CN101862664A - Preparation of fluorine and carbon co-doped nano-titanium dioxide visible light photocatalyst - Google Patents
Preparation of fluorine and carbon co-doped nano-titanium dioxide visible light photocatalyst Download PDFInfo
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- CN101862664A CN101862664A CN 201010207656 CN201010207656A CN101862664A CN 101862664 A CN101862664 A CN 101862664A CN 201010207656 CN201010207656 CN 201010207656 CN 201010207656 A CN201010207656 A CN 201010207656A CN 101862664 A CN101862664 A CN 101862664A
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Abstract
The invention relates to a preparation method of a fluorine and carbon co-doped nano-titanium dioxide visible light photocatalyst, comprising the following steps of: dropping an anhydrous alcohol solution of tetrabutyl titanate into an ammonium fluoride water solution and ethylene diamine by mixing; hydrolyzing by mixing at room temperature, wherein a mol ratio of fluorine to titanium is 0.05:1-0.2:1, and a mol ratio of the ethylene diamine to the tetrabutyl titanate is 0.16:1-0.48:1; obtaining collosol; obtaining flaxen gel by drying the collosol; and obtaining the fluorine and carbon co-doped nano-titanium dioxide photocatalyst by calcining the gel. In the preparation method, the reaction condition is mild and is easy to control, devices are simple, raw materials are easy to purchase, and a synthetic process is simple and is easy to industrially produce; the prepared fluorine and carbon co-doped nano-titanium dioxide photocatalyst has high specific surface, pure crystalling phase, more surface acid sites and visible light response.
Description
Technical field
The invention belongs to the preparation field of nano-titanium dioxide visible light photocatalyst, particularly the preparation method of fluorine, carbon co-doped nano-titanium dioxide visible light photocatalyst.
Background technology
Titanium dioxide has the focus that inexpensive, nontoxic and higher chemical stability becomes photocatalysis field research because of it.But the band-gap energy of titanium dioxide big (～3.2eV), only under the irradiation of ultraviolet light, just can be excited, and ultraviolet light only accounts for 3～5% of sunshine, therefore, it is greatly limited in actual applications.In order to make full use of sunshine, titanium dioxide is modified and modification, make its spectral absorption expand and to improve its visible light photocatalysis active be the present important topic that faces of this field to visible region.
Expand titanium dioxide spectrum absorb to the effective method of visible region be the doping extraneous element.From Asahi at Science, 2001, the last reported first of 293:269-271 behind the titanium dioxide that mixes of nitrogen, the doped with non-metals element as: nitrogen, carbon, boron, sulphur and fluorine have become the focus of everybody research.Though it is visible light-responded that the titanium dioxide of these doping has, can not guarantee the raising of photocatalysis performance.For guaranteeing that titanium dioxide promptly has the stronger visible light photocatalysis active of visible light-responded performance again, Domen seminar is at J.Phys.Chem.C 2007, reported the synthetic of nitrogen and fluorin-doped titanium dioxide optical catalyst on the 111:18264-18270 and be used for the visible light decomposition water, its quantum yield is enhanced.Cong etc. are at J.Phys.Chem.C 2007, and 111:10618-10623 has reported the TiO that has synthesized nitrogen and iron codope with the method for co-precipitation-hydro-thermal
2, the doping of dual element can suppress the compound of electron-hole pair, and degrade under the radiation of visible light activity of rhodamine B of this catalyst is greatly improved.Huo etc. are at Appl.Catal.B 2008, and 83:78-84 has reported the TiO that has synthesized lanthanum, boron codope under postcritical condition
2, the result shows: lanthanum is with isolated La
2O
3Form covers TiO
2The surface, boron then enters TiO
2Lattice in replace oxonium ion and form compound keys.This sample shows stronger photocatalytic activity at visible light light district degradation of methylene blue.Chen etc. are at Ind.Eng.Chem.Res.2007,46,2741-2746 has reported with the method for sol-gel and has synthesized carbon and nitrogen co-doped nano titanium dioxide photocatalyst, this photochemical catalyst shows visible light-responded preferably at visible region, show stronger visible light photocatalysis active simultaneously in the process of degradation of methylene blue solution.Reyes-Garcia etc. are at J.Phys.Chem.C 2007, and 111:17146-17154 has synthesized boron, fluorin-doped TiO with the sol-gel method
2Powder, the doping of boron and fluorine can make the spectral absorption generation red shift of titanium dioxide.Degradation results in visible light light district to methylene blue shows boron, fluorin-doped TiO
2Can improve photocatalytic activity.
