CN106582595B - A kind of blue TiO2The preparation method of catalyst - Google Patents

Abstract

The invention provides a preparation method of a blue TiO ₂ catalyst. TiCl ₄ and hydrazine hydrate are mixed according to a molar ratio of 1: (5-10) to obtain a TiCl ₄ hydrazine complex; according to the mass ratio of TiCl ₄ : Water=1:15-30, deionized water is added to the above-mentioned complex to obtain a precursor liquid of TiO ₂ ; Suction filtration, washing and drying to obtain blue TiO ₂ catalyst. The blue TiO ₂ catalyst obtained by the method of the present invention has better response to ultraviolet-visible light, and has better performance of photocatalytic degradation of wastewater dyes under ultraviolet-visible light. This kind of blue TiO ₂ powder can completely degrade 20mg/L methyl orange solution within 25min, and the photocatalytic effect is better than that of white TiO ₂ .

Description

A kind of preparation method of blue TiO2 catalyst

technical field

The invention belongs to the field of chemical industry, and relates to a catalyst, in particular to a preparation method of a blue _TiO2 catalyst.

Background technique

As a "green technology" and "environmentally friendly technology", _TiO2 photocatalysis technology has the advantages of simple operation, mild reaction conditions and no secondary pollution. It is one of the research directions of catalysis in the 21st century. It has great potential and broad application prospects in the industrial-scale application of nano-titanium dioxide, and the industrial production of nano-titanium dioxide P25 has been realized. However, as far as TiO ₂ is concerned, there are two problems that always restrict its performance. First, the band gap of TiO ₂ is wide, which is 3.2eV, which leads to its narrow photoresponse range and can only absorb sunlight. Ultraviolet light with a wavelength of less than 380nm, which only accounts for 4%-6% of the solar rays irradiated on the ground; second, photogenerated carriers are easy to recombine, resulting in very low photon efficiency. Therefore, solving the above two problems is the focus and focus of TiO ₂ research in the field of photocatalysis. The appearance of ordinary TiO ₂ powder is usually white, which is greatly affected by the above two factors. In order to better solve the above two problems, the research of non-white system TiO ₂ has attracted more and more attention. Blue TiO ₂ is TiO _{2 that has been specially treated. The blue appearance of this TiO 2 is} caused by the shift of the absorption wavelength from the ultraviolet region to the visible region. The blue _TiO2 retains the response to ultraviolet light while also realizing the response to visible light, and can effectively inhibit the recombination of photogenerated carriers, showing strong photocatalytic ability.

In patent CN103553124A, titanium trichloride is used as raw material, a certain molar ratio of equilibrium conjugated titanium tetrachloride is added, and sodium fluoride is used as stabilizer to synthesize blue titanium dioxide nanoparticles by solvothermal method. However, this method requires many raw materials, high temperature and long time. In patent CN103482698A, rutile phase titanium dioxide is mixed with deionized water, and then blue titanium dioxide is obtained under the irradiation of ultraviolet laser. Although this method has less raw materials, the required equipment is relatively harsh, which is not conducive to large-scale production.

SUMMARY OF THE INVENTION

In view of the above technical problems in the prior art, the present invention provides a preparation method of blue TiO ₂ powder, and the preparation method of the blue TiO ₂ powder should solve the problem of preparing blue TiO 2 powder in the prior art The method of TiO ₂ powder is complicated in process and harsh in conditions, which is not conducive to the technical problems of large-scale industrial production.

The invention provides a preparation method of a blue _TiO2 catalyst, comprising the following steps:

1) weigh _TiCl and hydrazine hydrate respectively, the mol ratio of described _TiCl and hydrazine hydrate is 1:5-10, mix _TiCl and hydrazine hydrate to obtain TiCl ₄ -hydrazine complex;

2) take by weighing deionized water, the mass ratio of described deionized water and _TiCl is 1:15-30, and deionized water is added to above-mentioned TiCl ₄ -hydrazine complex to obtain the precursor liquid of _TiO ;

3) The above-mentioned TiO ₂ precursor liquid is put into a hydrothermal kettle, and after 16-24 hours of reaction at 170-220° C., suction filtration, washing and drying are performed to obtain a blue TiO ₂ catalyst.

Further, in step 3), ethanol is used for washing.

The present invention adopts a one-pot method, through the coordination and reduction of hydrazine hydrate, through simple hydrothermal treatment, without the need for later high-temperature treatment, and synthesizes blue _TiO2 catalyst with anatase phase in the next step under milder conditions . The TiO ₂ powder prepared according to the method of the present invention has blue appearance, uniform particle size, no agglomeration, and has good photocatalytic effect under fluorescent lamp irradiation. This kind of blue TiO ₂ powder can completely degrade 20mg/L methyl orange solution within 30min.

Compared with the prior art, the present invention has significant technical progress. The blue TiO ₂ catalyst obtained by the method of the invention has better response to ultraviolet-visible light, and has better photocatalytic degradation performance of wastewater dye under ultraviolet-visible light. This kind of blue TiO ₂ powder can completely degrade 20mg/L methyl orange solution within 25min. The preparation method of the invention is simple in process and does not need special raw materials and equipment. The obtained blue _TiO2 catalyst powder has uniform particle size, no agglomeration, stable performance, high yield, and better photocatalytic effect than white _TiO2 .

