon-carbon double bonds and the fabric modified by the silane coupling agent containing sulfydryl are connected in a reaction way.

The preferred mode of the above preparation method is as follows:

the photocatalyst is Fe/BiVO₄Prepared by the following method (synthesizing Fe (III)/BiVO by a hydrothermal method₄Photocatalytic material): dropwise adding an ammonium vanadate solution into a bismuth nitrate solution, adjusting the pH value to 2-4, carrying out hydrothermal reaction, washing and drying to obtain bismuth vanadate, then dispersing the bismuth vanadate into an iron nitrate solution, reacting, washing and drying to obtain the bismuth vanadate; wherein the hydrothermal reaction temperature and time are respectively 160-; the reaction temperature and time of bismuth vanadate and ferric nitrate are 60-90 ℃ and 4-8 hours respectively. The ammonium vanadate solution is obtained by dissolving ammonium vanadate in a sodium hydroxide solution; the bismuth nitrate solution is obtained by dissolving bismuth nitrate in nitric acid.

The photocatalyst modified by the silane coupling agent containing the carbon-carbon double bond is Fe (III)/BiVO₄a/KH 570 complex; the fabric modified by the silane coupling agent containing the mercapto group is KH 580/cotton.

The photocatalyst modified by the silane coupling agent containing carbon-carbon double bonds is specifically as follows: adding the silane coupling agent containing carbon-carbon double bonds into the aqueous solution of the photocatalyst, stirring in a water bath at 50-80 ℃, washing and drying.

The mercapto silane coupling agent modified fabric is specifically as follows: adding the fabric into an ethanol-deionized water solution (volume ratio is 4:1-1: 1); then, adding a silane coupling agent (KH580) solution containing sulfhydryl groups into the solution, adjusting the pH value to 2-6 by using acetic acid, and continuing stirring; finally, curing in an oven; wherein the curing temperature and time are 100-130 ℃ and 3-10 min.

The fabric is one or two of cotton fabric, hemp fabric, polyester fabric, viscose fabric, silk fabric, spandex fabric, nylon fabric and vinylon fabric which are blended.

The cotton fabric is a treated cotton fabric, and specifically comprises the following components: pure cotton fabric washed with acetone and absolute ethanol.

The reaction connection is specifically as follows: dispersing a photocatalyst modified by a silane coupling agent containing carbon-carbon double bonds in an ethanol-deionized water solution (the volume ratio is 4:1-1:1), adding 2, 2-dimethylolpropionic acid, then soaking the photocatalyst into a sulfydryl-containing silane coupling agent modified fabric, and stirring the mixture for 2 to 6 hours under the irradiation of 400-W ultraviolet rays.

The invention relates to a photocatalytic functional fabric prepared by the method.

The photocatalytic functional fabric is applied to treating organic matters and heavy metal ions in sewage and degrading pollutants in soil.

Advantageous effects

(1) Compared with the existing loading method, the method modifies the cotton fabric and the photocatalyst, combines the modified cotton fabric and the photocatalyst in a covalent bond mode through thiol-sulfhydryl click chemical reaction, has stronger bonding capability compared with Van der Waals force and hydrogen bond, overcomes the defect of poor adsorption fastness of the traditional photocatalyst, and greatly improves the cycle stability;

(2) meanwhile, the invention is simple, convenient, low in cost and environment-friendly; the prepared iron ion doped bismuth vanadate photocatalyst loaded cotton fabric has excellent effects on dye degradation and hexavalent chromium ion reduction.

Drawings

FIG. 1 shows the production of Fe (III) @ BiVO₄Schematic representation of cotton fabric;

FIG. 2 is a schematic representation of the thiol-ene click reaction between KH570 and KH 580;

FIG. 3(a) FTIR spectra of prepared samples; (b) KH 580/cotton, BiVO₄Cotton and Fe (III) @ BiVO₄Raman spectrum of cotton; (b) inset in (a) shows the color reaction of pure cotton and KH 580/cotton after DTNB treatment; (c) KH570 and Fe (III) @ BiVO₄FTIR spectrum of cotton; (d) KH 580/cotton, BiVO₄Cotton and Fe (III) @ BiVO₄XRD pattern of cotton;

fig. 4(a) pure cotton; (b) KH 580/cotton and (c) Fe (III) @ BiVO₄SEM image of cotton; (d-e) enlarging the image and (f) mapping Fe (III) @ BiVO₄O, Bi, V and Fe elements in cotton;

FIG. 5 shows the degradation and kinetic fit of Cr (VI) (a, c) and RB-19(b, d) for the samples prepared;

FIG. 6(a) cycle performance and (b) XRD pattern of Fe (III) @ BiVO 4/cotton; (b) the inset shows SEM images before and after use.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

In the embodiment of the invention, plain pure cotton fabric (5 multiplied by 5 cm) provided by China Gaoming textile²,120g/m²) Other medicines are purchased from the Chinese medicine group, and all chemicals are reagent grade and can be used without further purification.