CN1116927C - Process for preparing visual light reaction type nm TiO2-base optical catalyst - Google Patents
Process for preparing visual light reaction type nm TiO2-base optical catalyst Download PDFInfo
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- CN1116927C CN1116927C CN 01113065 CN01113065A CN1116927C CN 1116927 C CN1116927 C CN 1116927C CN 01113065 CN01113065 CN 01113065 CN 01113065 A CN01113065 A CN 01113065A CN 1116927 C CN1116927 C CN 1116927C
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Abstract
The present invention relates to a method for preparing a visual light reaction type nm TiO2-base photocatalyst. The photocatalyst is a catalyst capable of decomposing indoor harmful gas, air pollution gas and organic pollutants in water under the irradiation of visible light. An improved cosolvent doping method and high temperature calcination are adopted for preparing the visual light reaction type nm TiO2-base photocatalyst doped with metal. The core of the preparation is to add a proper quantity of polyethylene glycol which is stirred evenly for preventing preparation time from being shortened due to the growth of particles in a drying process. The crystalline particles have average size of approximate 10 nm to 20 nm, strong photocatalysis activity and comparatively strong light absorption and photoresponse within a whole wavelength range of the visible light of 400 nm to 700 nm. The present invention has the advantages of high energy transformation efficiency, low production cost and short period; the present invention greatly reduces equipment investment and operation cost and establishes a scientific basis for large-scale industrialized popularization and application.
Description
Technical field
The present invention relates to a kind of photochemical catalyst, particularly a kind of preparation method of metal-doped visual light reaction type nm TiO 2-base optical catalyst.
Background technology
Under the ultraviolet ray irradiation, titanium dioxide (TiO
2But) organic pollution in photochemical catalyst catalytic decomposition indoor harmful gas, atmosphere pollution gas and the water, but this titanium dioxide optical catalyst can only be by wavelength less than 400nm (～387.5nm) ultraviolet ray excited, and this part ultraviolet light only accounts for 4～6% in the solar radiation total amount that arrives ground, and change in time obviously, as artificial ultraviolet light sources such as applying high voltage mercury lamps, energy consumption is too big.If can be with TiO
2The spectrum of photochemical catalyst utilizes range expansion to arrive visible region, then can make full use of solar source, if with excitation wavelength from the 387.5nm red shift to～443nm, then the sunshine utilization rate can be increased to tens percent by a few percent, can reduce equipment investment and operating cost significantly, apply for large-scale industrialization and lay scientific basic.On the other hand, since nano material exclusive quantum size effect and skin effect, nano titanium dioxide photocatalyst has higher photocatalysis efficiency than conventional titanium dioxide optical catalyst, therefore, can be by the titanium dioxide optical catalyst of the crystallite dimension of excited by visible light in nanometer scale, to be a kind of desirable photochemical catalyst, also be the problem that is worth research.
At present relevant document proposes to adopt the semiconductor surface modification technology to utilize scope to expand to visible region the spectrum of titanium dioxide optical catalyst, for example: (1) semiconductor surface noble metal loading, adopt deposition process such as immersion reduction method and photoreduction met hod, can improve photocatalytic activity, and make the absorbing wavelength expanded range of photochemical catalyst; (2) semi-conductive metal ion mixing adopts dipping back high-temperature roasting, light assistant depositing, is total to solute doping method etc., not only can strengthen semi-conductive photocatalysis, also may make semi-conductive absorbing wavelength range expansion to the visible region; (3) semi-conductive photoactivate, with Photoactive compounds with physics and chemisorbed in semiconductor surface.Photosensitizers such as the phthalein mountain valley with clumps of trees and bamboo, Porphyrins have bigger motivating factor under visible light, might make its excitation electron inject (conveying) to semi-conductive conduction band, thereby enlarge the semiconductor excitation wavelength range, make its reaction wavelength extend to the visible region; (4) composite semiconductor is prepared binary and polynary composite semiconductor with infusion process and mixed sols method, and its photocatalysis property is higher than single semiconductor ... or the like.But above-mentioned report not mentioned all the time in whole visible wavelength range 400～700nm light absorption and the effect of photoresponse.The Chinese patent literature application number is that " photochemical catalyst and utilization thereof with visible light activity " disclosed technology of 97181439.2 is by in plasma, gaseous mixture with methane and hydrogen carries out CVD processing acquisition to titanium dioxide, provide the photochemical catalyst that can utilize visible light, but can its prepared photochemical catalyst there be all the effect of visible light activity not to be reported in whole visible wavelength range 400～700nm.
Summary of the invention
The object of the present invention is to provide a kind of preparation method that the visual light reaction type nm TiO 2-base optical catalyst of stronger light absorption and photoresponse is all arranged in whole visible wavelength range 400～700nm.
