CN1275686C - TiO2 photocatalyst film with inhomogeneously-doped metal ions on base body and preparation process thereof - Google Patents
TiO2 photocatalyst film with inhomogeneously-doped metal ions on base body and preparation process thereof Download PDFInfo
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- CN1275686C CN1275686C CN 02152041 CN02152041A CN1275686C CN 1275686 C CN1275686 C CN 1275686C CN 02152041 CN02152041 CN 02152041 CN 02152041 A CN02152041 A CN 02152041A CN 1275686 C CN1275686 C CN 1275686C
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Abstract
The present invention relates to a TiO2 photocatalyst film with inhomogeneously-doped metal ions on a base body and a preparation method thereof. The film comprises a SiO2 film of a diaphragming layer; the present invention is characterized in that the TiO2 photocatalyst film also comprises at least a TiO2 photocatalyst film and at least a TiO2 film with doped metal ions, wherein the TiO2 photocatalyst film and the TiO2 film with the doped metal ions are spaced without an order; the nonuniform doping of metal ions is integrally formed; the atomic percentage of metal ions and Ti in the TiO2 film with the doped metal ions is from 0.01 to 5%. The preparation method comprises: a sol-gel method is used for preparing the SiO2 film of the diaphragming layer for 1 to 5 times on the base body; the TiO2 photocatalyst film is prepared for 2 to 20 times; the TiO2 film with the doped metal ions is prepared for 2 to 20 times, wherein the order and the frequency of step (b) and step (c) are determined according to the structure of the film. The photocatalytic activity of the TiO2 photocatalyst film inhomogeneously doped with the metal ions is greatly increased.
Description
Technical field
The present invention relates to metal ion non-uniform doping titanium dioxide optical catalyst film and preparation method thereof on a kind of matrix.
Background technology
TiO
2As a kind of semiconductor light-catalyst, in two more than ten years in the past, obtained extensively and in depth research.Titanium dioxide film photocatalyst has good chemical stability and mechanical strength owing to possessing, in various fields, has application prospects, particularly 1997, Fujshima found the self-cleaning anti-fog function of photocatalyst film, has more caused people's extensive concern.Yet the titanium deoxid film on the carrier still exists the not high problem of photocatalysis efficiency because its specific area is less, and the titanium deoxid film of preparing highlight catalytic active more and more becomes the emphasis of present research.
At present, Chang Yong raising TiO
2The method of catalytic activity is included in semiconductor surface and adds supported noble metal, compound other metal oxide or doped metal ion etc.Chinese invention patent 01109511.3, its publication number is CN1320557A, discloses the pyrogenic titanium dioxide that adopts aerosol to mix, doping component has: zinc oxide, platinum oxide, magnesia and/or aluminium oxide.Chinese invention patent 01113672.3, its publication number is CN1323046A, discloses nanometer magnetic titania material of manganese-zinc ferrite bluk recombination and preparation method thereof.The Chinese invention patent 00101041 of ULVAC Corp's application, its publication number is CN1260232, a kind of method of vacuum magnetic-control sputtering method light-plated catalytic film is provided, Chinese invention patent 98103510.8, its publication number is CN1243029A, a kind of spin-coating method coating semiconductive thin film is disclosed, the Chinese invention patent 96193834.x of Japan Toto Ltd application, its publication number is CN1184498, and sol-gel process, sol method, coating process, the magnetron sputtering method of preparation photocatalysis film is provided.Chinese patent database finds that domestic 15 patents that are detected all relate to photocatalysis film by retrieval, but the mode of all not mentioned employing non-uniform doping metal ion is with the method for the photocatalytic activity of raising titanium dioxide.
The content of invention
The objective of the invention is in order to overcome the not enough or difficult shortcoming of technical sophistication manufacturing of prior art photocatalytic activity, provide metal ion non-uniform doping titanium dioxide optical catalyst film on a kind of matrix to improve the photocatalytic activity of titanium dioxide, another object of the present invention is to provide the preparation method of this metal ion species non-uniform doping titanium dioxide optical catalyst film.