Summary of the invention
Technical problem to be solved by this invention provides the preparation of fluorine, carbon co-doped nano-titanium dioxide visible light photocatalyst, gentle and the control easily of this method reaction condition, equipment is simple, raw material sources are abundant, building-up process is simple, output is higher, can be used for large-scale production, and prepared fluorine, carbon co-doped nano titanium dioxide photocatalyst have specific surface height, crystalline phase is pure, surface acidity point is many, visible light-responded performance.
The preparation method of fluorine of the present invention, carbon co-doped nano-titanium dioxide visible light photocatalyst comprises:
(1) preparation of colloidal sol
At room temperature, the ethanol solution of butyl titanate under agitation is added drop-wise in the aqueous solution and ethylenediamine of ammonium fluoride, stir under the room temperature and be hydrolyzed in 8～12 hours, obtain colloidal sol, wherein the mol ratio of fluorine and titanium is 0.05: 1～0.2: 1, and the mol ratio of ethylenediamine and butyl titanate is 0.16: 1～0.48: 1;
(2) preparation of xerogel
Above-mentioned colloidal sol was obtained gel in 8～12 hours 70～100 ℃ of oven dry;
(3) calcining
Gel was obtained fluorine, carbon co-doped nano-titanium dioxide visible light photocatalyst in 1～3 hour 400～600 ℃ of calcinings.
The ethanol solution concentration of the butyl titanate in the described step (1) is 1M, and the concentration of aqueous solution of ammonium fluoride is 0.05～0.3M, and the concentration of ethylenediamine is 0.16～0.48M.
Beneficial effect
(1) this method reaction condition is room temperature, normal pressure, and the reaction condition gentleness is easy to control, and equipment is simple, and raw material is easy to buying, and building-up process is simple.Therefore, be easy to suitability for industrialized production.
(2) prepared fluorine, carbon co-doped nano titanium dioxide photocatalyst has specific surface height, crystalline phase is pure, surface acidity point is many, visible light-responded performance.
Description of drawings
Fig. 1 is the X-ray diffractogram of fluorine, carbon co-doped nano titanium oxide;
Fig. 2 is the ultraviolet-visible light spectrogram of fluorine, carbon co-doped nano titanium oxide;
Fig. 3 is the transmission electron microscope photo of fluorine, carbon co-doped nano titanium oxide;
Fig. 4 is the 1s track XPS spectrum figure of the fluorine of fluorine, carbon co-doped nano titanium oxide;
Fig. 5 is the 1s track XPS spectrum figure of the carbon of fluorine, carbon co-doped nano titanium oxide;
Fig. 6 is the visible light photocatalysis performance map of fluorine, carbon co-doped nano titanium oxide.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Measure 100mL 0.05M ammonium fluoride solution and 1mL content greater than the ethylenediamine of 99wt% in reactor.The ethanol solution of measuring 100mL 1M butyl titanate under the stirring at room, is added drop-wise to the ethanol solution of butyl titanate in the aqueous solution of ammonium fluoride and ethylenediamine in dropping funel, white precipitate occurs.After dropwising, at room temperature stirred 12 hours, make butyl titanate continue hydrolysis and obtain colloidal sol.Then colloidal sol was dried 12 hours at 80 ℃, boil off moisture and ethanol, obtain flaxen gel.400 ℃ of calcinings 2 hours the Powdered fluorine of light gray, carbon co-doped titanium dioxide.Fig. 1 is the synthetic fluorine of present embodiment, carbon co-doped titanium dioxide X-ray diffractogram, and the diffraction maximum among the figure shows: the crystalline phase of this sample is pure anatase phase.The uv-visible absorption spectra of the fluorine that Fig. 2 synthesizes for present embodiment, carbon co-doped titanium dioxide, as can be seen: certain red shift has taken place in its absorption spectrum.Fig. 3 is the transmission electron microscope photo of this sample, and as can be seen: the synthetic sample particle diameter of present embodiment is 13.1nm.Fig. 4 is the XPS spectrum figure of sample fluorine, and fluorine exists with physical absorption with two kinds of forms of titanium formation Ti-F as can be seen.Fig. 5 is the 1s binding energy collection of illustrative plates of this sample carbon, and Fig. 6 is the curve of the 4-chlorophenol of degrading under visible light of this sample, and its degradation rate reaches 73.8%.
