阅读说明：本技术 一种二氧化钛-贝壳粉复合材料及其制备方法与应用 (Titanium dioxide-shell powder composite material and preparation method and application thereof ) 是由 毕菲 王立艳 盖广清 陈欣 董相廷 赵丽 肖姗姗 于 2020-06-18 设计创作，主要内容包括：本发明公开了一种二氧化钛-贝壳粉复合材料及其制备方法,包括TiO<Sub>2</Sub>和贝壳粉,所述TiO<Sub>2</Sub>和贝壳粉的质量比为1：0.5-2,所述复合材料光催化性能优异,贝壳粉作为二氧化钛的载体,起到了抑制纳米TiO<Sub>2</Sub>团聚的作用,且与TiO<Sub>2</Sub>光催化纳米材料复合后双管齐下,既能吸附又能分解污染物。同时也为废弃贝壳资源的开发和利用提供新途径,兼具显著的社会、经济和环境效益,所述材料适用于涂料领域。(The invention discloses a titanium dioxide-shell powder composite material and a preparation method thereof, comprising TiO 2 And shell powder, said TiO 2 And shell powder in a mass ratio of 1: 0.5-2, the composite material has excellent photocatalytic performance, and the shell powder is used as a carrier of titanium dioxide and plays a role in inhibiting nano TiO 2 By agglomeration and with TiO 2 The photocatalysis nano material is compounded into two tubes, and can adsorb and decompose pollutants. Meanwhile, a new way is provided for the development and utilization of waste shell resources, the material has remarkable social, economic and environmental benefits, and is suitable for the field of coatings.)

1. The titanium dioxide-shell powder composite material is characterized by comprising TiO₂And shell powder, said TiO₂And shell powder in a mass ratio of 1: 0.5-2.

2. The composite material of claim 1, further comprising a metal ion, wherein the metal ion is Fe³⁺Or Cu²⁺In the composite material, the Fe³⁺Or Cu²⁺The molar concentration of (A) is 0.1-0.5%.

3. A method of preparing a composite material according to claim 1 or 2, comprising the steps of:

s1, uniformly mixing the butyl titanate and the solvent according to TiO₂And shell powder in a mass ratio of 1: 0.5-2, adding shell powder, and uniformly stirring to obtain a premix;

s2, adding a high-molecular template agent into the premix, and uniformly stirring to obtain a spinning solution;

s3, carrying out electrostatic spinning operation on the spinning solution to obtain a spinning material;

and S4, calcining the spinning material to obtain the titanium dioxide-shell powder composite material.

4. The method according to claim 3, wherein the step S1 further comprises a step of adding iron nitrate or copper nitrate to the mixture of butyl titanate and the solvent at a molar concentration of 0.1 to 0.5%.

5. The method according to claim 3 or 4, wherein in the step S3, the processing parameters in the electrostatic spinning process are as follows: the voltage is 10KV, the distance between the spinning nozzle and the collector is 18-20cm, the ambient temperature is 20-24 ℃, and the relative humidity is 30-40%.

6. The preparation method according to claim 5, wherein in the step S4, the calcination process is: spinning the filamentsThe material is placed in a high-temperature program temperature control box type furnace at 1 ℃ for min^-1The temperature is raised to 500 ℃ at the speed, and the heat is preserved for 3 hours, thus obtaining the titanium dioxide-shell powder composite material.

7. The method according to claim 6, wherein the solvent is ethanol, DMF or water, and the polymer template is polyvinylpyrrolidone.

8. The preparation method according to claim 7, wherein in the step S1, the shell powder is added, stirred for 20min and ultrasonically dispersed for 30min to obtain the premix.

9. The method according to claim 8, wherein the polymer template is added and stirred for 12 hours to obtain the spinning solution in step S2.

10. Use of a composite material according to claim 1 or 2 in a coating.

Technical Field

The invention belongs to the technical field of chemical materials, relates to a composite material for coating and a preparation method thereof, and particularly relates to a titanium dioxide-shell powder composite material and a preparation method and application thereof.

