CN1285405C - Photocatalyst of zinc oxide possessing visible light activity and preparation method - Google Patents
Photocatalyst of zinc oxide possessing visible light activity and preparation method Download PDFInfo
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- CN1285405C CN1285405C CN 200410077519 CN200410077519A CN1285405C CN 1285405 C CN1285405 C CN 1285405C CN 200410077519 CN200410077519 CN 200410077519 CN 200410077519 A CN200410077519 A CN 200410077519A CN 1285405 C CN1285405 C CN 1285405C
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Abstract
The present invention provides a preparation method of a zinc oxide photocatalyst with visible light activity. For preparing zinc oxide of the present invention, the method comprises the following steps: zinci acetas dihydricus and polyvinylpyrrolidone are respectively dissolved in glycol, and then mixed and stirred evenly; afterwards, the mixture is heated for the elevation of temperature and backflow so as to prepare the zinc oxide of the present invention. The degradation rate of the zinc oxide photocatalyst prepared by the present invention to methyl orange in water under visible light is two times higher than that of the existing titanium dioxide in markets. The present invention adopts the common zinc acetate as a raw material to prepare the zinc oxide without decoration with noble metal, etc.; thus, the present invention has the characteristics of easy and cheap implementation and highly activity to the oxidative degradation of organic matters.
Description
Technical field
The present invention relates to chemical field, specifically is a kind of photocatalyst of zinc oxide with visible light activity and preparation method thereof.
Background technology
Since the professor Fujishima of Tokyo Univ Japan in 1972 and Honda find TiO
2The monocrystalline electrode is since not only but decomposition water can also decompose other material under the effect of light, and light-catalyzed reaction is obtaining common attention aspect environmental improvement and the energy development, about the research and development of catalysis material, becomes at present the focus of research both at home and abroad.But now most photocatalysis efficiency of report is low, and greater band gap can only be in ultra-violet (UV) band display light chemism, however at solar spectrum medium ultraviolet light (below the 400nm) less than 5%, and wavelength to be the visible light of 400～750nm account for 43%.If photochemical catalyst can not utilize visible light, then just lost attraction as the photocatalytic hydrogen production by water decomposition that solves energy problem; With regard to the depollution of environment, owing to need UV-irradiation, its indoor application will be restricted.Therefore, in order to effectively utilize sunshine, research has the catalysis material of high efficiency photocatalysis activity under visible light very meaningful, and seeking cheapness, environmental friendliness and have high performance visible-light photocatalysis material will be the inexorable trend that practicability is further moved towards in the photocatalysis development.At present, the research of visible-light photocatalysis material is domestic just the symptom of a trend, but development in external nearly 3 years is very fast, is just becoming the focus of the research of photocatalysis in the future, mainly contains following four general orientation:
One: TiO
2The dye photoactivation of photochemical catalyst, sensibilization requires TiO
2Dyestuff is adsorbed, and still, they are difficult to be applied in the photocatalytic degradation reaction, and this is because they itself also can be degraded and photochemical catalyst is lost activity.
Its two: TiO
2Compound and the modification of mixing of photochemical catalyst is as adopting metal ion implantation, RF magnetron sputtering method new technology to TiO
2Carry out Electronic Performance and modify, can improve TiO
2Visible absorption and visible light photocatalysis performance.Asahi reported a kind of at the visible light (TiO that has highlight catalytic active and Superhydrophilic under the wavelength＜500nm)
2-XN
XPowder and film photocatalyst (Science, 2001,293:269-271).
Its three: ZnO photochemical catalyst system, α-Fe
2O
3, WO
3Can strengthen the photocatalysis performance of ZnO with CdS in the lip-deep deposition of ZnO, and its absorption region is moved to visible light, thereby strengthen visible light photocatalysis active.Relevant is that the research of the visible-light photocatalyst system of basic substance is not a lot of with ZnO, and concluding its report has: MO
X-ZnO compound (M=Fe, W, V, Cr, transition metal such as Cd), nitrogenous zinc oxide, metal ion mixing zinc oxide system, wherein the research of nitrogenous composite semiconductor quite has prospect.
Its four: novel photocatalysis agent system, this class catalyst is used for the photocatalysis Decomposition of water mostly.First series is pyrochlore crystal form B i
2MNbO
7(M=Al, Ga, In and Y, rare earth, Fe), it is cubic system and Fd3m space cohort (space group Fd3m).Second series is ferro tantalum acid antimony crystal form B iMO
4(M=Nb
5+, Ta
5+), when M=Ta, be anorthic system and PI space cohort, when M=Nb rhombic system and Pnna space cohort.The 3rd series is wolframite crystal formation InMO
4(M=Nb
5+, Ta
5+), it is monoclinic system and P2/a space cohort.Though these photochemical catalysts obviously have different crystal structures, they contain identical octahedra TaO
6(or) NbO
6Crystal.
