CN1613554A - Preparation of visual responsing titania light catalyst - Google Patents
Preparation of visual responsing titania light catalyst Download PDFInfo
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- CN1613554A CN1613554A CN 200410066813 CN200410066813A CN1613554A CN 1613554 A CN1613554 A CN 1613554A CN 200410066813 CN200410066813 CN 200410066813 CN 200410066813 A CN200410066813 A CN 200410066813A CN 1613554 A CN1613554 A CN 1613554A
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- ethyl orthosilicate
- titanate
- tio
- titanate esters
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Abstract
A process for preparing the TiO2 photocatalyst responsive to visual light includes such steps as hydrolyzing and condensation reacting between titanate and ethyl silicate in the aqueous solution of alcohol under existance of hydrochloric acid as catalyst to obtain TiO2 gel containing SiO2, heat treating to obtain TiO2 powder, and nitrifying it in the ammonia atmosphere at 550-700 deg.c. Its advantages are large specific surface area and high photocatalytic activity.
Description
Technical field
The present invention relates to a kind of preparation method of visual responsing titania light catalyst, make the octahedrite type titanium dioxide photocatalyst of nitrogenous and silica, belong to catalyst class field of new with visible light catalytic performance by sol-gel process.
Background technology
Since Honda and Fujishima in 1972 finds TiO
2Electrode can resolve into H to water
2And O
2Since, TiO
2Cause the interest that people are very big with the light-catalyzed reaction of other semi-conducting material as the potential approach that solves the energy and environmental problem.Semiconductor TiO wherein
2Because of its chemical property is stable, the nontoxic ideal material that becomes the solution energy and environmental problem with effectively removing the pollutant in the big G﹠W, and caused various countries researcher extensive interest.Present research has demonstrated TiO
2Wide application prospect, it can be numerous organic pollution photocatalytic degradations nontoxic micromolecular compound, as water, CO
2, inorganic acid etc.; Remove the heavy metal ion in the solution, it is reduced to nontoxic metal; Photodissociation water is H
2And O
2Obtain Hydrogen Energy; Be applied to solar cell solar energy effectively is converted to chemical energy.But TiO
2Be broad stopband (Eg=3.2eV) semiconducting compound, (λ＜387nm) just can be absorbed, and this part ultraviolet energy only accounts for and reaches 4%～6% of ground solar energy, solar energy utilization ratio is very low to have only the short solar energy of wavelength.And visible light has accounted for 45% of solar energy gross energy, and therefore preparing the highly efficient titania catalyst with visible light catalysis activity is present domestic and international research focus.Asahi etc. [Science 2001,293:p269] have proposed nitrogen doped Ti O
2Notion, they are by anatase TiO
2Powder (ST01) is placed on NH
3Heat-treating methods has prepared nitrogenous titanium deoxide catalyst in the atmosphere, with pure TiO
2Compare, nitrogenous titanium deoxide catalyst can absorb the energy of visible light wave range.But pure TiO
2In nitridation process, be transformed into the rutile facies pattern, and specific area reduces obviously by Detitanium-ore-type.General anatase phase TiO
2Photocatalysis performance be better than rutile phase TiO
2, and big specific area helps TiO
2With fully contacting and reaction of reactant, thus the appearance of rutile phase and specific area reduce all to be unfavorable for TiO
2Photocatalysis performance.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of preparation method of visual responsing titania light catalyst is proposed, the Detitanium-ore-type catalyst of the nitrogenous and silica that makes not only can absorb visible light, and has photocatalytic activity under visible light.
For realizing such purpose, the present invention utilizes SiO
2Can effectively stop TiO
2The phase transformation in heat treatment process and the characteristic of grain growth are raw material with titanate esters and ethyl orthosilicate respectively, are catalyst with hydrochloric acid, and hydrolysis and condensation reaction take place in alcohol and water solution, obtain containing SiO
2TiO
2Gel, to obtain titanium dioxide powder after the gel heat treatment again, at last titanium dioxide powder is carried out nitrogenize heat treatment in ammonia flow, it is little that the faint yellow nitrogenous titanium dioxide optical catalyst of the Detitanium-ore-type that obtains has particle size, characteristics such as specific area is big have higher photocatalytic activity under radiation of visible light.
