CN1557540A - Nitrogen doped titanium oxide mesoporous photocatalysis material and preparation method thereof - Google Patents
Nitrogen doped titanium oxide mesoporous photocatalysis material and preparation method thereof Download PDFInfo
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- CN1557540A CN1557540A CNA2004100163236A CN200410016323A CN1557540A CN 1557540 A CN1557540 A CN 1557540A CN A2004100163236 A CNA2004100163236 A CN A2004100163236A CN 200410016323 A CN200410016323 A CN 200410016323A CN 1557540 A CN1557540 A CN 1557540A
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Abstract
The present invention prepares nitrogen-doped mesoporous titania photocatalyst material with titanium alkoxide and thiourea as material to synthesize Ti-base precursor and through decomposing the precursor in furnace with ammonia atmosphere at 450-550 deg.c for 6-8 hr. The formation of nano titania crystal grain and the doping with nitrogen element are completed simultaneously, and N atom replaces O atom in TiO2 lattice effectively to form the doping energy level. The prepared material has titania as base, c anatase rystal phase, nitrogen content of 1.6-7.6 wt%, and mesopore size of 1-8 nm. The nitrogen-doped mesoporous titania photocatalyst has UV-vis absorption spectrum beginning at 735 nm, is used as photocatalyst and can degrade 90 % of methylthionine chloride in 4 hr.
Description
Technical field
The present invention relates to a kind of nitrogen adulterated TiOx mesoporous photocatalytic material and preparation method thereof, belong to field of fine chemical.
Background technology
Titanium oxide is commonly called as titanium white, is purposes functional material very widely, is used for building materials (coating), chemical industry (catalysis), the energy (solar cell, photolysis water hydrogen gas), environmental protection important industrial technology applications such as (mineralisings of pollutant) in a large number.The basis that this type of material is used is the character of their uniquenesses, as the material spectrum characteristic, can be with characteristic, surface state etc.
Titanium oxide has good active as the photochemical catalyst of ultraviolet excitation, has very high activity at aspects such as the mineralising of pollutant and hydrogen production by water decomposition gas, but ultraviolet light only accounts for 2～3% of sunshine spectrum, therefore, the photocatalysis performance of titanium oxide has run into very big obstacle in actual applications.Can change its surface characteristic by titanium oxide is mixed or sensitization etc., its absorption spectrum be expanded to visible region, and had visible light catalysis activity.Though metal-doped its absorption spectra that can make expands to visible region, the heat endurance of material is reduced, and the position of mixing become new carrier complex centre easily, so metal-doped effect is unsatisfactory.Present doping method to titanium oxide concentrates on anion doped, and its method has multiple.As TiO
2Target sputtering method (R.Asahi et al., science, 2001, vol.293, p2695-271), titanium sheet firing method (S.U.M.Khan et al., science, 2002, vol.297, p2243-2245), mechanochemistry (high-energy ball milling) method (J.Wang et al., J.Mater.Chem., 2003, vol.13, p2348-2352), ion implantation (M.Anpo et al., J.Catal.2003, vol.216, p505-516) etc.But these methods all come with some shortcomings.TiO
2The target sputter easily causes the titanium oxide lattice deformation, and the ratio of anatase and rutile mixed crystal is wayward; Ion implantation needs expensive ion implantation device etc.; Moreover present subject matter is which type of doping is the most effective, can improve the utilization ratio of sunshine and have high visible light catalysis activity.
Summary of the invention
The purpose of this invention is to provide a kind of nitrogen adulterated TiOx mesoporous photocatalytic material and preparation method thereof.
The present invention is a raw material with the alkoxide (comprising its various alkoxide etc.) and the sulphur urine of titanium, and the self-control organic compound is a presoma, is atmosphere with the ammonia, makes presoma decomposition reaction under suitable temperature, and its reaction condition is:
The ratio of the mole of titanium alkoxide and sulphur urine is 0.25～0.3: 1;
The mixture mixing time is 2～4 hours;
The predecessor bake out temperature is 60～80 ℃;
NH
3Gas velocity is 0.5～5 liter/minute;
NH
3Reaction temperature is 450～550 ℃ in the air-flow;
NH
3The reaction time is 6～8 hours in the air-flow.
Concrete technology as shown in Figure 1.Concrete steps are:
A. under the room temperature titanium alkoxide and sulphur are urinated with mol ratio 0.25～0.3: 1 ratio is mixed stirring 2～4 hours in ethanol.Evaporate ethanol then and obtain white predecessor powder.
B. the gained predecessor is 60～80 ℃ of oven dry down.
C. predecessor 450～550 ℃ of rufous materials of obtaining in 6～8 hours of reaction in the ammonia flow of 0.5～5 liter/minute of flow velocity are the titania meterial that nitrogen mixes.
D. adopt above prescription and reaction condition, through above-mentioned processing step, just can prepare the titania meterial of anatase phase, crystalline phase is single, and the absorption spectrum expansion is wide, has high visible light catalysis activity.
