CN101327425A - Method for preparing nitrogen-doped titanium dioxide photocatalyst - Google Patents
Method for preparing nitrogen-doped titanium dioxide photocatalyst Download PDFInfo
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- CN101327425A CN101327425A CNA2007100546449A CN200710054644A CN101327425A CN 101327425 A CN101327425 A CN 101327425A CN A2007100546449 A CNA2007100546449 A CN A2007100546449A CN 200710054644 A CN200710054644 A CN 200710054644A CN 101327425 A CN101327425 A CN 101327425A
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Abstract
The present invention relates to a preparation method of a nitrogen doped titanium dioxide photocatalyst. The preparation method comprises the steps as follows: firstly, nanotube titanic acid is used as a precursor to be processed for heat treatment under certain temperature to prepare for a novel titanium dioxide; secondly, the prepared novel titanium dioxide is processed for the heat treatment in NH3 airflow; thirdly, the novel titanium dioxide is cooled naturally under the protection of NH3, and the nitrogen doped titanium dioxide photocatalyst can be prepared. The nitrogen doped titanium dioxide photocatalyst prepared by the method of the present invention absorbs strongly in visible region; compared with the titanium dioxide (P25 type) N doped P25 catalyst which is prepared under the same NH3 treatment condition for commercial universal use, the eliminating specific rate constant of trace propylene in the air under visible light of the nitrogen doped titanium dioxide photocatalyst is improved by about four times. The nitrogen doped titanium dioxide photocatalyst prepared by the method of the present invention has wide application prospect as visible light catalyst material, has simple preparation technology, convenient operation and low cost and is fit for batch production.
Description
Technical field
The present invention relates to a kind of preparation method of nitrogen-doped titanium dioxide photocatalyst, belong to the optically catalytic TiO 2 technical field.
Background technology
In recent years,, develop visible light-responded efficiently photochemical catalyst, become the focus of people's research for utilizing this inexhaustible, nexhaustible clean energy resource of solar energy.Titanium dioxide is considered to that one of photochemical catalyst of application prospect is arranged most because have advantages such as oxidability is strong, stable, nontoxic, inexpensive.But because the band gap of titanium dioxide is bigger, can only utilize in the solar energy ultraviolet light, so people focus on exploitation and have on the visible light-responded titanium dioxide optical catalyst less than 5%.[R.Asahi such as calendar year 2001 Asahi, T.Morikawa, T.Ohwaki, K.Aoki, Y.Taga, Science 293 (2001) 269-271] reported with non-metal N and replaced the visible light activity work of an initiative beyond doubt that the Lattice Oxygen of a small amount of (0.75%) is brought, opened up a kind of photocatalytic method of new structure excited by visible light.Present nonmetalloid nitrogen doped Ti O
2Be considered to develop and have visible light-responded photochemical catalyst one of method preferably.
At present, prepare the titania-doped method of N have various, as: magnetron sputtering method, ion implantation, chemical vapor deposition method, sol-gal process, oxidation TiN method, directly ammoniation process and hydrolysis nitrogen containing metal organic precursor method or the like.The N doped Ti O of these method preparations
2All show visible light catalysis activity to some extent.
Summary of the invention
The object of the present invention is to provide a kind of is the preparation method of the nitrogen-doped titanium dioxide photocatalyst of presoma with the nanotube metatitanic acid.
To achieve these goals, technical program of the present invention lies in adopting a kind of preparation method of nitrogen-doped titanium dioxide photocatalyst, may further comprise the steps:
(1) with the nanotube metatitanic acid be presoma by heat-treating at a certain temperature, prepare a kind of Novel Titanium dioxide;
(2) with prepared Novel Titanium dioxide at NH
3Heat-treat in the air-flow;
(3) then at NH
3Protection under naturally the cooling, can make nitrogen-doped titanium dioxide photocatalyst.
Novel Titanium dioxide in the described step (1) be by the nanotube metatitanic acid in air, heat-treat 0.5-24h under 400-700 ℃ the temperature and prepare.
Novel Titanium dioxide in the described step (1) is at NH
3Before heat-treating in the air-flow, should feed NH in advance
3Clean the air displacement in the pipeline.
Heat treatment temperature in the described step (2) is 400-700 ℃.
Heat treatment time in the described step (2) is 0.5-24h.
