阅读说明：本技术 一种纱线保护型柔性光催化织物的制备方法 (Preparation method of yarn protection type flexible photocatalytic fabric ) 是由 胡晓霞 王耀村 邢彦军 于 2020-12-17 设计创作，主要内容包括：本发明提供了一种纱线保护型柔性光催化织物的制备方法。该方法先制备得到卤氧化铋/石墨烯/纱线柔性复合光催化材料,再将其编织成“光催化布”,主要包括如下步骤：步骤1,在纺织纱线表面包覆导电材料,得到导电纱线；步骤2,在导电纱线表面附着光催化材料,得到光催化纱线；步骤3,将光催化纱线制成织物。本发明的有益效果是：(1)运用本发明方法获得的光催化织物,在使用过程中可有效减少光催化剂的流失,减少外部环境对载体的损害,提高光催化织物的使用寿命。(2)此方法在为日益严重的环境污染治理提供一种新材料的同时,还可拓宽纺织纤维的应用领域,对纺织行业的可持续发展和产品转型、结构调整具有积极的现实意义。(The invention provides a preparation method of a yarn protection type flexible photocatalytic fabric. The method firstly prepares bismuth oxyhalide/graphene/yarn flexible composite photocatalytic material, and weaves the material into photocatalytic cloth, which mainly comprises the following steps: step 1, coating a conductive material on the surface of a textile yarn to obtain a conductive yarn; step 2, attaching a photocatalytic material to the surface of the conductive yarn to obtain a photocatalytic yarn; and 3, manufacturing the photocatalytic yarn into a fabric. The invention has the beneficial effects that: (1) the photocatalytic fabric obtained by the method can effectively reduce the loss of the photocatalyst in the use process, reduce the damage of the external environment to the carrier and prolong the service life of the photocatalytic fabric. (2) The method provides a new material for treating increasingly serious environmental pollution, can also widen the application field of textile fibers, and has positive practical significance for sustainable development, product transformation and structure adjustment of the textile industry.)

1. A preparation method of a yarn protection type flexible photocatalytic fabric is characterized by comprising the following steps:

step 1, coating a conductive material on the surface of a textile yarn to obtain a conductive yarn;

step 2, attaching a photocatalytic material to the surface of the conductive yarn to obtain a photocatalytic yarn;

and 3, manufacturing the photocatalytic yarn into a fabric.

2. The method for preparing the yarn-protecting flexible photocatalytic fabric according to claim 1, wherein the textile yarn is at least one of cotton, polyester, acrylic, nylon or regenerated cellulose fiber.

3. The method for preparing a yarn-protecting flexible photocatalytic fabric according to claim 1, wherein the conductive material is graphene.

4. The method for preparing a yarn-protecting flexible photocatalytic fabric according to claim 1, wherein the preparation of the conductive yarn comprises the following subdivision steps:

step 1.1, coating graphene oxide on the surface of the textile yarn by adopting an in-situ growth method;

and 1.2, reducing the graphene oxide on the surface of the textile yarn into graphene by using a reducing agent to obtain the conductive yarn.

5. The method for preparing the yarn-protecting flexible photocatalytic fabric according to claim 4, wherein the reducing agent is at least one of sodium borohydride, vitamin C, glucose, chitosan or sodium hydrosulfite.

6. The method for preparing the yarn-protecting flexible photocatalytic fabric according to claim 5, wherein the concentration of the reducing agent is 0.1-10%.

7. The method of claim 1, wherein the photocatalytic material comprises bismuth oxyhalide.

8. The method for preparing a yarn-protecting flexible photocatalytic fabric according to claim 1, wherein the preparation of the photocatalytic yarn comprises the following steps:

and (3) reacting bismuth nitrate and potassium halide according to a certain proportion by adopting a layer-by-layer self-assembly method, and loading the synthesized bismuth oxyhalide on the surface of the conductive yarn to prepare the bismuth oxyhalide loaded photocatalytic yarn.

9. The preparation method of the yarn-protecting flexible photocatalytic fabric according to claim 8, wherein the molar ratio of the bismuth nitrate to the potassium halide is 1: 1-1: 2.

10. The method of claim 8, wherein the potassium halide is at least one of potassium chloride, potassium bromide or potassium fluoride.

