阅读说明：本技术 一种用于催化降解抗生素废液的改性纳米二氧化钛材料的制备方法 (Preparation method of modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid ) 是由 于洪霞 张嘉琪 蔡天明 陈立伟 姜灿烂 丁大虎 罗静怡 张天宇 陆玲丽 于 2019-10-12 设计创作，主要内容包括：本发明涉及金属氧化物半导体技术领域,具体涉及一种用于催化降解抗生素废液的改性纳米二氧化钛材料的制备方法。本发明提供一种含氮掺杂改性TiO<Sub>2</Sub>的光催化材料,以钛酸四丁酯为TiO<Sub>2</Sub>的前驱体,采用溶胶-凝胶法制备得出纳米TiO<Sub>2</Sub>,然后在纳米TiO<Sub>2</Sub>中加入一定比例氮源,干法制备改性的TiO<Sub>2</Sub>的光催化材料；该制备工艺能够实现连续生产；制备的改性纳米TiO<Sub>2</Sub>材料表面活性大、纯度高、分散性好,且催化降解抗生素的效率高。(The invention relates to the technical field of metal oxide semiconductors, in particular to a preparation method of a modified nano titanium dioxide material for catalyzing and degrading antibiotic waste liquid. The invention provides nitrogen-doped modified TiO 2 The photocatalytic material of (1) is TiO with tetrabutyl titanate 2 The precursor is prepared into the nano TiO by adopting a sol-gel method 2 Then in the presence of nano TiO 2 Adding a certain proportion of nitrogen source, and preparing modified TiO by dry method 2 The photocatalytic material of (1); the preparation process can realize continuous production; prepared modified nano TiO 2 The material has the advantages of large surface activity, high purity, good dispersibility and high efficiency of catalyzing and degrading antibiotics.)

1. A preparation method of a modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid is characterized by comprising the following steps: the method comprises the following steps:

s01, accurately weighing hydroxypropyl cellulose (HPC) with a certain weight, placing the HPC in absolute ethyl alcohol with a certain volume, and fully stirring to prepare 0.004g/mL hydroxypropyl cellulose solution;

s02 distilled water was added to the hydroxypropylcellulose solution obtained in S01, followed by tetra-n-butyl titanate, hydroxypropylcellulose solution: distilled water: the volume ratio of the tetra-n-butyl titanate is as follows: 500:3 (1-15), stirring for 0-4h, centrifuging, removing supernatant, washing with anhydrous ethanol for several times, and adding 50-80^oC, drying in an oven to obtain a dried substance;

s03 taking out the dried substance obtained in S02, mixing the dried substance and the nitrogen source according to the mass ratio of (2:0) - (2:4), grinding, and placing in a muffle furnace for high-temperature calcination at the calcination temperature of 300-800-^oAnd C, grinding the mixture after the calcination time is 2-3h to obtain the nitrogen-doped modified nano titanium dioxide.

2. A preparation method of a modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid is characterized by comprising the following steps: hydroxypropyl cellulose solution in step S02: distilled water: the volume ratio of the tetra-n-butyl titanate is as follows: 500:3:(3-15).

3. A preparation method of a modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid is characterized by comprising the following steps: washing with anhydrous ethanol for 2-4 times in step S02.

4. The preparation method of the modified nano titanium dioxide material for catalyzing and degrading the antibiotic waste liquid according to claim 1, which is characterized in that: step S03, placing the mixture in a muffle furnace for high-temperature calcination at 400-600 deg.C^oC。

5. The preparation method of the modified nano titanium dioxide material for catalyzing and degrading the antibiotic waste liquid according to claim 1, which is characterized in that: in step S03, the nitrogen source is thiourea or urea.

6. The preparation method of the modified nano titanium dioxide material for catalyzing and degrading the antibiotic waste liquid according to claim 1, which is characterized in that: the mass ratio of the dried product to the nitrogen source in step S03 was (2:1) - (2: 4).

7. The application of the nano titanium dioxide material for catalytically degrading the antibiotic waste liquid is characterized in that: the nitrogen-containing doped modified nano titanium dioxide photocatalytic material is used for catalyzing and degrading antibiotic ciprofloxacin.

Technical Field

The invention relates to the technical field of metal oxide semiconductors, in particular to a preparation method of a modified nano titanium dioxide material for catalyzing and degrading antibiotic waste liquid.

Background

Ciprofloxacin is an artificially synthesized third-generation fluoroquinolone antibiotic and is mainly used for sexually transmitted diseases, urinary tract infection and skin infection. Most fluoroquinolone antibiotics are not completely metabolized in the human body and are discharged out of the body as metabolites, and flow into sewage treatment plants along with sewage. Traditional biological sewage treatment methods do not completely remove such antibiotics and may have long-term destructive effects on ecosystem and human health. Therefore, the pollution caused by the ciprofloxacin in the water is not easy to remove.

At present, most of the sewage treatment methods use traditional physical methods such as chemical adsorption and artificial landfill, and the methods have high cost and may cause secondary pollution to the environment. Semiconductor photocatalysis technology is widely applied to various fields, because of simple operation conditions, no secondary pollution, and the inexhaustible solar energy can be used as energy to degrade organic or inorganic substances, but simultaneously, the semiconductor photocatalysis technology has a very obvious defect that light can cause the rapid recombination of electrons and holes in a photocatalyst material, most of the research is focused on the modification of photocatalysis under visible light, and researchers carry out various modifications of the photocatalyst material, such as the modification by adding metal, so that the rapid combination of the electrons and the holes is effectively prevented. And the material is sensitized by organic dye, so that the material and the dye can absorb light energy to degrade pollutants, and the photocatalytic degradation capability is greatly enhanced. These methods do improve the photocatalytic performance of the material to some extent, but also bring about other problems, such as secondary pollution, and even if the conditions are not well controlled, the absorption activity of the material to visible light is still small.