Background

As the modern spends 80% -90% of the day indoors, indoor air pollution is harmful to human bodies greatly. In order to reduce indoor air pollution caused by decoration, China has strictly limited the content of harmful substances in various decorations since 2001. Over the past decade, the quality of indoor air in people's lives has improved greatly, but many households are still plagued by indoor air pollution due to the accumulation of pollutants in various materials and the improper selection of individual materials.

In recent years, research on indoor air purification has been actively conducted. At present, a plurality of indoor air purification products, such as active carbon, air purifier, various air treatment agents and functionalityWallpaper, diatom ooze, etc. Among a plurality of air purification products, the interior wall coating has the advantages of low cost, large indoor coating area and no secondary pollution as the most widely applied interior wall decoration product at present, so that the interior wall coating has great potential in air purification and is generally favored by consumers. TiO was discovered by Fujishima et al, Japan scientist since 1972₂Can decompose water into hydrogen and oxygen under the action of ultraviolet light, and is developed for decades by using nano TiO₂The semiconductor photocatalytic material and the photocatalytic technology thereof have achieved great research results. TiO 2₂Is an important inorganic chemical raw material, has a plurality of excellent characteristics of no toxicity, no harm, strong tinting strength, high covering power, good weather resistance and the like, is widely applied in various fields of the coating industry, and particularly has great development in the directions of organic pollutant degradation, sewage treatment, air purification and the like. TiO 2₂As an environment-friendly material, TiO is added with the enhancement of environmental consciousness of people₂TiO with integrated pigment performance and photocatalysis characteristic₂Photocatalytic coatings are also receiving increasing attention from the industry.

But nano TiO₂The use in coatings faces several important problems: (1) ordinary nano TiO₂The photocatalyst has excellent photocatalytic performance under ultraviolet light, has no obvious effect under visible light, and has extremely weak ultraviolet light intensity in common indoor environment, so that the photocatalyst needs to be applied to nano TiO₂And (5) carrying out modification treatment. (2) In TiO₂In the process of adding the nano material into the coating, agglomeration and cladding phenomena of nano ions inevitably exist, so that the photocatalysis effect of the photocatalyst is ineffective. (3) TiO 2₂When organic matters with low concentration are degraded, the adsorption capacity to the organic matters is poor, so that the collision probability with organic matter molecules in the photocatalytic reaction process is reduced, and the photocatalytic degradation efficiency is low.

Disclosure of Invention

Therefore, the present invention is to solve the above technical problems, and to provide a method for improving TiO content₂Titanium dioxide-shell powder composite material with excellent visible light absorption and photocatalytic performanceAnd a preparation method and application thereof.

In order to solve the technical problems, the technical scheme of the invention is as follows:

the invention provides a titanium dioxide-shell powder composite material which comprises TiO₂And shell powder, said TiO₂And shell powder in a mass ratio of 1: 0.5-2.

Further, the composite material also comprises metal ions, and the metal ions are Fe³⁺Or Cu²⁺In the composite material, the Fe³⁺Or Cu²⁺The molar concentration of (A) is 0.1-0.5%.

In another aspect, the present invention provides a method for preparing the composite material, which comprises the following steps:

s1, uniformly mixing the butyl titanate and the solvent according to TiO₂And shell powder in a mass ratio of 1: 0.5-2, adding shell powder, and uniformly stirring to obtain a premix;

s2, adding a high-molecular template agent into the premix, and uniformly stirring to obtain a spinning solution;

s3, carrying out electrostatic spinning operation on the spinning solution to obtain a spinning material;

and S4, calcining the spinning material to obtain the titanium dioxide-shell powder composite material.

Further, the step S1 includes a step of adding iron nitrate or copper nitrate to the mixture of butyl titanate and the solvent at a molar concentration of 0.1 to 0.5%.

Further, in step S3, the processing parameters in the electrospinning process are: the voltage is 10KV, the distance between the spinning nozzle and the collector is 18-20cm, the ambient temperature is 20-24 ℃, and the relative humidity is 30-40%.