Metal ion non-uniform doping titanium dioxide optical catalyst film comprises barrier layer SiO on a kind of matrix of the present invention
2Thin layer (ground floor) is characterized in that also comprising one deck TiO at least
2Photocatalyst film layer and one deck metal ion mixing TiO at least
2Thin layer, TiO
2Photocatalyst film layer and metal ion mixing TiO
2Thin layer is alternate, successively all can, formed the metal ion non-uniform doping on the whole, metal ion mixing TiO
2Metal ion in the thin layer is that (said here " layer " is meant the identical overlapping again calculation one deck of chemical analysis to 0.01-5% with the atomic percent of Ti, no matter its dipping lifts preparation how many times (every dipping lifts preparation once increases by a substratum) and all calculates one deck, as SiO
2Thin layer, TiO
2Thin layer, metal ion mixing TiO
2Thin layer).
Described metal ion chosen from Fe ion, vanadium ion, cadmium ion, chromium ion, cobalt ions, manganese ion, nickel ion, copper ion, zinc ion, tungsten ion or gold ion a kind of or two kinds.Preferred vanadium ion is or/and iron ion.
Described matrix is selected from glass, stainless steel, pottery or plastics.
The preferred version second layer of metal ion non-uniform doping titanium dioxide optical catalyst film is the TiO that V/Ti=0.1-1.3% mixes vanadium on the described matrix
2Film, the 3rd layer are titanium dioxide optical catalyst film, the 3rd layer of titanium dioxide optical catalyst film of mixing iron for Fe/Ti=1.3-1.8% for titanium dioxide optical catalyst film or the second layer.
Described SiO
2Thin layer thickness is 50-80nm, described TiO
2The photocatalyst film layer thickness is 150nm-500nm, described metal ion mixing TiO
2Thin layer thickness is 150nm-500nm.
The preparation method of metal ion non-uniform doping titanium deoxide catalyst film comprises the following steps: successively on the above-mentioned matrix
(a) on matrix, prepare ground floor SiO with sol-gel process
2The thin-film barrier layer is for 1-5 time thickness 50nm-80nm;
(b) prepare TiO according to membrane structure successively with sol-gel process
2Photocatalyst film or metal ion mixing TiO
2Film is for 2-20 time thickness 150nm-500nm.
Preferred version lifts preparation 1-3 time for dipping in (a) among the described preparation method, (b) middle TiO
2Photocatalyst film or metal ion mixing TiO
2Thin film dipped lifting prepares 3-8 time (every dipping lifts preparation once increases by a substratum).
Concrete embodiment
The following example will further specify the present invention, but the present invention is not construed as limiting.
The titanium deoxid film of embodiment 1 preparation surface doping comprises the following steps: successively
(a) barrier layer SiO
2The preparation of film
The preparation of Ludox: get 100ml absolute ethyl alcohol, 104ml ethyl orthosilicate, 160ml absolute ethyl alcohol 900rpm in the 500ml triangular flask successively and stir 1hr, getting 26ml HCl (2M) slowly is added dropwise in the above triangular flask when evenly stirring, drip off the back and continue to stir 1hr, the dark place is left standstill 24hr and is got Ludox.
Barrier layer SiO
2The preparation of film
(200mm * 34mm * 2mm) soaked two days in concentrated nitric acid solution the simple glass sheet, took out afterwash, soaked about two hours with washing lotion again, cleaned with distilled water, and oven for drying is then promptly finished the preprocessing process of sheet glass.Adopt dip-coating method, pull rate is 2mms
-1, sheet glass is at SiO
2Lift in the colloidal sol once, wet film is put into 500 ℃ of Muffle furnaces behind 100 ℃ baking oven inner drying 5min, is incubated and naturally cools to room temperature after 1 hour.Repeat aforesaid operations once, can obtain SiO
2Film.
(b) preparation TiO
2Photocatalyst film
TiO
2The preparation of colloidal sol: earlier positive four butyl esters of metatitanic acid, diethanol amine, water are mixed with absolute ethyl alcohol, stirred 1 hour, obtain solution (1).Distilled water mixes with remaining ethanol, obtains solution (2).The solution (2) that will move under vigorous stirring again in the separatory funnel slowly is added drop-wise in the solution (1), continues to stir promptly to get TiO 2 sol half an hour.Wherein, Ti (OC
4H
9)
4: EtOH: H
2O: NH (C
2H
5OH)
2=1: 26.5: 1: 1 (mol ratio).
Adopt dip-coating method, pull rate is 2mms
-1, above-mentioned sheet glass flooded in this colloidal sol lifting once, 100 ℃ of baking 10min will lift drying course 4 times repeatedly in electrically heated drying cabinet, place 2 ℃ of min of Muffle furnace
-1Temperature programming to 500 ℃, constant temperature 1hr obtains TiO
2Film.