Description of drawings:

Figure 1 is the XRD patterns of the blue _TiO2 catalysts prepared in Examples 1-4.

Detailed ways

Below in conjunction with embodiment and relevant chart, the present invention is elaborated, but the present invention is not limited to given example:

Example 1

1) mixing TiCl ₄ and hydrazine hydrate in a molar ratio of 1:8 to obtain a TiCl ₄ -hydrazine complex;

2) according to the mass ratio of TiCl ₄ : water=1:20, deionized water is added to the complex in the above (1) to obtain a precursor liquid of TiO ₂ ;

3) Put the obtained precursor liquid in 2) into a hydrothermal kettle, and after reacting at 180° C. for 20 h, suction filtration, washing with ethanol and drying to obtain a blue TiO ₂ catalyst.

The XRD patterns of the obtained samples were tested with Bruker D8 Advance from Germany, and the results are shown in Figure 1. The XRD pattern is consistent with the standard card of anatase TiO ₂ , indicating that in Example 1, blue anatase TiO ₂ was synthesized by one-step method; Small.

The blue TiO ₂ powder prepared in this example was added to a 20 mg/L methyl orange solution at a mass ratio of 0.1 g/100 mL. Under ultraviolet-visible light, the methyl orange solution was Degradable is completed.

Example 2

1) mixing TiCl ₄ and hydrazine hydrate in a molar ratio of 1:10 to obtain a TiCl ₄ -hydrazine complex;

2) according to mass ratio TiCl ₄ : water=1:25, deionized water is added to the above-mentioned (1) in the complex to obtain TiO Precursor liquid;

3) The precursor liquid obtained in 2) was put into a hydrothermal kettle, and after reacting at 220° C. for 16 h, suction filtration, washing with ethanol, and drying were performed to obtain a blue TiO ₂ catalyst.

The XRD patterns of the obtained samples were tested with Bruker D8 Advance from Germany, and the results are shown in Figure 1. The XRD pattern is consistent with the standard card of anatase TiO ₂ , indicating that in Example 2, blue anatase TiO ₂ was synthesized by one-step method; from the broadening of the diffraction peak, it can be seen that the grain size of the sample is larger than Small.

The blue TiO ₂ powder prepared in this example was added to a 20 mg/L methyl orange solution at a mass ratio of 0.1 g/100 mL. Under ultraviolet-visible light, the methyl orange solution was Degradable is completed.

Example 3

1) mixing TiCl ₄ and hydrazine hydrate in a molar ratio of 1:8 to obtain a TiCl ₄ -hydrazine complex;

2) according to mass ratio TiCl ₄ : water=1:15, deionized water is added to the above-mentioned (1) in the complex to obtain TiO Precursor liquid;

3) The precursor liquid obtained in (2) was put into a hydrothermal kettle, and after 16 hours of reaction at 220 °C, suction filtration, ethanol washing, and drying were performed to obtain a blue TiO ₂ catalyst.

The XRD patterns of the obtained samples were tested with Bruker D8 Advance from Germany, and the results are shown in Figure 1. The XRD pattern is consistent with the standard card of anatase TiO ₂ , indicating that in Example 3, blue anatase TiO ₂ was synthesized by one-step method; Small.

The blue TiO ₂ powder prepared in this example was added to a 20 mg/L methyl orange solution at a mass ratio of 0.1 g/100 mL. Under ultraviolet-visible light, the methyl orange solution was Degradable is completed.

Example 4

1) mixing TiCl ₄ and hydrazine hydrate in a molar ratio of 1:5 to obtain a TiCl ₄ -hydrazine complex;

2) according to mass ratio TiCl ₄ : water=1:20, deionized water is added to the above-mentioned (1) in the complex to obtain TiO Precursor liquid;

3) Put the obtained precursor liquid in 2) into a hydrothermal kettle, react at 220° C. for 20 hours, filter with suction, wash with ethanol, and dry to obtain a blue TiO ₂ catalyst.

The XRD patterns of the obtained samples were tested with Bruker D8 Advance from Germany, and the results are shown in Figure 1. The XRD pattern is consistent with the standard card of anatase TiO2, indicating that in Example 4, blue anatase _TiO2 was synthesized by one-step method; from the broadening of the diffraction peaks, it can be seen that the grain size of the sample is small .

The blue TiO ₂ powder prepared in this example was added to a 20 mg/L methyl orange solution at a mass ratio of 0.1 g/100 mL. Under ultraviolet-visible light, the methyl orange solution was Degradable is completed.

Claims (2)

1. a preparation method of blue TiO ₂ catalyst is characterized in that comprising the steps: 1) Weigh TiCl ₄ and hydrazine hydrate respectively, the molar ratio of TiCl ₄ and hydrazine hydrate is 1:5-10, and mix TiCl ₄ and hydrazine hydrate to obtain TiCl ₄ -hydrazine complex; 2) Weighing deionized water, the mass ratio of the deionized water and TiCl ₄ is 1:15-30, adding the deionized water to the above-mentioned TiCl ₄ -hydrazine complex to obtain the precursor liquid of TiO ₂ ; 3) Load the above-mentioned TiO ₂ precursor liquid into a hydrothermal kettle, react at 170-220° C. for 16-24 hours, filter, wash and dry to obtain a blue TiO ₂ catalyst. 2. the preparation method of a kind of blue _TiO catalyst according to claim 1, is characterized in that: In step 3), wash with ethanol.