Method of the present invention is to be predecessor with nanotube metatitanic acid (NTA), prepare Novel Titanium dioxide through the Overheating Treatment dehydration with special light electrical property, its crystal formation is to contain a large amount of stable lattice defects in anatase structured and the lattice: and constraint single electron oxygen room (single-electron-trapped oxygenvacancy, SETOV) and Ti
3+, because this titanium dioxide character is more active, therefore, by its nitrogen-doped titanium dioxide photocatalyst (N-TiO for preparing
2-1) with commercial general titanium dioxide (P25 type) at identical NH
3The nitrogen doping P25 catalyst (N-TiO that treatment conditions prepare
2-2) compare, its under visible light to air in the elimination specific rate constant of propylene gas of trace improved about 4 times.With the Novel Titanium dioxide with special light electrical property used in the present invention is that presoma also can be used to prepare novel metalloid C, S, F doping titanium dioxide catalyst, and novel nitrogen-doped titanium dioxide of the present invention can be used as the carrier of catalyst and uses.Adopt the prepared N of method of the present invention titania-doped, its crystal formation is anatase structured; Has the visible absorption performance; Has visible light photocatalysis active.The nitrogen-doped titanium dioxide catalyst that method of the present invention prepares is having wide application prospect aspect visible light catalytic material.
Predecessor of the present invention---nanotube metatitanic acid (NTA) is a kind of novel one dimension tubular material, and the nanotube metatitanic acid dehydration takes place after Overheating Treatment changes into TiO
2(anatase), this new Ti O that changes into by NTA
2(anatase) contain in the lattice a large amount of stable constraint single electron oxygen rooms (single-electron-trapped oxygen vacancy, SETOV) and Ti
3+[S.L.Zhang, W.Li, Z.S.Jin, J.J.Yang, J.W.Zhang, Z.L.Du, Z.J.Zhang, Journal of Solid State Chemistry177 (2004) 1365-1371.Q.Y, Li, X.D.Wang, Z.S.Jin, D.GYang, S.L.Zhang, X.Y Guo, J.J.Yang and Z.J.Zhang, J.nanoparticle.rese].Just because of containing stable SETOV and Ti
3+Lattice defect, new Ti O
2(anatase) demonstrate some special photoelectric properties.
Preparation method's technical process of the present invention is simple, easy to operate, and cost is low, has favorable social and economic worth, is easy to apply.
Description of drawings
Fig. 1 is the XRD spectrum of the prepared nitrogen-doped titanium dioxide photocatalyst of the present invention;
Fig. 2 is the DRS spectrum of the prepared nitrogen-doped titanium dioxide photocatalyst of the present invention;
(unstripped gas consists of air+600ppm propylene to the curve of Fig. 3 visible light elimination propylene under identical condition for nitrogen-doped titanium dioxide photocatalyst of the present invention under the different material gas velocity and nitrogen doping P25 catalyst, light source is the 500W xenon lamp, filter through λ 〉=420nm edge filter, light intensity is 1.9mw/cm
2, the coated amount of catalyst is 31mg ± 1mg.With CO in propylene before and after the GC-9A gas chromatograph detection reaction of Tianjin, island and the product
2Concentration);
Fig. 4 is for to eliminate the CO that propylene produced at nitrogen-doped titanium dioxide photocatalyst of the present invention under the different feed gas flow rates and nitrogen doping P25 photochemical catalyst under visible light
2Amount;
Fig. 5 be nitrogen-doped titanium dioxide photocatalyst of the present invention therewith nitrogen doping P25 catalyst to the visible light photocatalysis active test result of methylene blue.
Wherein, it is X ' pert pro type x-ray diffractometer (XRD that X-ray diffraction (XRD) is analyzed used instrument, Holland Philips company), adopt CuK α line excitaton source, λ=0.15418366nm, voltage 40kV, electric current 40mA, sample can be powder and places pressing of sample platform groove or sample dispersion to drip on slide in acetone, dries the back and becomes film, directly detects.
Ultraviolet-visible scattered reflection spectrum (DRS) is measured on day island proper Tianjin U3010 ultraviolet-visible scattered reflection instrument.
Absorbance is measured at the 722 type visible spectrophotometers that the Shanghai precision instrument factory produces.
The specific embodiment
Preparation method of the present invention is as follows:
(1) preparation of nanotube metatitanic acid
3.0g titanium dioxide slowly joined fill in the polytetrafluoroethylcontainer container that 300ml concentration is 40% NaOH solution, place oil bath to be warming up to 118 ℃, add hot reflux 24h, cooling-sedimentation, inclining supernatant, is washed with distilled water to PH=8.0, filter, use the salt acid soak 5 hours of 0.1mol/L then, filtration, washing, drying promptly get presoma nanotube metatitanic acid.