In the disclosed known technology, " a kind of preparation method of the catalysis material to the visible light sensitivity " disclosed among the Chinese patent CN1507943A, it is characterized in that adopting hydrated titanium dioxide is raw material, mixed gas with ammonia and argon gas in high temperature reaction stove reacts, a kind of nitrating photocatalysis material of titanium dioxide that contains can be got, a kind of catalysis material can be obtained the visible light sensitivity." a kind of visible light photo catalyzed photo catalyst pigment and manufacture method thereof " disclosed among the Chinese patent CN1478826A, it is by to technical process such as inorganic pigment preliminary treatment, coating, immersion, drying, calcining, pulverizing and post processings, is that 0.2～0.3 micron inorganic pigment surface cladding titanium dioxide nano particle is made at particle diameter." photo-catalyst pesticide and method for making and purposes with visible light activity " disclosed among the Chinese patent CN1358440A, its preparation method be with modifying titanium dioxide suspension or modifying titanium dioxide colloidal sol high degree of dispersion on the nanometer titanium dioxide silicon substrate, synthetic uniform titanium-silicon composite particles, formation has the cancellated suspension of Ti-O-Si.Disclose " nitrogenous optically catalytic TiO 2 film and preparation method thereof " among the Chinese patent CN1454710A, it is characterized in that, it contains the nitrogen element, and the mass percent of nitrogen element in described film is 0.1%～5%; The preparation method of this film is to adopt magnetically controlled sputter method.Disclose " a kind of method for preparing the Photocatalytic Activity for Degradation plastics " among the Chinese patent CN1405214A, this method is with TiO
2/ organic dyestuff mixes with plastics and is dissolved in the oxolane, then this solution is dripped equably on polyfluortetraethylene plate, takes off behind the natural air drying, makes the plastics of Photocatalytic Activity for Degradation.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with Zinc oxide catalytic of visible light activity, prepare a kind of under visible light (sunshine) have the zinc oxide of high oxidation activity, as the photochemical catalyst of degradation of organic substances in the environmental improvement.
The present invention also aims to provide the Zinc oxide catalytic of described method preparation.
Zinc oxide catalytic preparation method with visible light activity of the present invention comprises the steps: the polyvinylpyrrolidone of (1) two water zinc acetate and molecular weight 2～60,000, be dissolved in the ethylene glycol, mix then, wherein the weight ratio of two water zinc acetates and polyvinylpyrrolidone is 0.2～4: 1, and the weight ratio of ethylene glycol and two water zinc acetates is 300～50: 1; (2) stir heating down by the prepared mixed liquor to 140 of step (1)～200 ℃, behind condensing reflux 1～5h, the sediment suction filtration is separated, absolute ethanol washing, drying 300～700 ℃ of calcination process, obtain having the Zinc oxide catalytic of visible light activity.
Preferred plan is: the weight ratio of two water zinc acetates and polyvinylpyrrolidone is 0.5～2: 1, the weight ratio of ethylene glycol and two water zinc acetates is 200～100: 1, be heated to 160～195 ℃ under stirring, behind condensing reflux 3～5h, the sediment suction filtration is separated, absolute ethanol washing, drying are 400～600 ℃ of calcination process.
The polyvinylpyrrolidone optimum weight is 3～50,000.
The present invention compared with prior art has following advantage and effect:
(1) photochemical catalyst is the focus of at present domestic and international nano material and environmental catalysis research, it is carried out as seen photochemical, utilize sunshine or general visible source to realize that light-catalyzed reaction is the key of photocatalysis technology practical application, the present invention modifies nano titanium oxide at present and improves on the visible light catalysis activity present Research, prepare a kind of zinc oxide visible light catalyst, enrich the research and the application content of photochemical catalyst, promoted the development of photocatalysis technology.
(2) Zinc oxide catalytic of the present invention preparation adopts common zinc acetate as raw material, it is not carried out modifications such as noble metal, modifies oxide/titanium dioxides with present various visible lights, composite mixed zinc oxide is compared easier enforcement and cheapness.
(3) Zinc oxide catalytic of the present invention's preparation has high activity to organic oxidative degradation under visible light.As shown in table 1, the zinc oxide of the present invention's preparation is higher 8～9 times than commercially available titanium dioxide to the degradation rate of methyl orange in the water, and is higher 2 times than commercially available zinc oxide.
Description of drawings
The stereoscan photograph of the zinc oxide that Fig. 1 makes for the present invention;
The zinc oxide that Fig. 2 makes for the present invention sweep ultraviolet-visible absorption spectroscopy figure.
