阅读说明：本技术 高暴露｛001}晶面Fe-TiO2光催化材料及制备方法和用途 (High-exposure {001} crystal face Fe-TiO2Photocatalytic material, preparation method and application ) 是由 欧玉静 赵丹 郑毅 李春雷 石俊青 邵怡亮 金兴智 何航党 张变红 于 2020-06-23 设计创作，主要内容包括：高暴露｛001}晶面Fe-TiO2光催化材料及制备方法和用途,属于光催化环境修复技术,该光催化材料的使用简便的一步水热法制备了高暴露｛001}晶面Fe-TiO<Sub>2</Sub>光催化材料。由于光催化材料中铁离子的引入降低了光生载流子的复合效率,从而使该光催化材料具有高效的光催化活性,且高于纯相物质的光催化活性。所制备的光催化材料能够在15 min时对玫瑰红染料降解率达到95%以上。该光催化材料的制备方法简便且原材料廉价。(A high-exposure {001} crystal face Fe-TiO2 photocatalytic material, a preparation method and application belong to photocatalytic environment restoration technology, and the high-exposure {001} crystal face Fe-TiO is prepared by a simple one-step hydrothermal method 2 A photocatalytic material. The introduction of iron ions in the photocatalytic material reduces the recombination efficiency of photon-generated carriers, so that the photocatalytic material has high-efficiency photocatalytic activity which is higher than that of a pure-phase substance. The prepared photocatalytic material can achieve a rose bengal dye degradation rate of more than 95% in 15 min. The preparation method of the photocatalytic material is simple and convenient, and the raw materials are cheap.)

1. High-exposure {001} crystal face Fe-TiO₂A photocatalytic material characterized by: Fe-TiO₂The photocatalytic material is formed by doping titanium dioxide nanosheets with ferric ions, wherein the molar ratio of iron to titanium is 5%: 1.

2. the high exposure {001} crystal plane Fe-TiO of claim 1₂The preparation method of the photocatalytic material is characterized by comprising the following steps:

step (1), taking 10mL of tetrabutyl titanate and adding into a beaker, and then dropwise adding 1.2 mL of 40% hydrofluoric acid solution into the beaker;

step (2) according to the molar ratio of the iron element to the titanium element of 5%: 1, adding a preset amount of ferric nitrate nonahydrate into a beaker;

continuously stirring for 30min by magnetic force;

transferring the mixed solution into a reaction kettle, and keeping the mixed solution at 180 ℃ for 24 hours to obtain a primary sample;

and (4) washing the initial sample with water and alcohol, drying at 80 ℃, and grinding to obtain the final photocatalytic material.

3. The high-exposure {001} crystal face Fe-TiO of claim 2₂The preparation method of the photocatalytic material is characterized by comprising the following steps: the titanium dioxide with hydrofluoric acid exposed high-energy crystal face is used as a substrate.

4. The high-exposure {001} crystal face Fe-TiO of claim 2₂The preparation method of the photocatalytic material is characterized by comprising the following steps: the method is a one-step hydrothermal method, namely, a certain amount of tetrabutyl titanate, hydrofluoric acid and ferric nitrate nonahydrate are sequentially added into a reactor.

5. The high-exposure {001} crystal face Fe-TiO of claim 2₂The preparation method of the photocatalytic material is characterized by comprising the following steps: what is needed isThe molar ratio of the iron element to the titanium element is 5%: 1, in a ratio of 1.

6. The high-exposure {001} crystal face Fe-TiO of claim 2₂The preparation method of the photocatalytic material is characterized by comprising the following steps: the stirring is carried out for 30min by adopting magnetic stirring, and the hydrothermal reaction is carried out in a forced air oven at 180 ℃ and is kept for 24 h.

7. The high-exposure {001} crystal face Fe-TiO of claim 2₂The preparation method of the photocatalytic material is characterized by comprising the following steps: 1.2 mL of 40% hydrofluoric acid solution was added dropwise to 10mL of tetrabutyltitanate.

8. The high-exposure {001} crystal face Fe-TiO of claim 2₂The preparation method of the photocatalytic material is characterized by comprising the following steps: the washing method comprises three times of washing respectively by distilled water and absolute ethyl alcohol.