Measure 100mL 0.1M ammonium fluoride solution and 1mL content greater than the ethylenediamine of 99wt% in reactor.The ethanol solution of butyl titanate of measuring 100mL 1M under the stirring at room, is added drop-wise to the ethanol solution of butyl titanate in ammonium fluoride and the ethylenediamine solution in dropping funel, white precipitate occurs.After dropwising, at room temperature stirred 10 hours, make butyl titanate continue hydrolysis and obtain colloidal sol.Then colloidal sol was dried 10 hours at 100 ℃, boil off moisture and ethanol, obtain flaxen gel.400 ℃ of calcinings 2 hours the Powdered fluorine of light gray, carbon co-doped nano titanium dioxide photocatalyst.
Measure 100mL 0.05M ammonium fluoride solution and 2mL content greater than the ethylenediamine of 99wt% in reactor.The ethanol solution of butyl titanate of measuring 100mL 1M under the stirring at room, under the stirring at room, is added drop-wise to the ethanol solution of butyl titanate in the aqueous solution of ammonium fluoride and ethylenediamine in dropping funel, white precipitate occurs.After dropwising, at room temperature stirred 8 hours, make butyl titanate continue hydrolysis and obtain colloidal sol.Then colloidal sol was dried 10 hours at 100 ℃, boil off moisture and ethanol, obtain flaxen gel.400 ℃ of calcinings 2 hours light brown powder shape fluorine, carbon co-doped nano titanium dioxide photocatalyst.
Measure 100mL 0.15M ammonium fluoride solution and 3mL content greater than the ethylenediamine of 99wt% in reactor.The ethanol solution of butyl titanate of measuring 100mL 1M under the stirring at room, is added drop-wise to the ethanol solution of butyl titanate in ammonium fluoride and the ethylenediamine solution in dropping funel, white precipitate occurs.After dropwising, at room temperature stirred 12 hours, make butyl titanate continue hydrolysis and obtain colloidal sol.Then colloidal sol was dried 10 hours at 100 ℃, boil off moisture and ethanol, obtain flaxen gel.500 ℃ of calcinings 2 hours brown ceramic powder shape fluorine, carbon co-doped nano titanium dioxide photocatalyst.
Embodiment 5:
Measure 100mL 0.05M ammonium fluoride solution and 1mL content greater than the ethylenediamine of 99wt% in reactor.The ethanol solution of butyl titanate of measuring 100mL 1M under the stirring at room, is added drop-wise to the ethanol solution of butyl titanate in the aqueous solution of ammonium fluoride and ethylenediamine in dropping funel, white precipitate occurs.After dropwising, at room temperature stirred 12 hours, make butyl titanate continue hydrolysis and obtain colloidal sol.Then colloidal sol was dried 10 hours at 90 ℃, boil off moisture and ethanol, obtain flaxen gel.600 ℃ of calcinings 2 hours white powder fluorine, carbon co-doped nano titanium dioxide photocatalyst.