(c) TiO of preparation doping
2Photocatalyst film
The preparation metal ion carries out the TiO of doping vario-property
2Colloidal sol: earlier positive four butyl esters of metatitanic acid, diethanol amine, water are mixed with absolute ethyl alcohol, stirred 1 hour, obtain solution (1).Distilled water mixes with remaining ethanol, obtains solution (2).The solution (2) that will move under vigorous stirring in the separatory funnel slowly is added drop-wise in the solution (1) again, after waiting to dropwise, adds the metal ion that will mix, and continues to stir promptly to get metal ion doped titanium dioxide colloidal sol half an hour.Wherein, Ti (OC
4H
9)
4: EtOH: H
2O: NH (C
2H
5OH)
2=1: 26.5: 1: 1 (mol ratio).In the present invention, preferred V
5+, adopt metavanadic acid ammonia to mix, wherein V/Ti (atom%) elects 0.1,0.25,0.5,1,1.5 as.And Fe
3+, adopt Fe (NO)
39H
2O mixes, and Fe/Ti (atom%) elects 0.05,0.1,0.25,0.5,1,1.5,2,2.5 as.
Above-mentioned sheet glass is being mixed V
5+Or mix Fe
3+TiO
2Dipping lifts once in the colloidal sol, and 100 ℃ of baking 10min will lift drying course 4 times repeatedly in electrically heated drying cabinet, place 2 ℃ of min of Muffle furnace
-1Temperature programming to 500 ℃, constant temperature 1hr, the TiO that obtains mixing
2Film.
The titanium deoxid film that embodiment mixes 2 preparation bottoms comprises the following steps: successively
(a) barrier layer SiO
2The preparation of film: same with embodiment 1;
(b) TiO of preparation doping
2Photocatalyst film: same with (c) among the embodiment 1;
(c) preparation TiO
2Photocatalyst film: same with (b) among the embodiment 1.
The bulk phase-doped titanium deoxid film of embodiment 3 preparations comprises the following steps: successively
(a) barrier layer SiO
2The preparation of film: same with embodiment 1;
(b) TiO of preparation doping
2Photocatalyst film: same with (c) among the embodiment 1;
(c) TiO of preparation doping
2Photocatalyst film: same with (c) among the embodiment 1.
Embodiment 4 photocatalysis performances
The dominant wavelength that adopts 125W is that the high-pressure sodium lamp (the inferior bright electric light source in Beijing Development Co., Ltd) of 365nm is light source, and the photocatalytic degradation of methyl orange solution is a model reaction.Detailed process is: mix iron TiO
2(35 * 200mm) put into vertically that initial concentration is housed is 10mg/L to the sheet glass of film, and in the teat glass of 400ml methyl orange solution, sheet glass is placed according to wall, and high-pressure sodium lamp is vertically put into test tube central authorities.With air pump bubbling air in the solution.Timing sampling in the light-catalyzed reaction process, the mensuration of methyl orange concentration adopt 752 type ultraviolet grating spectrophotometric determination 446nm place light absorption values, and its absorbance and concentration have good linear relationship.According to first order kinetics relational expression (lnC
0/ C=kt), adopt linear regression analysis can use the apparent speed constant k of methyl orange solution decolouring when respectively organizing catalyst, come the photocatalytic activity of comparison catalyst with this.
The apparent speed constant of table 1 photocatalytic degradation methyl orange and the relation of V/Ti ratio
The apparent speed constant of table 2 photocatalytic degradation methyl orange and the relation of Fe/Ti ratio
The drawing explanation
Fig. 1 is the difference along with doping content, body mix mutually vanadium film, surface mix vanadium film and bottom mix vanadium film degradation methyl orange the changing trend diagram of apparent speed constant.As seen from Figure 1, when V/Ti=0.9-1.0%, the photocatalytic activity that the vanadium film is mixed in the bottom has reached maximum.The surface is mixed the vanadium film and is then constantly reduced with the photocatalytic activity that body is mixed the vanadium film mutually.Wherein the TiO of vanadium is mixed in the bottom
2The maximum photocatalysis apparent speed constant of film is than pure TiO
2The apparent speed constant of film will exceed about 2.3 times.