9. The high-exposure {001} crystal face Fe-TiO of claim 1₂Use of a photocatalytic material, said highly exposed {001} crystal plane Fe-TiO₂The photocatalytic material is used for carrying out a photodegradation experiment under a 300W xenon lamp.

10. The high exposure {001} crystal plane Fe-TiO of claim 9₂Use of a photocatalytic material, said highly exposed {001} crystal plane Fe-TiO₂The photocatalytic material degrades rose bengal dye under simulated sunlight of a xenon lamp.

Technical Field

The invention belongs to a photocatalytic environment restoration technology, and particularly relates to a preparation technology of a high-exposure {001} titanium dioxide doped iron ion photocatalytic material.

Technical Field

TiO₂As a new photocatalyst, people are attracting more and more attention because of its advantages of good stability, low cost, no toxicity, and the like. TiO2₂The high photocatalytic activity of the compound makes the compound have obvious advantages in photocatalytic reactions. By direct use of TiO₂The utilization rate of the photocatalyst on the solar energy is low due to TiO₂The forbidden band width of the solar energy collector is large, the solar energy collector can only be excited by ultraviolet light with the wavelength of less than 385nm, and visible light accounting for 45 percent of the solar energy can not be effectively utilized. And the photo-generated electrons and holes generated by light excitation are easy to recombine, so that TiO₂The photocatalytic activity of (a) is further decreased. The nanometer titanium dioxide has the defects of too high recombination rate of generated electron-hole pairs under the excitation of a light source, poor adsorption affinity, insufficient reaction active sites contacted with pollutants and reduction of the photocatalytic activity, so that the practical application of the nanometer titanium dioxide photocatalytic technology is limited. Therefore, how to effectively widen the nanometer TiO₂The spectral response range and the rate of inhibiting the recombination of the photo-generated electron-hole pairs become the key for improving the photocatalytic performance of the photo-generated electron-hole pairs.

In 2008, Lu and the like found that HF can significantly reduce the surface energy of a {001} crystal face through calculation, and prepared TiO with the {001} crystal face exposure ratio of 47%₂Microcrystals of the TiO₂The microcrystal has higher catalytic activity in the aspect of hydrogen production by photolysis of water. The research results inspire people to prepare anatase TiO dominated by {001} crystal face with micron and nanometer sizes₂The study of (1). 2009, Han et alTitanium acid n-butyl ester and HF as raw materials, TiO with {001} crystal face exposure ratio up to 89% is synthesized under the hydrothermal condition of 180 DEG C₂The titanium dioxide nanosheet shows good photocatalytic performance when used for photocatalytic degradation of methyl orange solution, researches also find that after surface fluoride is removed, the degradation effect of the catalyst is better, and the degradation efficiency is almost unchanged after 7 times of repeated use. Luan's findings differ from that of Han in that he found that the presence of surface fluorides increased O in air₂The adsorption capacity of the molecule is to maintain TiO₂The key of high catalytic activity of the nano-flake. Therefore, titanium dioxide with a high exposure {001} crystal face is used as a reaction substrate for modification.

At present, the main research methods aiming at the functional modification of the nano titanium dioxide comprise ion doping, precious metal deposition, semiconductor compounding, morphology regulation and the like. The ion doping is one of the most effective means for improving the photocatalytic performance of the nano titanium dioxide and widening the spectral response range. The ion-doped modified nano titanium dioxide mainly comprises metal ion doping, non-metal ion doping, co-doping and the like. The method selects metal ion doping to modify a reaction substrate, thereby improving the photocatalytic activity of the reaction substrate.

Disclosure of Invention

The invention aims to solve the problem that the photocatalytic degradation efficiency of a single photocatalyst is low under the irradiation of visible light, and provides a preparation method for simply, conveniently and efficiently synthesizing an iron ion doped titanium dioxide photocatalytic material.

