阅读说明：本技术 一种光催化水凝胶粒子的制备方法 (Preparation method of photocatalytic hydrogel particles ) 是由 郭赞如 蒋勇 于 2021-08-12 设计创作，主要内容包括：本发明公开了一种光催化水凝胶粒子的制备方法,该方法利用聚合单体、含有TiO-(2)可聚合复合物等反应溶液在油相中沉降过程聚合,得到光催化水凝胶粒子。本发明的制备工艺简单,制备的水凝胶粒子包含有纳米二氧化钛,能够作为光催化材料对水中污染物进行光催化降解。(The invention discloses a preparation method of photocatalytic hydrogel particles, which utilizes a polymerized monomer and TiO-containing 2 And polymerizing the reaction solution such as the polymerizable compound and the like in the oil phase in a sedimentation process to obtain the photocatalytic hydrogel particles. The preparation process is simple, and the prepared hydrogel particles contain nano titanium dioxide and can be used as a photocatalytic material to carry out photocatalytic degradation on pollutants in water.)

1. A preparation method of photocatalytic hydrogel particles is characterized by comprising the following preparation steps:

s1, dissolving the nano titanium dioxide, the graphene oxide and the amino polyethylene glycol acrylate in water, and ultrasonically dispersing for 30min at 40 DEG^oC, reacting for 6 hours, standing and filtering to obtain a polymerizable graphene oxide compound;

s2, uniformly mixing acrylamide, N-methylene-bisacrylamide, a polymerizable graphene oxide compound, an initiator and deionized water in a reactor according to a certain proportion under the ultrasonic action to obtain a reaction solution;

s3, dropping the reaction liquid into a heatable glass tube filled with oil at the speed of 1 drop/30-60S by using an injector, and washing a product collected at the lower end of the glass tube with water to obtain the photocatalytic hydrogel particles.

2. The method for preparing photocatalytic hydrogel particles as claimed in claim 1, wherein in step S1, the mass ratio of nano titanium dioxide to graphene oxide is (4: 1) - (1: 4), the mass ratio of amino polyethylene glycol acrylate to graphene oxide is (0.5-2): 1.

3. the method of claim 1, wherein in step S2, the mass of N, N-methylenebisacrylamide is 2-20% of the mass of acrylamide, the amount of the polymerizable graphene oxide compound is 1-10% of the mass of acrylamide, and the mass of deionized water is 0.5-2 times of the mass of acrylamide.

4. The method of claim 1, wherein in step S2, the initiator is a water-soluble initiator, and one of potassium persulfate, ammonium persulfate, azobisisobutylimidazoline hydrochloride (V044) and azobisisobutylamidine hydrochloride (V50) is used, and the mass of the initiator is 0.1-5% of the mass of acrylamide.

5. The method of claim 1, wherein in step S3, the length of the glass tube is 25-50 cm, and the temperature of the oil is 80-95%^oC。

6. The method of claim 1, wherein in step S3, the oil in the heatable glass tube is one of soybean oil, corn oil, or rapeseed oil.

Technical Field

The invention relates to the technical field of photocatalytic materials, in particular to a preparation method of photocatalytic hydrogel particles.

Background

The problem of water pollution caused by industrial wastewater discharge has attracted global attention, wherein industries such as paper making, leather, textile, plastic, cosmetics and electroplating industries generate a large amount of industrial wastewater, and main pollutant organic compounds in the industrial wastewater. In order to remove these pollutants, researchers have studied a series of methods and applied to the treatment of industrial wastewater to reduce its harmful effects on the water resource environment. At present, the effective methods comprise a membrane filtration method, a chemical oxidation biological method, an adsorption method and the like, and the methods all have the situations of incomplete degradation and the like.