The concrete technology that the present invention prepares the titanium deoxide catalyst of the nitrogenous and silica of visible-light response type is:
1) getting percent by volume is that 1: 1 titanate esters and ethanolic solution mix and stir, and is mixed with the titanate esters alcohol mixeding liquid.
2) measure the ethanolic solution that volume equals 1/4 times of above-mentioned mixeding liquid volume in addition, add ethyl orthosilicate, making the mol ratio of ethyl orthosilicate and titanate esters is 0.03～0.05: 1, is mixed with the ethanolic solution of ethyl orthosilicate, stirs 15 minutes.
3) in the ethanolic solution of ethyl orthosilicate, add the hydrolyzation catalysis agent solution, strong agitation 2 hours, catalyst solution is made up of hydrochloric acid, water and ethanol, and the mol ratio of hydrochloric acid, water and ethanol and titanate esters is 2～3: 10～12: 5～8: 1, obtain the ethyl orthosilicate mixed liquor.
4) the titanate esters alcohol mixeding liquid with preparation in the step 1 all splashes in the above-mentioned ethyl orthosilicate mixed liquor, and strong agitation left standstill after 2 hours, obtained SiO
2/ TiO
2Gel.
5) with SiO
2/ TiO
2Gel was heat-treated in 500 ℃ atmosphere 2～4 hours, obtained containing SiO
2TiO
2Powder.
6) with above-mentioned TiO
2Powder was placed in the tube furnace that is connected with the ammonia that flows nitrogenize heat treatment 1～3 hour, and ammonia flow is 20～40ml/min, and nitriding temperature is 550～700 ℃, finally obtained the titania powder of faint yellow nitrogenous and silica.
The titanate esters that adopts among the present invention is butyl titanate, tetraethyl titanate or isopropyl titanate.
The present invention adopts sol gel process at TiO
2The middle SiO that adds
2, can guarantee inorganic molecule TiO
2And SiO
2Compound at molecular level, SiO
2Can effectively stop TiO
2Contingent phase transformation and grain growth in the nitrogen treatment process, Zhi Bei nitrogenous TiO like this
2Not only since the N that mixes at TiO
2Formed new energy level in the forbidden band, can absorb visible light, and be the anatase phase entirely, crystallite dimension is little, and specific area is big, has higher photocatalysis performance under radiation of visible light.
The specific embodiment
Further describe technical scheme of the present invention below by specific embodiment.
Embodiment 1:
1) 44ml butyl titanate and 44ml ethanolic solution are mixed, stir;
2) 1ml ethyl orthosilicate and 22ml ethanolic solution are mixed, stirred 15 minutes;
3) 8ml hydrochloric acid, 24ml water and 40ml ethanol are formulated as the hydrolyzation catalysis agent solution, add in the above-mentioned teos solution, vigorous stirring 2 hours;
4) with 1) in the titanate esters ethanolic solution all splash in the above-mentioned ethyl orthosilicate mixed liquor, strong agitation left standstill after 2 hours, obtained SiO
2/ TiO
2Gel;
5) the above-mentioned gel that obtains was heat-treated in 500 ℃ atmosphere 2 hours, obtain SiO
2Molar content be 3% TiO
2Powder;
6) with above-mentioned TiO
2Powder is placed on and carries out nitrogen treatment in the tube furnace that is connected with ammonia flow, and ammonia flow is 20ml/min, 700 ℃ of following nitrogenize 3 hours, finally obtains the titanium dioxide powder of flaxen nitrogenous and silica.
Embodiment 2:
1) 30ml tetraethyl titanate and 30ml ethanolic solution are mixed, stir;
2) 1.5ml ethyl orthosilicate and 15ml ethanolic solution are mixed, stirred 15 minutes;
3) 10ml hydrochloric acid, 26ml water and 60ml ethanol are formulated as the hydrolyzation catalysis agent solution, add in the above-mentioned teos solution, vigorous stirring 2 hours;
4) with 1) in the tetraethyl titanate ethanolic solution all splash in the above-mentioned ethyl orthosilicate mixed liquor, strong agitation left standstill after 2 hours, obtained SiO
2/ TiO
2Gel;
5) the above-mentioned gel that obtains was heat-treated in 500 ℃ atmosphere 3 hours, obtain SiO
2Molar content be 5% TiO
2Powder;
6) with above-mentioned TiO
2Powder is placed on and carries out nitrogen treatment in the tube furnace that is connected with ammonia flow, and ammonia flow is 40ml/min, 550 ℃ of following nitrogenize 3 hours, finally obtains the titanium dioxide powder of flaxen nitrogenous and silica.