Claims (4)
1. the preparation method of fluorine, carbon co-doped nano-titanium dioxide visible light photocatalyst comprises:
(1) preparation of colloidal sol
At room temperature, the ethanol solution of butyl titanate under agitation is added drop-wise in the aqueous solution and ethylenediamine of ammonium fluoride, stir under the room temperature and be hydrolyzed in 8～12 hours, obtain colloidal sol, wherein the mol ratio of fluorine and titanium is 0.05: 1～0.2: 1, and the mol ratio of ethylenediamine and butyl titanate is 0.16: 1～0.48: 1;
(2) preparation of xerogel
Above-mentioned colloidal sol was obtained gel in 8～12 hours 70～100 ℃ of oven dry;
(3) calcining
Gel was obtained fluorine, carbon co-doped nano-titanium dioxide visible light photocatalyst in 1～3 hour 400～600 ℃ of calcinings.
2. the preparation method of fluorine according to claim 1, carbon co-doped nano-titanium dioxide visible light photocatalyst, it is characterized in that: the ethanol solution concentration of the butyl titanate in the described step (1) is 1M.
3. the preparation method of fluorine according to claim 1, carbon co-doped nano-titanium dioxide visible light photocatalyst, it is characterized in that: the concentration of aqueous solution of the ammonium fluoride in the described step (1) is 0.05～0.3M.
4. the preparation method of fluorine according to claim 1, carbon co-doped nano-titanium dioxide visible light photocatalyst is characterized in that: the concentration of the ethylenediamine in the described step (1) is for greater than 99wt%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527421A (en) * | 2011-11-10 | 2012-07-04 | 重庆工商大学 | C and N dual-doped nano TiO2 photochemical catalyst and preparation method thereof |
| CN103638916A (en) * | 2013-11-01 | 2014-03-19 | 河南大学 | Bound single electron oxygen vacancy-containing titanium dioxide/carbon composite visible-light-induced photocatalyst and preparation method thereof |
| CN107999129A (en) * | 2018-01-24 | 2018-05-08 | 常州市新鸿医药化工技术有限公司 | A kind of modified SrTiO3Photochemical catalyst and preparation method thereof |
Citations (3)
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| US20060210798A1 (en) * | 2005-03-16 | 2006-09-21 | Clemens Burda | Doped metal oxide nanoparticles and methods for making and using same |
| CN101444724A (en) * | 2008-12-24 | 2009-06-03 | 南开大学 | Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst |
| CN101474556A (en) * | 2009-01-13 | 2009-07-08 | 东华大学 | Preparation method of fluorine and lanthanum co-doped nano titanic oxide visible light photocatalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060210798A1 (en) * | 2005-03-16 | 2006-09-21 | Clemens Burda | Doped metal oxide nanoparticles and methods for making and using same |
| CN101444724A (en) * | 2008-12-24 | 2009-06-03 | 南开大学 | Method for preparing high activity non-metallic ion co-doped titanium dioxide photochemical catalyst |
| CN101474556A (en) * | 2009-01-13 | 2009-07-08 | 东华大学 | Preparation method of fluorine and lanthanum co-doped nano titanic oxide visible light photocatalyst |
Non-Patent Citations (2)
| Title |
|---|
| 《Catalysis Today》 20090131 Miguel Pelaez et al Visible light-activated N-F-codoped TiO2 nanoparticles for the photocatalytic degradation of microcystin-LR in water 1-4 第144卷, 2 * |
| 《硅酸盐通报》 20100228 曹广秀等 氟、硼共掺杂对纳米TiO2能带结构与可见光光催化性能的影响 1-4 第29卷, 第01期 2 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102527421A (en) * | 2011-11-10 | 2012-07-04 | 重庆工商大学 | C and N dual-doped nano TiO2 photochemical catalyst and preparation method thereof |
| CN103638916A (en) * | 2013-11-01 | 2014-03-19 | 河南大学 | Bound single electron oxygen vacancy-containing titanium dioxide/carbon composite visible-light-induced photocatalyst and preparation method thereof |
| CN107999129A (en) * | 2018-01-24 | 2018-05-08 | 常州市新鸿医药化工技术有限公司 | A kind of modified SrTiO3Photochemical catalyst and preparation method thereof |
| CN107999129B (en) * | 2018-01-24 | 2020-08-04 | 常州市新鸿医药化工技术有限公司 | Modified SrTiO3Photocatalyst and preparation method thereof |
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