The photocatalysis technology is a means which is developed in the last decade and can effectively treat water pollution and air pollution, and the photocatalysis principle is that high oxidation active species are generated in water under the solar radiation by means of a photocatalyst so as to reduce organic pollutantsDecomposed into CO₂And water, and pollutants are degraded more thoroughly, so the photocatalysis technology is a simple and environment-friendly method for solving the problems of water pollution. Nano titanium dioxide (TiO)₂) Because of the advantages of high efficiency, no toxicity, stable chemical property and the like, the photocatalyst is a photocatalyst with large-scale application potential, however, the nano TiO₂In view of the disadvantages that they are generally in the form of powder and are not easily recycled in use, it is necessary to develop a method for preparing hydrogel particles supporting nano-titania.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide a preparation method of photocatalytic hydrogel particles, which can realize photocatalytic degradation of pollutants under ultraviolet and visible light and can realize recycling of nano titanium dioxide.

In order to achieve the above object, the present invention adopts the following technical solutions:

a preparation method of photocatalytic hydrogel particles is characterized by comprising the following preparation steps:

s1, dissolving nano titanium dioxide, graphene oxide and amino polyethylene glycol acrylate in water, performing ultrasonic dispersion for 30min, reacting at 40 ℃ for 6h, standing and filtering to obtain a polymerizable graphene oxide compound;

s2, uniformly mixing acrylamide, N-methylene-bisacrylamide, a polymerizable graphene oxide compound, an initiator and deionized water in a reactor according to a certain proportion under the ultrasonic action to obtain a reaction solution;

s3, dropping the reaction liquid into a heatable glass tube filled with oil at the speed of 1 drop/30-60S by using an injector, and washing a product collected at the lower end of the glass tube with water to obtain the photocatalytic hydrogel particles.

Preferably, in the step S1, the mass ratio of the nano titanium dioxide to the graphene oxide is (4: 1) - (1: 4), and the mass ratio of the amino polyethylene glycol acrylate to the graphene oxide is (0.5-2): 1.

more preferably, in the step S2, the mass of the N, N-methylenebisacrylamide is 2 to 20% of the mass of the acrylamide, the amount of the graphene oxide composite is 1 to 10% of the mass of the acrylamide, and the mass of the deionized water is 0.5 to 2 times of the mass of the acrylamide.

More preferably, in the step S2, the initiator is a water-soluble initiator, and one of potassium persulfate, ammonium persulfate, azobisisobutylimidazoline hydrochloride (V044) and azobisisobutylamidine hydrochloride (V50) is used, and the mass of the initiator is 0.1-5% of the mass of the acrylamide.

More preferably, in the step S3, the length of the glass tube is 25 to 50cm, and the temperature of the oil is 80 to 95 ℃.

6. The method of claim 1, wherein in step S3, the oil in the heatable glass tube is one of soybean oil, corn oil, or rapeseed oil.

The invention has the advantages that: the technological process of the invention has simple operation and low cost, and can be suitable for large-scale actual production; the photocatalytic hydrogel particles prepared by the invention contain nano titanium dioxide, can be used as a photocatalytic material to carry out photocatalytic degradation on pollutants in water, have the advantages of water absorption expansion and easy separation and recovery, can realize photocatalytic degradation of pollutants under ultraviolet and visible light, can realize cyclic utilization of the nano titanium dioxide, and can avoid corrosion of photocatalysis on hydrogel under the isolation of graphene oxide; according to the invention, the nano titanium dioxide is stably loaded on the graphene oxide, and the polymerizable double bond functional group is introduced into the nano titanium dioxide loaded graphene oxide, so that the nano titanium dioxide loaded graphene oxide participates in polymerization, stable dispersion is formed in gel particles, and the catalytic effect and stability are improved.

Drawings

FIG. 1 is a photomicrograph of photocatalytic hydrogel particles prepared in example 1 of the present invention;

FIG. 2 is a graph of the removal rate of allura red dye for the photocatalytic hydrogel particles prepared in example 1 of the present invention and a control sample;

FIG. 3 is a graph showing the recycling of the decoy red dye by the photocatalytic hydrogel particles and the nano titanium dioxide prepared in example 1 of the present invention.

Detailed Description

The invention is described in detail below with reference to the figures and the embodiments.