Embodiment 3:
1) 36ml isopropyl titanate and 36ml ethanolic solution are mixed, stir;
2) 1ml ethyl orthosilicate and 18ml ethanolic solution are mixed, stirred 15 minutes;
3) 12ml hydrochloric acid, 28ml water and 50ml ethanol are formulated as the hydrolyzation catalysis agent solution, add in the above-mentioned teos solution, vigorous stirring 2 hours;
4) with 1) in the titanate esters ethanolic solution all splash in the above-mentioned ethyl orthosilicate mixed liquor, strong agitation left standstill after 2 hours, obtained SiO
2/ TiO
2Gel;
5) the above-mentioned gel that obtains was heat-treated in 500 ℃ atmosphere 4 hours, obtain SiO
2Molar content be 3.5% TiO
2Powder;
6) with above-mentioned TiO
2Powder is placed on and carries out nitrogen treatment in the tube furnace that is connected with ammonia flow, and ammonia flow is 40ml/min, 700 ℃ of following nitrogenize 1 hour, finally obtains the titanium dioxide powder of flaxen nitrogenous and silica.
Claims (2)
1, a kind of preparation method of visual responsing titania light catalyst is characterized in that comprising the steps:
1) getting percent by volume is that 1: 1 titanate esters and ethanolic solution mix and stir, and is mixed with the titanate esters alcohol mixeding liquid;
2) measure the ethanolic solution that volume equals 1/4 times of above-mentioned mixeding liquid volume in addition, add ethyl orthosilicate, making the mol ratio of ethyl orthosilicate and titanate esters is 0.03～0.05: 1, is mixed with the ethanolic solution of ethyl orthosilicate, stirs 15 minutes;
3) in the ethanolic solution of ethyl orthosilicate, add the hydrolyzation catalysis agent solution, strong agitation 2 hours, catalyst solution is made up of hydrochloric acid, water and ethanol, and the mol ratio of hydrochloric acid, water and ethanol and titanate esters is 2～3: 10～12: 5～8: 1, obtain the ethyl orthosilicate mixed liquor;
4) the titanate esters alcohol mixeding liquid with preparation in the step 1 all splashes in the above-mentioned ethyl orthosilicate mixed liquor, and strong agitation left standstill after 2 hours, obtained SiO
2/ TiO
2Gel;
5) with SiO
2/ TiO
2Gel was heat-treated in 500 ℃ atmosphere 2～4 hours, obtained containing the TiO2 powder of SiO2;
6) above-mentioned TiO2 powder was placed in the tube furnace that is connected with the ammonia that flows nitrogenize heat treatment 1～3 hour, ammonia flow is 20～40ml/min, and nitriding temperature is 550～700 ℃, finally obtains the titania powder of faint yellow nitrogenous and silica.
2, the preparation method of the visual responsing titania light catalyst of claim 1 is characterized in that described titanate esters is butyl titanate, tetraethyl titanate or isopropyl titanate.