Technical Field

The invention relates to a preparation method of a photocatalytic material, in particular to a preparation method of a yarn protection type flexible photocatalytic fabric, and belongs to the novel technical field of combination of inorganic nano materials and textile materials.

Background

With the rapid development of industrialization, toxic and harmful sewage is increased gradually, and pollution seriously threatens human physical and psychological health. In recent years, the application of semiconductor photocatalytic oxidation technology to the treatment of printing and dyeing wastewater has been widely studied. The narrow band gap semiconductor bismuth oxyhalide (BiOX ═ Cl, Br, I) has attracted much attention for its higher visible light photocatalytic activity.

Graphene is an excellent conductive material, and has a very perfect and characteristic sp due to the fact that carbon atoms in the structure tightly form a two-dimensional honeycomb structure²Hybridization, the specific surface area of graphene is theoretically as high as 2600m²(g) carrier mobility up to 200000cm at room temperature²V^-1s^-1. Graphene and a semiconductor are compounded, and a regular two-dimensional planar structure of the graphene is used as a carrier of the photocatalyst, so that on one hand, the dispersion degree of the catalyst can be improved, on the other hand, the conductivity of the photocatalyst can accelerate the rate of photon-generated electron migration, the photon-generated carriers are separated efficiently, and the photocatalytic activity of the composite material is improved.

The photocatalytic degradation of pollutants in water by using powder generally has the problems of easy agglomeration and low activity, and the particles are fine and difficult to recover, so that the loss of active ingredients of the catalyst is large, secondary pollution is easy to cause, the regeneration and the reutilization of the photocatalyst are not facilitated, and the resource waste is caused.

The photocatalytic material is loaded on the carrier, so that adsorption, degradation and separation can be organically combined, the difficult problem of catalyst separation and recovery can be solved, and the defects of poor stability and easy poisoning of a suspended phase catalyst are overcome. Therefore, the loading and regeneration of the photocatalyst is one of the key technologies to achieve its efficient application.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: a novel, efficient and reproducible photocatalytic fabric with visible light response and a preparation method thereof are provided.

In order to solve the technical problem, the invention provides a preparation method of a yarn protection type flexible photocatalytic fabric. The method firstly prepares bismuth oxyhalide/graphene/yarn flexible composite photocatalytic material, and weaves the material into photocatalytic cloth, which mainly comprises the following steps:

step 1, coating a conductive material on the surface of a textile yarn to obtain a conductive yarn;

step 2, attaching a photocatalytic material to the surface of the conductive yarn to obtain a photocatalytic yarn;

and 3, manufacturing the photocatalytic yarn into a fabric.

In some embodiments, the textile yarns are selected from at least one of cotton, polyester, acrylic, nylon, or regenerated cellulose fibers.

In some embodiments, the conductive material is graphene.

In some embodiments, the preparation of the conductive yarn comprises the following subdivided steps:

step 1.1, coating graphene oxide on the surface of the textile yarn by adopting an in-situ growth method;

and 1.2, reducing graphene oxide on the surface of the textile yarn into graphene by using a reducing agent to obtain the conductive yarn.

In some embodiments, the reducing agent is at least one of sodium borohydride, vitamin C, glucose, chitosan, or sodium hydrosulfite.

In some embodiments, the concentration of the reducing agent is 0.1% to 10%.

In some embodiments, the photocatalytic material comprises bismuth oxyhalide.

In some embodiments, the preparation of the photocatalytic yarn comprises the steps of:

and (3) reacting bismuth nitrate and potassium halide according to a certain proportion by adopting a layer-by-layer self-assembly method, and loading the synthesized bismuth oxyhalide on the surface of the conductive yarn to prepare the bismuth oxyhalide loaded photocatalytic yarn.

In some embodiments, the molar ratio of the bismuth nitrate to the potassium halide is 1:1 to 1: 2.

In some embodiments, the potassium halide is at least one of potassium chloride, potassium bromide, or potassium fluoride.

The invention has the beneficial effects that:

(1) the photocatalytic fabric obtained by the method can effectively reduce the loss of the photocatalyst in the use process, reduce the damage of the external environment to the carrier and prolong the service life of the photocatalytic fabric.