The material of preparation gained is used XRD respectively, XPS, and nitrogen adsorption desorption curve, UV-vis absorb its structure and spectrum property are characterized, and the result invests Fig. 2～Fig. 5, and the XRD figure spectrum of Fig. 2 shows that prepared material is single anatase phase.Elementary analysis shows that the prepared material of this method contains 1.6～7.6% nitrogen elements, and the material mesopore orbit is of a size of 1～8nm.
TiO with prepared material and Degussa company
2(trade names P-25, anatase is compared 4: 1 with rutile, specific area 55m mutually
2/ g) direct nitrogen treatment products therefrom is used separately as photochemical catalyst is measured its degraded methylene blue dyestuff under radiation of visible light photocatalytic activity in ammonia flow.The result shows: this nitrating titanium oxide powder demonstrates good photocatalytic activity, and result of experiment as shown in Figure 6.
Characteristics of the present invention are:
1) this method makes nitrogen effectively replace the oxygen in the titanium oxide lattice easily and forms the titanium oxide that nitrogen mixes.
2) the prepared nitrating titanium oxide of this method has tangible meso-hole structure, and the duct is of a size of about 1～8nm, and specific area can reach 217m
2/ g.
The UV-vis absorption spectrum of the nitrating titanium oxide powder that 3) this method obtained just begins to absorb from 735nm, has improved the utilization ratio of sunshine greatly.
4) the prepared powder of this method has high photocatalytic activity in the experiment of the radiation of visible light degraded methylene blue of the above wave band of 400nm.
5) preparation technology of this method and equipment are simple, only relate to an atmosphere furnace, and great industrial production prospects is arranged.
Description of drawings
Fig. 1 process chart;
The XRD figure spectrum of Fig. 2 material is shown as single anatase phase;
Fig. 3 nitrogen adsorption/desorption curve map and corresponding graph of pore diameter distribution show that this material possesses typical meso-hole structure;
Fig. 4 UV-vis absorption spectrum just begins to absorb from 735nm;
Fig. 5 XPS collection of illustrative plates is obviously observed the existence at Ti-N key peak;
Fig. 6 visible light catalytic effect contrast figure (a) embodiment 1, (b) Comparative Examples, the sample of Ti Base Metal organic compound decomposition method nitrating shows good catalytic activity.
The specific embodiment
Further specify embodiment and effect with following non-limiting embodiment:
Comparative Examples
The TiO of Degussa company
2(trade names P-25, anatase is compared 4: 1 with rutile, specific area 55m to powder mutually
2/ g) in ammonia flow 550 ℃ handled 3 hours, the gained powder is as a comparison case.
Embodiment 1
34.0g urinating to mix in alcohol solvent with 30.4g sulphur, stirred 2 hours butyl titanate, ethanol is removed in evaporation then, obtain white predecessor powder 80 ℃ of dryings, then in ammonia flow 450 ℃ handled 6 hours, obtain being the titanium oxide powder that N mixes after the rufous material grinds.The particle diameter of powder is 10～40nm.The 300W high-pressure sodium lamp that filters for 400nm glass with the cutoff wavelength is done light source, and the 0.3g photochemical catalyst is suspended in the aqueous solution of methylene blue of 400 milliliter of 50 mg/litre, tests its photocatalysis performance.Fig. 2 is its XRD figure spectrum, is shown as the titanium oxide of anatase phase.Fig. 3 is nitrogen adsorption/desorption curve map and corresponding graph of pore diameter distribution, shows that average duct is of a size of 4.2nm, and specific surface reaches 217m
2/ g.Elementary analysis shows that this sample contains 2.2% nitrogen element.Fig. 4 is the UV-vis absorption spectra, and wherein (c) curve shows that its absorption expands to visible light and partly reaches 735nm, (b) is TiO
2Directly the doping of handling in ammonia flow (a) is P-25.Fig. 5 is a N 1s XPS spectrum, shows that N replaces the oxygen of titanium oxide lattice position effectively and forms doped energy-band, thereby makes titanium oxide have visible light catalysis activity.Fig. 6 is that the effect of its degraded methylene blue under the light source irradiation that filters for 400nm glass with the cutoff wavelength compares, and the sample of Ti Base Metal organic compound decomposition method nitrating shows good catalytic activity.Through 4 hours, the prepared photochemical catalyst of this method made 90% methylene blue degraded, and Comparative Examples has only 35% degraded.
Embodiment 2
Presoma 500 ℃ of processing in ammonia flow made nitrating anatase titanium oxide powder in 3 hours.Other experimental procedures are with embodiment 1.Elementary analysis shows that this sample contains 7.6% nitrogen element.Prepared photochemical catalyst makes 89% methylene blue degraded through 4 hours radiation of visible light.
Embodiment 3
Presoma 550 ℃ of processing in ammonia flow made nitrating anatase titanium oxide powder in 3 hours.Other experimental procedures are with embodiment 1.Elementary analysis shows that this sample contains 1.6% nitrogen element.Prepared photochemical catalyst makes 85% methylene blue degraded through 4 hours radiation of visible light.