The invention is Fe-TiO with high exposure {001} crystal face₂Photocatalytic material, preparation method and application thereof, and high-exposure {001} crystal face Fe-TiO₂In the photocatalytic material, Fe-TiO₂The photocatalytic material is formed by doping titanium dioxide nanosheets with ferric ions, wherein the molar ratio of iron to titanium is 5%: 1.

the high-exposure {001} crystal face Fe-TiO₂The preparation method of the photocatalytic material comprises the following steps:

step (1), taking 10mL of tetrabutyl titanate and adding into a beaker, and then dropwise adding 1.2 mL of 40% hydrofluoric acid solution into the beaker;

step (2) according to the molar ratio of the iron element to the titanium element of 5%: 1, adding a preset amount of ferric nitrate nonahydrate into a beaker;

continuously stirring for 30min by magnetic force;

transferring the mixed solution into a reaction kettle, and keeping the mixed solution at 180 ℃ for 24 hours to obtain a primary sample;

and (4) washing the initial sample with water and alcohol, drying at 80 ℃, and grinding to obtain the final photocatalytic material.

The high-exposure {001} crystal face Fe-TiO₂Use of a photocatalytic material, said highly exposed {001} crystal plane Fe-TiO₂The photocatalytic material is used for carrying out a photodegradation experiment under a 300W xenon lamp.

The invention has the advantages of high exposure of {001} crystal face Fe-TiO₂The photocatalytic material improves the utilization rate of sunlight, greatly reduces the recombination rate of photon-generated carriers, further improves the photocatalytic activity to a great extent, and lays a good foundation for further practical application.

The high-exposure {001} crystal face Fe-TiO prepared by the invention₂The photocatalytic activity of the photocatalytic material is obviously superior to that of pure-phase titanium dioxide, and the degradation rate of the rose red dye in a short time under a 300W xenon lamp reaches over 95 percent.

The sample prepared by the method is flaky in appearance, and the high-exposure {001} crystal face Fe-TiO prepared by the experiment₂The photocatalytic material has excellent recyclability and stability.

Drawings

FIG. 1 shows an XRD spectrum of a sample prepared by the present invention, FIG. 2 shows a TEM photograph of a sample prepared by the present invention, FIG. 3 shows a UV-DRS spectrum of a sample prepared by the present invention, and FIG. 4 shows a degradation pattern of a sample prepared by the present invention irradiated with rose bengal under a 300W xenon lamp.

Detailed Description

The invention is Fe-TiO with high exposure {001} crystal face₂Photocatalytic material, preparation method and application thereof, and high-exposure {001} crystal face Fe-TiO₂In the photocatalytic material, Fe-TiO₂The photocatalytic material is formed by doping titanium dioxide nanosheets with ferric ions, wherein the molar ratio of iron to titanium is 5%: 1.

the high-exposure {001} crystal face Fe-TiO₂The preparation method of the photocatalytic material comprises the following steps:

step (1), taking 10mL of tetrabutyl titanate and adding into a beaker, and then dropwise adding 1.2 mL of 40% hydrofluoric acid solution into the beaker;

step (2) according to the molar ratio of the iron element to the titanium element of 5%: 1, adding a preset amount of ferric nitrate nonahydrate into a beaker;

continuously stirring for 30min by magnetic force;

transferring the mixed solution into a reaction kettle, and keeping the mixed solution at 180 ℃ for 24 hours to obtain a primary sample;

and (4) washing the initial sample with water and alcohol, drying at 80 ℃, and grinding to obtain the final photocatalytic material.

The high-exposure {001} crystal face Fe-TiO₂The preparation method of the photocatalytic material adopts titanium dioxide with hydrofluoric acid exposed high-energy crystal faces as a substrate.

The high-exposure {001} crystal face Fe-TiO₂The preparation method of the photocatalytic material is a one-step hydrothermal method, namely, a certain amount of tetrabutyl titanate, hydrofluoric acid and ferric nitrate nonahydrate are sequentially added into a reactor.

The high-exposure {001} crystal face Fe-TiO₂The preparation method of the photocatalytic material comprises the following steps of (1) preparing the photocatalytic material, wherein the molar ratio of the iron element to the titanium element is 5%: 1, in a ratio of 1.

The high-exposure {001} crystal face Fe-TiO₂The preparation method of the photocatalytic material comprises the steps of stirring for 30min by adopting magnetic force, carrying out hydrothermal reaction at 180 ℃ in a blast oven, and keeping for 24 h.