(2) preparation of Novel Titanium dioxide
The nanotube metatitanic acid that 1.5g is prepared is placed in the tube furnace as presoma, at room temperature with the heating rate of 20 ℃/min, temperature programming to 600 ℃, keep 2h, and then naturally cool to room temperature, promptly prepare the Novel Titanium dioxide with special light electrical property, the prepared titanium dioxide of present embodiment turns out to be anatase structured through X-ray diffraction analysis.
(3) preparation of nitrogen-doped titanium dioxide photocatalyst
The preparation-obtained Novel Titanium dioxide powder with special light electrical property of 1.0g is placed in the tube furnace, and feeds NH simultaneously
3Clean displacement in the air in the tube furnace, then at room temperature with the heating rate of 20 ℃/min, temperature programming to 600 ℃ keeps 4h, and then NH
3Naturally cool to room temperature under the protection of air-flow, can prepare a kind of novel nitrogen-doped titanium dioxide photocatalyst with high visible activity.
The XRD spectra of Fig. 1 shows: the crystal formation of the nitrogen-doped titanium dioxide that the present invention is prepared is anatase structured.
Fig. 2 DRS shows: the prepared nitrogen-doped titanium dioxide of the present invention has tangible absorbent properties at visible region.
Application Example 1
Nitrogen-doped titanium dioxide photocatalyst of the present invention is coated on the frosted glass plate, (λ 〉=420nm) airborne micro-propylene gas is eliminated under visible light, the elimination factor of propylene is seen Fig. 3 under different feed gas flow rates, as can be seen from Figure 3 when feed gas flow rates was 100ml/h, the elimination factor of propylene was up to 58%.The elimination factor of propylene is compared obvious raising with the N doping P25 catalyst that the same terms prepares down to the elimination factor of propylene, and specific rate constant is about 5 times of (see figure 3)s of N doping P25 catalyst.When propylene during by complete oxidation, 1mol propylene (C
3H
6) should generate 3molCO
2Fig. 4 is CO
2Growing amount with the variation of feed gas flow rates, thus CO
2Generate selectivity and be respectively 73% (nitrogen-doped titanium dioxide of the present invention) and 43% (N doping P25), propylene (C is described
3H
6) the visible light catalytic oxidation be incomplete, but compare nitrogen-doped titanium dioxide photocatalyst of the present invention to propylene (C with N doping P25 catalyst
3H
6) mineralization ability obviously improve.
Application Example 2
The methylene blue solution of measuring 80mL, concentration and be 10mg/L adds quartz reactor, prepared nitrogen-doped titanium dioxide photocatalyst and the nitrogen doping P25 catalyst of the present invention that adds 80mg more respectively, each ultrasonic dispersion 30min, under dark attitude magnetic agitation, after treating that methylene blue absorption reaches balance, add visible light, topple at regular intervals a certain amount of solution and carry out centrifugation, measure the absorbance that clear liquid is located at 662nm (maximum absorption wavelength of methylene blue).Visible light source is the 500W xenon lamp, and light beam obtains visible light by λ 〉=420nm edge filter again after the pond absorption is infrared, and the light intensity that shines on the reaction vessel is 1.2mw/cm
2Two kinds of catalyst decolour to the photocatalysis of methylene blue and all show higher activity, and specific rate constant is respectively k
1=1.5 * 10
-2(N-TiO
2-1), k
2=1.1 * 10
-2(N-TiO
2-2), the former is 1.4 times of the latter.(see figure 5)
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to the foregoing description, those of ordinary skill in the art is to be understood that: still can make amendment or be equal to replacement the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (5)
1, a kind of preparation method of nitrogen-doped titanium dioxide photocatalyst is characterized in that: may further comprise the steps:
(1) is presoma with the nanotube metatitanic acid,, prepares a kind of Novel Titanium dioxide by heat-treating at a certain temperature;
(2) with prepared Novel Titanium dioxide at NH
3Heat-treat in the air-flow;
(3) then at NH
3Protection under naturally the cooling, can make nitrogen-doped titanium dioxide photocatalyst.
2, the preparation method of nitrogen-doped titanium dioxide photocatalyst according to claim 1, it is characterized in that: the Novel Titanium dioxide in the described step (1) be by the nanotube metatitanic acid in air, heat-treat 0.5-24h under 400-700 ℃ the temperature and prepare.