According to the foregoing invention purpose, preparation method of the present invention: the preparation method of visual light reaction type nm TiO 2-base optical catalyst is characterized in that:
A. the pure salt with titanium adds in the solvent alcohols by 1～2: 1 (volume ratio), adds a certain amount of acid again and stirs;
The soluble-salt of metallic element copper that b. will be to be mixed or iron or vanadium or nickel or strontium or cadmium dissolves in the deionized water by 1: 50～400 (weight ratios);
C. press doping ratio in stirring, according to the doping ratio 1～2% of metallic element to titanium dioxide, the b that gets respective numbers adds among a, obtains oolemma look solution, adds an amount of polyethylene glycol again and stirs;
D. moisture is removed in above-mentioned mixed solution heating and obtained the solid drying thing;
E. dry thing is calcined in 500～600 ℃ of air atmosphere and promptly obtained metal-doped visual light reaction type nm TiO 2-base optical catalyst in 2～4 hours.
The present invention is owing to adding an amount of polyethylene glycol in preparation process and stirring, it is a kind of modified solute doping method altogether, prevented in the dry run that particle grows up and whole preparation time is shortened greatly, the average grain size of photochemical catalyst is about 10～20nm, has very strong photocatalytic activity, in whole visible wavelength range 400～700nm, stronger light absorption and photoresponse are arranged all, can make full use of visible light sources such as sunshine and indoor incandescent lamp, its energy conversion efficiency improves greatly, low cost of manufacture, cycle is short, can reduce equipment investment and operating cost significantly, applies for large-scale industrialization and lays scientific basic.
Description of drawings
Accompanying drawing 1 is the ultraviolet-visible absorption spectroscopy contrast schematic diagram of doping 1% bronze medal and the nano titanium dioxide photocatalyst that undopes.
The specific embodiment
As can be seen from Figure 1, in whole visible wavelength range 400～700nm, the absorbance A of 1% bronze medal that mixes is much higher than plain, improves 4～6 times than unadulterated nano titanium dioxide photocatalyst.
Below will further understand preparation method of the present invention by embodiment.
Embodiment 1:
A. with the 10mL tetra-n-butyl titanate, add in the 10mL ethanol, add a certain amount of concentrated hydrochloric acid again and stir about 5min till evenly;
B. with 50mg copper chloride (CuCl
2) dissolve in the 20mL deionized water;
C. b is added among a in stirring by doping ratio, stir and take 5min, obtain the oolemma green solution, add an amount of polyethylene glycol again and stir;
D. the direct heating evaporation of above-mentioned mixed solution is removed moisture and obtain the solid drying thing;
E. dry thing is calcined the visual light reaction type nm TiO 2-base optical catalyst of 1% metallic copper that promptly obtained in 2 hours mixing in 550 ℃ of air atmosphere.
Embodiment 2:
A. with the 10mL tetra-n-butyl titanate, add in the 10mL ethanol, add a certain amount of concentrated hydrochloric acid again and stir about 5min till evenly;
B. with 119.1mg iron chloride (Fecl
3) dissolve in the 20mL deionized water;
C. b is added among a in stirring by doping ratio, stir and take 5min, obtain the oolemma yellow solution, add an amount of polyethylene glycol again and stir;
D. the direct heating evaporation of above-mentioned mixed solution is removed moisture and obtain the solid drying thing;
E. dry thing is calcined the visual light reaction type nm TiO 2-base optical catalyst of 1.5% metallic iron that promptly obtained in 2～4 hours mixing in 550 ℃ of air atmosphere.
Embodiment 3:
A. with the 100L tetra-n-butyl titanate, add in the 50L ethanol, add a certain amount of concentrated hydrochloric acid again and stir about 5min till evenly;
B. with 1kg copper chloride (CuCl
2) dissolve in the 50L deionized water;
C. b is added among a in stirring by doping ratio, stir and take 15min, obtain the oolemma green solution, add an amount of polyethylene glycol again and stir;
D. with above-mentioned mixed solution spray drying process drying;
E. with dry thing in 550 ℃ of air atmosphere in pushed bat kiln calcining promptly obtained in 4 hours the mixing visual light reaction type nm TiO 2-base optical catalyst of 2% metallic copper.
Claims (6)
1. the preparation method of a visual light reaction type nm TiO 2-base optical catalyst is characterized in that:
A. the pure salt with titanium adds in the solvent alcohols by 1～2: 1 (volume ratio), adds a certain amount of acid again and stirs;
The soluble-salt of metallic element copper that b. will be to be mixed or iron or vanadium or nickel or strontium or cadmium dissolves in the deionized water by 1: 50～400 (weight ratios);
C. press doping ratio in stirring, according to the doping ratio 1～2% of metallic element to titanium dioxide, the b that gets respective numbers adds among a, obtains oolemma look solution, adds an amount of polyethylene glycol again and stirs;
D. moisture is removed in above-mentioned mixed solution heating and obtained the solid drying thing;
E. dry thing is calcined in 500～600 ℃ of air atmosphere and promptly obtained metal-doped visual light reaction type nm TiO 2-base optical catalyst in 2～4 hours.