Further, in step S4, the calcination process is: placing the spinning material in a high-temperature program temperature control box type furnace at 1 ℃ for min^-1The temperature is raised to 500 ℃ at the speed, and the heat is preserved for 3 hours, thus obtaining the titanium dioxide-shell powder composite material.

Further, the solvent is ethanol, and the polymer template agent is polyvinylpyrrolidone.

Further, in the step S1, after adding shell powder, stirring for 20min, and performing ultrasonic dispersion for 30min to obtain a premix.

Further, in step S2, a polymer template is added and stirred for 12 hours to obtain a spinning solution.

The invention also provides an application of the composite material in coating.

Compared with the prior art, the technical scheme of the invention has the following advantages:

(1) the titanium dioxide-shell powder composite material comprises TiO₂And shell powder, said TiO₂And shell powder in a mass ratio of 1: 0.5-2, the composite material has excellent photocatalytic performance, and the shell powder is used as a carrier of titanium dioxide and plays a role in inhibiting nano TiO₂By agglomeration and with TiO₂The photocatalysis nano material is compounded into two tubes, and can adsorb and decompose pollutants. Meanwhile, a new way is provided for the development and utilization of waste shell resources, and the method has remarkable social, economic and environmental benefits.

(2) The titanium dioxide-shell powder composite material also comprises metal ions, wherein the metal ions are Fe³⁺Or Cu²⁺The composite material doped with metal ions further improves the photocatalytic performance of the composite material, and the composite material modifies the interior wall coating to obtain a novel metal ion doped TiO with low cost, which integrates multiple functions of physical formaldehyde adsorption, photocatalytic formaldehyde decomposition, antibiosis and the like into a whole₂Shell powder composite coating.

(3) The preparation method adopts an electrostatic spinning technology, which utilizes a high-voltage electric field to charge the surface of a spinning solution, and the spinning solution is sprayed out from a nozzle under the induction of the electric field and then is stretched to form the nano-fiber. The electrostatic spinning technology has simple equipment operation and low price, and is an ideal method for preparing inorganic substance/polymer composite nano materials and pure inorganic substance nano materials, and the industrial production is easy to realize.

Drawings

In order that the present disclosure may be more readily and clearly understood, reference is now made to the following detailed description of the embodiments of the present disclosure taken in conjunction with the accompanying drawings, in which

FIG. 1 is an XRD pattern of a composite material according to example 1 of the present invention;

FIG. 2 is an infrared spectrum of a composite material according to example 1 of the present invention;

FIG. 3 is a photocatalytic absorption curve of the composite material according to example 1 of the present invention;

FIG. 4 is a graph comparing the degradation rate of the composite material of example 1 of the present invention to rhodamine B;

FIG. 5 shows TiO described in example 2 of the present invention₂:x％Fe³⁺XRD pattern of the shell powder composite material;

FIG. 6 shows TiO described in example 2 of the present invention₂:x％Cu²⁺XRD pattern of the shell powder composite material;

FIG. 7 shows TiO described in example 2 of the present invention₂:x％Fe³⁺An infrared spectrogram of the shell powder composite material;

FIG. 8 shows TiO described in example 2 of the present invention₂:x％Cu²⁺An infrared spectrogram of the shell powder composite material;

FIG. 9 shows TiO described in example 2 of the present invention₂:x％Fe³⁺An absorption curve of the shell powder composite material under photocatalysis;

FIG. 10 shows TiO described in example 2 of the present invention₂:x％Fe³⁺A shell powder composite material is used for comparing the degradation rate of rhodamine B;

FIG. 11 shows TiO described in example 2 of the present invention₂:x％Cu²⁺An absorption curve of the shell powder composite material under photocatalysis;

FIG. 12 shows TiO described in example 2 of the present invention₂:x％Cu²⁺And a comparison graph of the degradation rate of the shell powder composite material on rhodamine B.

Detailed Description