(2) The method provides a new material for treating increasingly serious environmental pollution, can also widen the application field of textile fibers, and has positive practical significance for sustainable development, product transformation and structure adjustment of the textile industry.

Detailed Description

Unless otherwise defined, technical or scientific terms used in the claims and the specification of this patent shall have the ordinary meaning as understood by those of ordinary skill in the art to which this patent belongs.

The invention provides a preparation method of a yarn protection type flexible photocatalytic fabric, which comprises the steps of taking graphene oxide, bismuth nitrate, potassium halide, a reducing agent and the like as reaction raw materials, taking textile yarns as carriers, firstly preparing conductive yarns and photocatalytic yarns, and then weaving the yarns to obtain the photocatalytic fabric.

The preparation method of the yarn protection type flexible photocatalytic fabric provided by the invention comprises the following three steps:

the method comprises the following steps: and covering the surface of the yarn with graphene to obtain the conductive yarn.

The preparation method of the conductive yarn comprises the following steps: graphene oxide is coated on the surface of the yarn by an in-situ growth method, and then the yarn is reduced by a certain amount of reducing agent to prepare the graphene-coated conductive yarn. The yarn is at least one of cotton, terylene, acrylic fiber, chinlon or regenerated cellulose fiber. The reducing agent is at least one of sodium borohydride, vitamin C, glucose, chitosan or sodium hydrosulfite. The concentration of the reducing agent is 0.1% -10%, and the concentration refers to: the percentage by mass of the reducing agent in the solution is, for example, 5g of glucose dissolved in 100g of water, and the glucose solution thus obtained is used as the reducing agent at a concentration of 5%.

The sodium hydrosulfite is sodium hydrosulfite with chemical formula of Na₂S₂O₄It is a chemical product of white sand-like crystal or light yellow powder, and sodium dithionite is often used as a reducing agent.

The graphene oxide is coated on the surface of the yarn, so that the yarn can be protected, and certain conductivity can be given to the yarn. Meanwhile, the graphene structure has rich pi conjugated system, and can adsorb BiO through electrostatic attraction⁺And the BiOX and the graphene are combined more firmly and are loaded on the graphene intermediate layer without falling off.

Step two: and attaching a photocatalytic material to the surface of the conductive yarn to obtain the photocatalytic yarn.

The preparation method of the photocatalytic yarn comprises the following steps: and loading bismuth oxyhalide synthesized by bismuth nitrate and potassium halide according to a certain proportion on the conductive yarn by adopting a layer-by-layer self-assembly method to prepare the bismuth oxyhalide loaded photocatalytic yarn. The potassium halide is at least one of potassium chloride, potassium bromide or potassium fluoride. The molar ratio of the bismuth nitrate to the potassium halide is 1: 1-1: 2.

The layer-by-layer self-assembly method is a technology which utilizes a substrate to alternatively adsorb two or more substances from a solution and complement other multivalent substances, and can be used in various fields such as optics, catalysis, energy sources, biomedicine and the like because a functional film can be generated on the surface of a solid.

Step three: and preparing the photocatalytic yarn into fabric to obtain the photocatalytic cloth.

The photocatalytic fabric is obtained by preparing the photocatalytic yarn with excellent performance and then weaving, and the fabric can effectively protect the yarn in the using process.

The photocatalytic cloth provided by the invention is flexible. Compared with the rigid inorganic carrier in the prior art, the flexible textile carrier has the characteristics of large specific surface area, porosity, easy chemical modification of the surface and the like, can efficiently adsorb pollutants, and greatly accelerates the photocatalytic degradation reaction rate. The fiber material also has the advantages of being capable of being woven, easy to cut, easy to form and the like, and can meet the requirements of different forms.

The finished yarn is woven into the photocatalytic cloth with visible light response, so that the loss of the photocatalyst can be effectively reduced in the using process, the damage of the external environment to the yarn is reduced, and the service life of the photocatalytic fabric is prolonged. Meanwhile, as each yarn has good electric conductivity and photocatalytic activity, the photocatalytic cloth shows more excellent photocatalytic performance than the directly loaded cloth.

The invention will be further illustrated with reference to the following specific examples.