The high-exposure {001} crystal face Fe-TiO₂A preparation method of a photocatalytic material comprises the step of dropwise adding 1.2 mL of 40% hydrofluoric acid solution to 10mL of tetrabutyl titanate.

The high-exposure {001} crystal face Fe-TiO₂Method for preparing photocatalytic material, saidThe washing method comprises three times of washing with distilled water and absolute ethyl alcohol respectively.

The high-exposure {001} crystal face Fe-TiO₂Use of a photocatalytic material, said highly exposed {001} crystal plane Fe-TiO₂The photocatalytic material is used for carrying out a photodegradation experiment under a 300W xenon lamp.

The high-exposure {001} crystal face Fe-TiO₂Use of a photocatalytic material, said highly exposed {001} crystal plane Fe-TiO₂The photocatalytic material degrades rose bengal dye under simulated sunlight of a xenon lamp.

The invention is Fe-TiO with high exposure {001} crystal face₂The photocatalytic material is prepared by taking titanium dioxide with hydrofluoric acid exposed high-energy crystal faces as a substrate, and the molar ratio of iron to titanium is 5%: 1.

the high-exposure {001} crystal face Fe-TiO₂The preparation method of the photocatalytic material comprises the following steps: first, 10mL of tetrabutyltitanate was added to a beaker, and 1.2 mL of 40% hydrofluoric acid solution was added dropwise to the beaker. Then, according to the molar ratio of the iron element to the titanium element being 5%: 1, adding a certain amount of ferric nitrate nonahydrate into a beaker. Magnetic stirring was continued for 30 min. And finally, transferring the mixed solution into a reaction kettle, and keeping the temperature at 180 ℃ for 24 hours to obtain a primary sample. And (3) washing the initial sample with water and alcohol, drying at 80 ℃, and grinding to obtain the final photocatalytic material.

The titanium dioxide with hydrofluoric acid exposed high-energy crystal face is used as a substrate.

The method is a one-step hydrothermal method, namely, a certain amount of tetrabutyl titanate, hydrofluoric acid and ferric nitrate nonahydrate are sequentially added into a reactor.

The molar ratio of the iron element to the titanium element is 5%: 1, in a ratio of 1.

The stirring is carried out for 30min by adopting magnetic stirring, and the hydrothermal reaction is carried out in a forced air oven at 180 ℃ and is kept for 24 h.

1.2 mL of 40% hydrofluoric acid solution was added dropwise to 10mL of tetrabutyltitanate.

The washing method comprises three times of washing respectively by distilled water and absolute ethyl alcohol.

The high-exposure {001} crystal face Fe-TiO₂The photocatalytic material was subjected to a photodegradation experiment under a 300W xenon lamp.

High-exposure {001} crystal face Fe-TiO₂Use of a photocatalytic material, said highly exposed {001} crystal plane Fe-TiO₂The photocatalytic material is applied to degrading rose bengal dye. The 300W xenon lamp is used for simulating sunlight to degrade the rose red dye to realize practical application.

High-exposure {001} crystal face Fe-TiO₂The photocatalytic material is applied to degrading rose bengal dye, and a 300W xenon lamp is adopted to simulate a natural light source. The concentration of the rose bengal dye is 5mg/L, and the high-exposure {001} crystal face Fe-TiO₂The amount of the photocatalyst used was 0.5 mg/L. The specific test method for the photocatalytic activity comprises the following steps: A300W xenon lamp is used as a simulated light source, 100mL rose red dye is poured into a beaker, and the exposed {001} crystal face Fe-TiO is heightened₂And (3) opening a magnetic stirrer for the photocatalyst, carrying out dark adsorption until the photocatalyst is balanced, opening a xenon lamp to vertically irradiate the rose red dye, and sampling once at intervals until the rose red dye is completely degraded. And finally, measuring the absorbance of the sample by using an ultraviolet-visible spectrophotometer.

The present invention will be further described with reference to specific embodiments thereof, which are not intended to limit the invention, and any simple modifications and equivalents of the above-described embodiments may be made by anyone within the technical scope of the present invention.