Claims (6)
1, a kind of nitrogen adulterated TiOx mesoporous photocatalytic material is characterized in that with the titanium oxide being matrix, and crystalline phase is the anatase phase, and is nitrogenous 1.6～7.6%, and mesopore orbit is of a size of 1～8nm.
2, a kind of nitrogen adulterated TiOx mesoporous photocatalytic preparation methods is characterized in that comprising the steps:
(1) is raw material with titanium alkoxide and sulphur urine, makes presoma after in ethanol, mixing, stir, drying;
(2) be atmosphere with the ammonia, presoma is reacted under this atmosphere, make the titania meterial that nitrogen mixes.
3,, it is characterized in that the ratio of the mole of described titanium alkoxide and sulphur urine is 0.25～0.3: 1 by the described a kind of nitrogen adulterated TiOx mesoporous photocatalytic preparation methods of claim 2.
4, by the described a kind of nitrogen adulterated TiOx mesoporous photocatalytic preparation methods of claim 2, it is characterized in that described bake out temperature is 60～80 ℃.
5, by claim 2 or 3 or 4 described a kind of nitrogen adulterated TiOx mesoporous photocatalytic preparation methods, it is characterized in that used titanium alkoxide is a butyl titanate.
6, by claim 2 or 3 or 4 described a kind of nitrogen adulterated TiOx mesoporous photocatalytic preparation methods, it is characterized in that described NH
3Gas velocity is 0.5～5 liter/minute, NH
3Reaction temperature is 450～550 ℃ in the air-flow, NH
3The reaction time is 6～8 hours in the air-flow.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890358A (en) * | 2010-06-23 | 2010-11-24 | 南京大学 | Leafing type N-TiO2/cenosphere photocatalyst, preparation method thereof and use thereof |
| CN102078806A (en) * | 2011-01-06 | 2011-06-01 | 华东师范大学 | Method for preparing doped mesoporous titanium photocatalyst |
| CN102327779A (en) * | 2011-07-04 | 2012-01-25 | 山东轻工业学院 | Preparation method and application of nitrogen-doped titanium dioxide heterojunction structure |
| CN103861631A (en) * | 2014-03-12 | 2014-06-18 | 北京理工大学 | Preparation method of nitrogen-doped titanium dioxide nanoribbon visible light photocatalyst |
| CN105002599A (en) * | 2015-06-30 | 2015-10-28 | 宁波工程学院 | Preparation method of high-purity N-doped TiO2 mesoporous nanofiber |
| 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 |
| CN105478151A (en) * | 2014-09-15 | 2016-04-13 | 中国科学院大连化学物理研究所 | Crystal phase controllable nitrogen-doped titanium dioxide preparation method |
| CN107723678A (en) * | 2017-10-09 | 2018-02-23 | 复旦大学 | A kind of method that high pressure ammonia passivation improves titanium oxide photochemical catalyst efficiency |
-
2004
- 2004-02-13 CN CN 200410016323 patent/CN1274410C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890358A (en) * | 2010-06-23 | 2010-11-24 | 南京大学 | Leafing type N-TiO2/cenosphere photocatalyst, preparation method thereof and use thereof |
| CN102078806A (en) * | 2011-01-06 | 2011-06-01 | 华东师范大学 | Method for preparing doped mesoporous titanium photocatalyst |
| CN102327779A (en) * | 2011-07-04 | 2012-01-25 | 山东轻工业学院 | Preparation method and application of nitrogen-doped titanium dioxide heterojunction structure |
| CN102327779B (en) * | 2011-07-04 | 2013-01-02 | 山东轻工业学院 | Preparation method and application of nitrogen-doped titanium dioxide heterojunction structure |
| CN103861631A (en) * | 2014-03-12 | 2014-06-18 | 北京理工大学 | Preparation method of nitrogen-doped titanium dioxide nanoribbon visible light photocatalyst |
| CN105478151A (en) * | 2014-09-15 | 2016-04-13 | 中国科学院大连化学物理研究所 | Crystal phase controllable nitrogen-doped titanium dioxide preparation method |
| CN105478151B (en) * | 2014-09-15 | 2018-12-07 | 中国科学院大连化学物理研究所 | A kind of preparation method for the nitrogen-doped titanium dioxide that crystal phase is controllable |
| CN105002599A (en) * | 2015-06-30 | 2015-10-28 | 宁波工程学院 | Preparation method of high-purity N-doped TiO2 mesoporous nanofiber |
| CN105002599B (en) * | 2015-06-30 | 2018-05-22 | 宁波工程学院 | High purity N adulterates the preparation method of the full meso-porous nano fibers of TiO2 |
| 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 |
| CN107723678A (en) * | 2017-10-09 | 2018-02-23 | 复旦大学 | A kind of method that high pressure ammonia passivation improves titanium oxide photochemical catalyst efficiency |
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|---|---|
| CN1274410C (en) | 2006-09-13 |
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