Example 1

The method comprises the following steps of pretreating cotton yarns in a sodium hydroxide solution with the concentration of 10g/L for 15min at the temperature of 80 ℃, hydrolyzing ester bonds on the surfaces of cotton fibers after treatment, roughening the surfaces of the fibers, and providing more active sites for loading and coating graphene oxide on the cotton yarns.

The cotton yarn is soaked in 0.5g/L graphene oxide dispersion liquid for 30 min. Taking out and drying. And then soaking the cotton yarn in a vitamin C solution with the concentration of 5%, reacting at 90 ℃ for 30min, taking out, washing with deionized water, and drying to obtain the graphene-coated cotton yarn.

Impregnating cotton yarn with 0.5mol/L Bi (NO)₃)₃The immersion time in the solution was 30 min. Taking out, cleaning and drying. And then soaking the cotton yarn in a KCl solution with the concentration of 0.7mol/L, reacting at room temperature for 30min, taking out, washing with deionized water, and drying to obtain the bismuth oxychloride loaded photocatalytic cotton yarn.

The cotton yarn is woven into fabric, so that the flexible photocatalytic fabric can be obtained.

Example 2

Pretreating the polyester yarn in a sodium hydroxide solution with the concentration of 10g/L at the temperature of 80 ℃ for 15min, hydrolyzing ester bonds on the surface of the treated polyester yarn, roughening the surface of the fiber, and providing more active sites for the load coating of graphene oxide on the polyester yarn.

Soaking the polyester yarns in 0.5g/L graphene oxide dispersion liquid for 30 min. Taking out and drying. And then soaking the polyester yarn in sodium hydrosulfite solution with the concentration of 0.1%, reacting at 90 ℃ for 30min, taking out, washing with deionized water, and drying to obtain the graphene-coated polyester yarn.

Soaking polyester yarn in 0.5mol/L Bi (NO)₃)₃The immersion time in the solution was 30 min. Taking out and drying. And then soaking the polyester yarn in a KBr solution with the concentration of 0.8mol/L, reacting for 30min at room temperature, taking out, washing with deionized water, and drying to obtain the bismuth oxybromide loaded photocatalytic polyester yarn.

The polyester yarns are woven into fabrics, and the flexible photocatalysis polyester fabrics can be obtained.

Example 3

Pretreating the acrylic fiber yarn in a sodium hydroxide solution with the concentration of 10g/L at the temperature of 80 ℃ for 15min, hydrolyzing ester bonds on the surface of the treated acrylic fiber yarn, roughening the surface of fiber, and providing more active sites for the load coating of graphene oxide on the acrylic fiber yarn.

The acrylic fiber filaments were dipped in 0.5g/L dispersion of graphene oxide for 30 min. Taking out and drying. And then soaking the acrylic fiber yarn in a glucose solution with the concentration of 10%, reacting for 30min at 90 ℃, taking out, washing with deionized water, and drying to obtain the graphene-coated acrylic fiber yarn.

Dipping acrylic fiber filaments in 0.5mol/L Bi (NO)₃)₃The immersion time in the solution was 30 min. Taking out and drying. And then dipping the acrylic fiber yarn in a KF solution with the concentration of 0.8mol/L, reacting for 30min at room temperature, taking out, washing with deionized water, and drying to obtain the bismuth oxyfluoride-loaded photocatalytic acrylic fiber yarn.

The acrylic fiber is woven into fabric, and the flexible photocatalysis acrylic fiber fabric can be obtained.

Compared with the prior art, the invention has the following advantages in several aspects:

(1) the photocatalytic cloth prepared by the method is easy to recycle and reuse after being used, so that the pollution is reduced, and the cost is reduced.

(2) The graphene yarn protection material is used, so that the conductivity of the yarn can be improved, the load of bismuth oxyhalide is facilitated, the loss of a photocatalyst in the using process is reduced, and the service life is prolonged.

(3) The conductivity of the graphene can promote the separation of photon-generated carriers, so that the light absorption range of the bismuth oxyhalide is widened, and the photocatalytic efficiency and capability of the bismuth oxyhalide are improved.

(4) The method provides a new material for the increasingly serious environmental pollution treatment, can also widen the application field of textile fibers, and has positive practical significance for the sustainable development of the textile industry, the product transformation and the structure adjustment.

The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.