Priority Applications (1)
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|---|---|---|---|
| CN 200410066813 CN1273214C (en) | 2004-09-29 | 2004-09-29 | Preparation of visual responsing titania light catalyst |
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|---|---|---|---|
| CN 200410066813 CN1273214C (en) | 2004-09-29 | 2004-09-29 | Preparation of visual responsing titania light catalyst |
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| CN1613554A true CN1613554A (en) | 2005-05-11 |
| CN1273214C CN1273214C (en) | 2006-09-06 |
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|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875563B (en) * | 2009-04-29 | 2013-05-01 | 研能科技股份有限公司 | Composite capable of increasing high temperature resistance degree of object and preparation method thereof |
| CN103130267A (en) * | 2013-02-19 | 2013-06-05 | 上海师范大学 | Preparation method for visible-light response black titanium dioxide photocatalyst |
| CN103691472A (en) * | 2013-12-29 | 2014-04-02 | 镇江东艺机械有限公司 | Preparation method of nitrogen-doped titanium dioxide mesoporous visible light photocatalyst |
| CN103831123A (en) * | 2014-02-17 | 2014-06-04 | 中国科学院过程工程研究所 | Co-doped titanium dioxide catalyst and a preparing method |
| CN104001470A (en) * | 2014-05-21 | 2014-08-27 | 华南理工大学 | Ti-Si-O difunctional photocatalysis adsorbent as well as preparation method and application thereof in fuel oil desulphurization |
| CN104923271A (en) * | 2014-03-20 | 2015-09-23 | 哈尔滨工业大学深圳研究生院 | Supported fluorine-doped and nitrogen-fluorine co-doped titanium dioxide for acrylonitrile photocatalytic degradation |
| CN106362784A (en) * | 2016-08-01 | 2017-02-01 | 中国科学院宁波材料技术与工程研究所 | TiO2-SiO2 visible-light-driven photocatalytic composite film and preparation method thereof |
| CN108134104A (en) * | 2017-12-26 | 2018-06-08 | 成都新柯力化工科技有限公司 | Composite catalyst carrier for fuel cell and preparation method and application thereof |
| CN108666588A (en) * | 2018-05-10 | 2018-10-16 | 东北师范大学 | A kind of three-dimensional substrates material load Ag doping titanium dioxide optical catalyst and the preparation method and application thereof |
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2004
- 2004-09-29 CN CN 200410066813 patent/CN1273214C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101875563B (en) * | 2009-04-29 | 2013-05-01 | 研能科技股份有限公司 | Composite capable of increasing high temperature resistance degree of object and preparation method thereof |
| CN103130267A (en) * | 2013-02-19 | 2013-06-05 | 上海师范大学 | Preparation method for visible-light response black titanium dioxide photocatalyst |
| CN103691472A (en) * | 2013-12-29 | 2014-04-02 | 镇江东艺机械有限公司 | Preparation method of nitrogen-doped titanium dioxide mesoporous visible light photocatalyst |
| CN103831123B (en) * | 2014-02-17 | 2015-12-30 | 中国科学院过程工程研究所 | A kind of codope TiO 2catalysts and its preparation method |
| CN103831123A (en) * | 2014-02-17 | 2014-06-04 | 中国科学院过程工程研究所 | Co-doped titanium dioxide catalyst and a preparing method |
| CN104923271A (en) * | 2014-03-20 | 2015-09-23 | 哈尔滨工业大学深圳研究生院 | Supported fluorine-doped and nitrogen-fluorine co-doped titanium dioxide for acrylonitrile photocatalytic degradation |
| CN104001470A (en) * | 2014-05-21 | 2014-08-27 | 华南理工大学 | Ti-Si-O difunctional photocatalysis adsorbent as well as preparation method and application thereof in fuel oil desulphurization |
| CN104001470B (en) * | 2014-05-21 | 2016-10-05 | 华南理工大学 | Difunctional photocatalytic adsorbent of a kind of Ti-Si-O and preparation method thereof and its application in fuel desulfuration |
| CN106362784A (en) * | 2016-08-01 | 2017-02-01 | 中国科学院宁波材料技术与工程研究所 | TiO2-SiO2 visible-light-driven photocatalytic composite film and preparation method thereof |
| CN106362784B (en) * | 2016-08-01 | 2019-03-05 | 中国科学院宁波材料技术与工程研究所 | A kind of TiO2-SiO2Visible light photocatalysis laminated film and preparation method thereof |
| CN108134104A (en) * | 2017-12-26 | 2018-06-08 | 成都新柯力化工科技有限公司 | Composite catalyst carrier for fuel cell and preparation method and application thereof |
| CN108134104B (en) * | 2017-12-26 | 2020-05-12 | 成都新柯力化工科技有限公司 | Composite catalyst carrier for fuel cell and preparation method and application thereof |
| CN108666588A (en) * | 2018-05-10 | 2018-10-16 | 东北师范大学 | A kind of three-dimensional substrates material load Ag doping titanium dioxide optical catalyst and the preparation method and application thereof |
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| CN1273214C (en) | 2006-09-06 |
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Granted publication date: 20060906 Termination date: 20091029 |