3, the preparation method of nitrogen-doped titanium dioxide photocatalyst according to claim 1 and 2 is characterized in that: the Novel Titanium dioxide in the described step (1) is at NH
3Before heat-treating in the air-flow, should feed NH in advance
3Clean the air displacement in the pipeline.
4, the preparation method of nitrogen-doped titanium dioxide photocatalyst according to claim 1 is characterized in that: the heat treatment temperature in the described step (2) is 400-700 ℃.
5, the preparation method of nitrogen-doped titanium dioxide photocatalyst according to claim 4 is characterized in that: the heat treatment time in the described step (2) is 0.5-24h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101922037A (en) * | 2010-09-26 | 2010-12-22 | 武汉大学 | Method for preparing nitrogen-doped titanium dioxide nanotube array |
| CN102277609A (en) * | 2011-08-02 | 2011-12-14 | 复旦大学 | Preparation method of carbon-nitrogen co-doped TiO2 nano-tube thin film with visible light activity |
| TWI409100B (en) * | 2010-08-13 | 2013-09-21 | Nat Univ Chung Hsing | Method of visible-light response of n-doped titanium dioxide photocatalyst and its application to removing ethylene |
| CN103521251A (en) * | 2013-10-15 | 2014-01-22 | 杭州电子科技大学 | Method for preparing photocatalyst with nanotube photocell structure |
| CN103614759A (en) * | 2013-11-22 | 2014-03-05 | 西北师范大学 | Preparation method and application of N-doped titanium dioxide nano-composite structure |
| CN103691469A (en) * | 2013-12-20 | 2014-04-02 | 海安县吉程机械有限公司 | Preparation method for nitrogen-doped mesoporous cerium dioxide photocatalyst |
| CN104043470A (en) * | 2014-05-28 | 2014-09-17 | 华中科技大学 | Preparation method of nano titanium dioxide photocatalyst capable of degradation of high-concentration benzene |
| CN104174391A (en) * | 2014-08-21 | 2014-12-03 | 华中科技大学 | Nanometer titania photocatalyst for degrading VOC and preparation method of nanometer titania photocatalyst for degrading VOC |
| CN105170171A (en) * | 2015-08-24 | 2015-12-23 | 哈尔滨工业大学 | Preparation method of rare earth composite boron-nitrogen co-doped titanium dioxide catalyst |
-
2007
- 2007-06-21 CN CNA2007100546449A patent/CN101327425A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI409100B (en) * | 2010-08-13 | 2013-09-21 | Nat Univ Chung Hsing | Method of visible-light response of n-doped titanium dioxide photocatalyst and its application to removing ethylene |
| CN101922037A (en) * | 2010-09-26 | 2010-12-22 | 武汉大学 | Method for preparing nitrogen-doped titanium dioxide nanotube array |
| CN101922037B (en) * | 2010-09-26 | 2012-02-15 | 武汉大学 | Method for preparing nitrogen-doped titanium dioxide nanotube array |
| CN102277609A (en) * | 2011-08-02 | 2011-12-14 | 复旦大学 | Preparation method of carbon-nitrogen co-doped TiO2 nano-tube thin film with visible light activity |
| CN103521251A (en) * | 2013-10-15 | 2014-01-22 | 杭州电子科技大学 | Method for preparing photocatalyst with nanotube photocell structure |
| CN103521251B (en) * | 2013-10-15 | 2015-04-29 | 杭州电子科技大学 | Method for preparing photocatalyst with nanotube photocell structure |
| CN103614759A (en) * | 2013-11-22 | 2014-03-05 | 西北师范大学 | Preparation method and application of N-doped titanium dioxide nano-composite structure |
| CN103691469A (en) * | 2013-12-20 | 2014-04-02 | 海安县吉程机械有限公司 | Preparation method for nitrogen-doped mesoporous cerium dioxide photocatalyst |
| CN104043470A (en) * | 2014-05-28 | 2014-09-17 | 华中科技大学 | Preparation method of nano titanium dioxide photocatalyst capable of degradation of high-concentration benzene |
| CN104043470B (en) * | 2014-05-28 | 2016-04-13 | 华中科技大学 | A kind of preparation method of nano titanium dioxide photocatalyst of energy degrading high concentration benzene |
| CN104174391A (en) * | 2014-08-21 | 2014-12-03 | 华中科技大学 | Nanometer titania photocatalyst for degrading VOC and preparation method of nanometer titania photocatalyst for degrading VOC |
| CN105170171A (en) * | 2015-08-24 | 2015-12-23 | 哈尔滨工业大学 | Preparation method of rare earth composite boron-nitrogen co-doped titanium dioxide catalyst |
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