Example 1

A preparation method of photocatalytic hydrogel particles comprises the following preparation steps:

s1, dissolving 4g of nano titanium dioxide, 1g of graphene oxide and 0.5g of amino polyethylene glycol acrylate in 200mL of water, ultrasonically dispersing for 30min, and dissolving the mixture in water at 40 DEG^oC, reacting for 6 hours, standing and filtering to obtain a graphene oxide compound;

s2, adding 10 g of acrylamide, 0.2g of N, N-methylene bisacrylamide, 0.01g of potassium persulfate, 0.1g of graphene oxide compound and 5g of deionized water into a reactor, and uniformly mixing under the action of ultrasound to obtain a reaction solution;

s3, dripping the reaction solution into a heatable glass tube which is 25cm long and filled with soybean oil with the temperature of 80 ℃ at the speed of 60S per drop by using an injector^oAnd C, washing a product collected at the lower end of the glass tube with water to obtain the photocatalytic hydrogel particles.

The morphology of the photocatalytic hydrogel particles prepared in example 1 is shown in fig. 1, and it can be seen that the material is spherical.

Example 2

A preparation method of photocatalytic hydrogel particles comprises the following preparation steps:

s1, dissolving 1g of nano titanium dioxide, 4g of graphene oxide and 8g of amino polyethylene glycol acrylate in 750mL of water, ultrasonically dispersing for 30min, and dispersing in water at 40%^oC, reacting for 6 hours, standing and filtering to obtain a graphene oxide compound;

s2, adding 10 g of acrylamide, 2g of N, N-methylene bisacrylamide, 0.01g of ammonium persulfate, 1g of graphene oxide compound and 20g of deionized water into a reactor, and uniformly mixing under the action of ultrasound to obtain a reaction solution;

s3, dropping the reaction solution into a heatable glass tube with length of 50cm and containing soybean oil at the speed of every 30S by using an injectorThe temperature of the soybean oil was 95 deg.C^oAnd C, washing a product collected at the lower end of the glass tube with water to obtain the photocatalytic hydrogel particles.

Example 3

A preparation method of photocatalytic hydrogel particles comprises the following preparation steps:

s1, dissolving 2g of nano titanium dioxide, 2g of graphene oxide and 2g of amino polyethylene glycol acrylate in 500mL of water, ultrasonically dispersing for 30min, and dispersing in 40%^oC, reacting for 6 hours, standing and filtering to obtain a graphene oxide compound;

s2, adding 10 g of acrylamide, 0.5g of N, N-methylene bisacrylamide, 0.02g of V40, 0.5g of graphene oxide compound and 15g of deionized water into a reactor, and uniformly mixing under the action of ultrasound to obtain a reaction solution;

s3, dripping the reaction solution into a heatable glass tube which is 30cm long and filled with soybean oil at the temperature of 90 ℃ at the speed of 40S per drop by using an injector^oAnd C, washing a product collected at the lower end of the glass tube with water to obtain the photocatalytic hydrogel particles.

Performance detection test:

(1) the removal effect of the contaminants was tested by adding 2g of the hydrogel particles prepared in example 1 to 100mL of a decoy red dye solution having a concentration of 10 mg/L, and a blank experiment (hydrogel particles containing no nano-titania) was set, and the graph of the removal rate of the decoy red dye is shown in FIG. 2.

As shown in fig. 2, the removal rate of the blank experiment without the nano titanium dioxide hydrogel particles is only 38%, and the removal rate of the dye by the hydrogel particles prepared in example 1 can reach 97.5%, which indicates that the removal rate of the pollutants can be significantly improved by adding the nano titanium dioxide into the hydrogel particles.

(2) The hydrogel particles prepared in example 1 and the same amount of nano-titanium dioxide were subjected to a cycle test experiment for the removal of decoy red dye, and the removal rate of decoy red dye is shown in fig. 3.

As shown in fig. 3, the hydrogel particles prepared in example 1 showed good recycling performance, and pure nano titanium dioxide was lost during the use process, so that the catalytic effect gradually decreased with the increase of the recycling times, which indicates that the nano titanium dioxide supported in the porous hydrogel can significantly improve the recycling performance.

The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.