TiO₂The photocatalyst has the advantages of high catalytic activity, stable photochemical property, strong oxidation resistance and the like, is one of the most common semiconductor photocatalysts, and has great application value in the aspects of pollutant treatment, light energy conversion and the like. But pure TiO₂The catalytic efficiency is low, and the application of the photocatalyst is limited under visible light, so that how to effectively improve the solar utilization rate of titanium dioxide is a key scientific problem for promoting the large-scale application of the titanium dioxide photocatalyst in the fields of environment and energy.

Disclosure of Invention

The invention aims to provide a preparation method of a modified nano titanium dioxide material for catalyzing and degrading antibiotic waste liquid; the method for preparing the nitrogen-doped modified nano titanium dioxide visible light catalytic material by adopting the sol-gel and dry method has the advantages of capability of realizing continuous production, and large prepared surface activity, high purity and good dispersibility.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a preparation method of a modified nano titanium dioxide material for catalytic degradation of antibiotic waste liquid comprises the following steps:

s01, accurately weighing hydroxypropyl cellulose (HPC) with a certain weight, placing the HPC in absolute ethyl alcohol with a certain volume, and fully stirring to prepare 0.004g/mL hydroxypropyl cellulose solution;

s02 distilled water was added to the hydroxypropylcellulose solution obtained in S01, followed by tetra-n-butyl titanate, hydroxypropylcellulose solution: distilled water: the volume ratio of the tetra-n-butyl titanate is as follows: 500:3, (1-15), stirring for 0-4h, centrifuging, removing supernatant, washing with absolute ethyl alcohol for several times, and then putting into an oven at 50-80 ℃ for drying to obtain a dried substance;

s03, taking out the dried substance obtained in S02, mixing the dried substance and the nitrogen source according to the mass ratio of (2:0) - (2:4), grinding, placing the mixture in a muffle furnace for high-temperature calcination at the temperature of 300-800 ℃ for 2-3h, and grinding to obtain the nitrogen-doped modified nano titanium dioxide.

Preferably, the hydroxypropyl cellulose solution in step S02: distilled water: the volume ratio of the tetra-n-butyl titanate is as follows: 500:3:(3-15).

Preferably, the washing with absolute ethanol in step S02 is performed 2 to 4 times.

Preferably, the step S03 is implemented by placing in a muffle furnace for high-temperature calcination, wherein the calcination temperature is 400-600 ℃.

Preferably, the nitrogen source in step S03 is thiourea or urea.

Preferably, the mass ratio of the dried product to the nitrogen source in step S03 is (2:1) - (2: 4).

Preferably, the nitrogen-containing doped modified nano titanium dioxide photocatalytic material is used for catalyzing and degrading antibiotic ciprofloxacin.

After the technical scheme is adopted, the invention has the following beneficial effects:

(1) the invention creatively adopts a nitrogen source as a doping agent and adopts a dry method to treat TiO₂The modification is carried out, the preparation process of the nitrogen-doped modified nano titanium dioxide visible light catalytic material is simple, and continuous production can be realized; the prepared material has the advantages of large surface activity, high purity and good dispersibility.

(2) The invention adopts solution polymerization and dry method to prepare nano TiO₂And performing TEM representation and photocatalytic performance test on the material prepared by standing and stirring synthesis, and obtaining the result that the material synthesized in the stirring state has better shape, better dispersibility and better photocatalytic performance.

(3) The invention introduces a nitrogen source in the muffle furnace calcination process to stir the prepared nano TiO₂Modifying the material, researching the influence of different calcining temperatures and N/Ti ratios on the photocatalytic performance, adopting a Transmission Electron Microscope (TEM), scanning electron microscope analysis (SEM), X-ray diffraction (XRD), surface chemical element analysis and energy spectrum analysis, and obtaining a characterization result of the modified nano TiO₂The photocatalyst sample has more dispersivity and rougher surface, and the modified nitrogen content is obviously increased.

Drawings

FIG. 1 shows that (a) and (b) show nano TiO synthesized under stirring and standing conditions₂A material.

FIG. 2 Effect of the state of standing and stirring on the photocatalytic performance of the material produced.

FIG. 3(a) is a diagram showing a TiO solution having a TBOT content of 0.3mL₂Material, (b) is TiO with TBOT content of 0.85mL₂Material, (c) TiO with TBOT content of 1.5mL₂A material.

FIG. 4 modified TiO₂And (4) TEM characterization images of samples.

FIG. 5 SEM image of unmodified material and elemental surface distributions of N-K, O-K, Ti-K in corresponding regions.

FIG. 6 is SEM image of modified material and corresponding element surface distribution of N-K, O-K and Ti-K in corresponding area.

FIG. 7a is a synthetic TiO₂The materials b and c are unmodified and modified materials prepared by muffle furnace calcination at 500 ℃.

FIG. 8 Effect of unmodified and modified on photocatalytic Properties of materials

EDS map of the material of figure 9.

FIG. 10 effect of materials of different Ti/N ratios on photocatalytic performance.

FIG. 11 shows the nano TiO compound₂XRD pattern of (a).

FIG. 12 the effect of different calcination temperatures on the photocatalytic performance of a material.

Detailed Description

The present invention will be further described with reference to the accompanying drawings.