Fig. 2 is the difference along with doping content, and body is mixed iron thin film and the surperficial changing trend diagram of mixing the apparent speed constant of iron thin film degraded methyl orange mutually.As seen from Figure 2, when Fe/Ti=0.12%, the photocatalytic activity that body is mixed iron thin film has mutually reached maximum.When Fe/Ti=1.5%, the photocatalytic activity that iron thin film is mixed on the surface has also reached maximum.And when Fe/Ti more than or equal to 0.5% the time, the photocatalytic activity that iron thin film is mixed on the surface is mixed the photocatalytic activity of iron thin film mutually apparently higher than body.When Fe/Ti is the photocatalytic activity height of bulk phase-doped film less than 0.5% the time.And the maximum that the surperficial maximum photocatalysis apparent speed constant of mixing iron thin film is mixed iron mutually than body will exceed 1.5 times.
Claims (4)
1. metal ion non-uniform doping titanium dioxide optical catalyst film on the matrix comprises ground floor SiO
2The thin-film barrier layer is characterized in that the second layer is the TiO that V/Ti=0.1-1.3% mixes vanadium
2Film, the 3rd layer for titanium dioxide optical catalyst film or the second layer be titanium dioxide optical catalyst film, the 3rd layer for the titanium dioxide optical catalyst film that Fe/Ti=1.3-1.8% mixes iron, formed the metal ion non-uniform doping on the whole.
2. according to metal ion non-uniform doping titanium dioxide optical catalyst film on a kind of matrix described in the claim 1, it is characterized in that described matrix is selected from glass, stainless steel, pottery or plastics.
3. according to metal ion non-uniform doping titanium dioxide optical catalyst film on a kind of matrix in claim 1 or 2, it is characterized in that SiO
2Thin layer thickness is 50-80nm, TiO
2The photocatalyst film layer thickness is 150nm-500nm, metal ion mixing TiO
2Thin layer thickness is 150nm-500nm.
4. the preparation method of metal ion non-uniform doping titanium dioxide optical catalyst film on the matrix described in the claim 1 is characterized in that comprising the following steps:
(a) on matrix, prepare ground floor SiO with sol-gel processing
2The thin-film barrier layer is for 1-5 time thickness 50nm-80nm;
(b) prepare TiO according to membrane structure successively with sol-gel processing
2Photocatalyst film or metal ion mixing TiO
2Film is for 2-20 time thickness 150nm-500nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02152041 CN1275686C (en) | 2002-11-26 | 2002-11-26 | TiO2 photocatalyst film with inhomogeneously-doped metal ions on base body and preparation process thereof |
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|---|---|---|---|
| CN 02152041 CN1275686C (en) | 2002-11-26 | 2002-11-26 | TiO2 photocatalyst film with inhomogeneously-doped metal ions on base body and preparation process thereof |
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| CN1275686C true CN1275686C (en) | 2006-09-20 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323752C (en) * | 2005-04-30 | 2007-07-04 | 中国地质大学（武汉） | Manufacture of Ag+-Fe+ dosed TiO2 weakly exciting catalytic luminating film |
| EP1965202B1 (en) | 2007-02-27 | 2016-04-13 | Horiba, Ltd. | Glass electrode |
| CN102294234A (en) * | 2011-07-15 | 2011-12-28 | 刘凡新 | Composite titanium dioxide photocatalyst and preparation method thereof |
| CN102407105B (en) * | 2011-10-27 | 2013-03-27 | 济南大学 | Nanometer titanium dioxide modified film and gradient doping modification method of nanometer titanium dioxide film |
| CN102407107B (en) * | 2011-11-10 | 2013-06-19 | 苏州大学 | Metal/TiO2 composite multilayer film photocatalyst and preparation method thereof |
| CN103359955B (en) * | 2012-03-31 | 2016-04-13 | 江南大学 | A kind of preparation method mixing zinc anti-reflection emitting automatic cleaning coating |
| CN103007948A (en) * | 2012-12-18 | 2013-04-03 | 湖北工业大学 | Preparation method of glass loaded copper/chromium ion double doped nano titanium dioxide photocatalysis film |
| CN103638930A (en) * | 2013-11-28 | 2014-03-19 | 陕西科技大学 | Preparation method and application of CO<2+>-doped titanium dioxide self-cleaning film |
| CN104258837B (en) * | 2014-10-21 | 2016-05-04 | 辽宁工业大学 | The preparation method of carbon-silicon coblended nano TiO 2 |
| CN105413690A (en) * | 2015-10-26 | 2016-03-23 | 湖南永清环保研究院有限责任公司 | Catalyst for degrading organic wastewater and preparation method thereof |
| CN108147677A (en) * | 2017-12-06 | 2018-06-12 | 吕莉 | A kind of preparation method of high efficiency photocatalysis glass with clean |
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