2. the preparation method of visual light reaction type nm TiO 2-base optical catalyst according to claim 1 is characterized in that the pure salt of described titanium includes metatitanic acid four positive fourth fat, metatitanic acid second fat, metatitanic acid isopropyl ester.
3. the preparation method of visual light reaction type nm TiO 2-base optical catalyst according to claim 1 is characterized in that described solvent alcohols includes ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol.
4. the preparation method of visual light reaction type nm TiO 2-base optical catalyst according to claim 1 is characterized in that described acid includes hydrochloric acid, acetic acid, nitric acid, sulfuric acid.
5. the preparation method of visual light reaction type nm TiO 2-base optical catalyst according to claim 1 is characterized in that described soluble-salt includes villaumite, acetate, nitrate, sulfate.
6. the preparation method of visual light reaction type nm TiO 2-base optical catalyst according to claim 1 is characterized in that described mixed solution heats anhydrate branch directly heating evaporation or spray drying process.
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| CN 01113065 CN1116927C (en) | 2001-05-31 | 2001-05-31 | Process for preparing visual light reaction type nm TiO2-base optical catalyst |
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| CN 01113065 CN1116927C (en) | 2001-05-31 | 2001-05-31 | Process for preparing visual light reaction type nm TiO2-base optical catalyst |
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| CN1116927C true CN1116927C (en) | 2003-08-06 |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7175911B2 (en) * | 2002-09-18 | 2007-02-13 | Toshiba Ceramics Co., Ltd. | Titanium dioxide fine particles and method for producing the same, and method for producing visible light activatable photocatalyst |
| WO2005014170A1 (en) * | 2003-08-08 | 2005-02-17 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Photocatalyst material being activated by visible light, raw material for the same and method for producing the same |
| CN100475335C (en) * | 2003-09-22 | 2009-04-08 | 中国科学院化学研究所 | Photocatalyst responding to visible light, and preparation method and application thereof |
| CN1327953C (en) * | 2004-08-30 | 2007-07-25 | 中国科学院上海硅酸盐研究所 | Photocatalyst of nano titanium oxide modifed by cadmium selenide and preparation method |
| CN100346874C (en) * | 2005-03-17 | 2007-11-07 | 华中科技大学 | Compound photocatalyst using titanium dioxide as its base, and its prepn. method |
| CN101347732B (en) * | 2008-09-04 | 2010-06-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for preparing porous iron-doped titanic oxide photocatalyst |
| CN101774635A (en) * | 2010-03-15 | 2010-07-14 | 彩虹集团公司 | Method for preparing titanium dioxide microballoon sphere modified with noble metals |
| CN102631949B (en) * | 2011-02-12 | 2013-08-14 | 首都师范大学 | Modified visible-light responsive titania doped photocatalyst and production method and uses thereof |
| CN102974355B (en) * | 2012-12-11 | 2014-06-25 | 常州大学 | Loaded nano TiO2 photocatalyst turntable |
| US11446640B2 (en) | 2015-03-23 | 2022-09-20 | Shin-Etsu Chemical Co., Ltd. | Visible-light-responsive photocatalytic-titanium- oxide-particulate dispersion liquid, manufacturing method therefor, and member having thin photocatalytic film on surface thereof |
| CN105195124B (en) * | 2015-10-10 | 2017-06-16 | 中国科学院水生生物研究所 | A kind of preparation method and application of the photochemical catalyst for removing hardly degraded organic substance |
| CN105562039B (en) * | 2016-01-31 | 2018-09-25 | 苏州大学 | A kind of telluric acid titanium photochemical catalyst, preparation method and applications |
| CN109420499A (en) * | 2017-09-05 | 2019-03-05 | 张家港市沐和新材料技术开发有限公司 | A kind of preparation method of copper oxide-nano titania catalysis material |
| CN109577095B (en) * | 2018-11-29 | 2021-04-02 | 河北宇达防锈科技有限公司 | Gas phase antirust paper suitable for high-humidity environment and preparation method thereof |
| CN111925033B (en) * | 2020-08-12 | 2023-04-07 | 四川鸿鹏新材料有限公司 | Treatment process of morpholine-containing wastewater |
| CN112094577A (en) * | 2020-09-01 | 2020-12-18 | 姜跃跃 | Fuel vehicle tail gas adsorption degradation coating and preparation method and application thereof |
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