The specific embodiment
Embodiment 1
In the flask of 500ml, add 1.0g two water zinc acetates, 5g polyvinylpyrrolidone (molecular weight 20,000), be dissolved in the ethylene glycol respectively and mix, wherein the weight ratio of two water zinc acetates and polyvinylpyrrolidone is 0.2: 1, and the weight ratio of ethylene glycol and two water zinc acetates is 300: 1; The powerful stirring begins heat temperature raising to 140 ℃ down, behind the condensing reflux 5h, and with sediment suction filtration separation while hot, absolute ethanol washing 3 times, 120 ℃ of dry 30min are after 300 ℃ of calcination process make the zinc oxide with visible light activity.
Embodiment 2
In the flask of 500ml, add 1.0g two water zinc acetates, 2.0g polyvinylpyrrolidone (molecular weight 30,000), be dissolved in the ethylene glycol respectively and mix, wherein the weight ratio of two water zinc acetates and polyvinylpyrrolidone is 0.5: l, and the weight ratio of ethylene glycol and two water zinc acetates is 200: 1; The powerful stirring begins heat temperature raising to 195 ℃ down, behind the condensing reflux 3, and with sediment suction filtration separation while hot, absolute ethanol washing 3 times, 120 ℃ of dry 30min are after 600 ℃ of calcination process make the zinc oxide with visible light activity.
Embodiment 3
In the flask of 500ml, add 1.0g two water zinc acetates, 0.25g polyvinylpyrrolidone (molecular weight 60,000), be dissolved in the ethylene glycol respectively and mix, wherein the weight ratio of two water zinc acetates and polyvinylpyrrolidone is 4: 1, and the weight ratio of ethylene glycol and two water zinc acetates is 50: l; The powerful stirring begins heat temperature raising to 200 ℃ down, behind the condensing reflux 1h, and with sediment suction filtration separation while hot, absolute ethanol washing 3 times, 120 ℃ of dry 30min are after 700 ℃ of calcination process make the zinc oxide with visible light activity.
In the flask of 500ml, add 1.0g two water zinc acetates, 0.5g polyvinylpyrrolidone (molecular weight 50,000), be dissolved in the ethylene glycol respectively and mix, wherein the weight ratio of two water zinc acetates and polyvinylpyrrolidone is 2: l, and the weight ratio of ethylene glycol and two water zinc acetates is l00: 1; The powerful stirring begins heat temperature raising to 160 ℃ down, behind the condensing reflux 4h, and with sediment suction filtration separation while hot, absolute ethanol washing 3 times, 120 ℃ of dry 30min are after 500 ℃ of calcination process make the zinc oxide with visible light activity.
Adopt the zinc oxide of the foregoing description preparation to carry out methyl orange performance evaluation in the photocatalytic degradation water, the XPA-II type photochemical reaction instrument that adopts Xu Jiang dynamo-electric factory in Nanjing to produce, reactor configurations has magnetic stirring apparatus, quartzy cold well, condenser pipe.The 1000W xenon lamp is as visible light source, and dominant wavelength is 600nm.Photocatalytic reaction conditions; Methyl orange concentration 20mg/L in the water, catalyst amount 0.1g/L, oxygen flow 250mL/min, 30～40 ℃ of reaction temperatures, reaction time 2h.The result shows that the Zinc oxide catalytic of invention has high visible light catalysis activity.
Company difficult to understand field emission scanning electron microscope (LEO1530VP) in the above-mentioned zinc oxide employing Germany that makes is carried out ESEM (SEM) analysis, observe and find the spherical particle of zinc oxide, granular size is 40～100nm, on average 80nm (as Fig. 1, amplifying 30,000 times).Zinc oxide powder of the present invention is dispersed in the absolute ethyl alcohol, and after disperseing with ultrasonic wave is powerful, the absorbance with WGZ-8 type dual-beam ultraviolet one visible spectrophotometer working sample compares with nano titanium oxide (as Fig. 2) simultaneously.From scheming visible TiO
2Absorption to light is little, only at the 215nm place in extreme ultraviolet light district a little absworption peak is arranged; Zinc oxide of the present invention has an absworption peak respectively at 220nm and 380nm place, and has stronger absorption in 200～400nm scope, has the visible absorption performance.
As shown in table 1, the zinc oxide of embodiment preparation has high activity to organic oxidative degradation under visible light.Degradation rate to methyl orange in the water is higher 8～9 times than commercially available titanium dioxide, and is higher 2 times than commercially available zinc oxide.
Several photochemical catalysts of table 1 under visible light to water in the comparison of methyl orange degradation rate
| Photochemical catalyst | The methyl orange degradation rate |
| Market titanium dioxide | 11.2％ |
| Market zinc oxide | 42.6％ |
| The zinc oxide that the embodiment of the invention 1 makes | 82.5％ |
| The zinc oxide that the embodiment of the invention 2 makes | 99.0％ |
| The zinc oxide that the embodiment of the invention 3 makes | 84.5％ |
| The zinc oxide that the embodiment of the | 90.5％ |
Claims (4)
1, a kind of Zinc oxide catalytic preparation method with visible light activity is characterized in that comprising the steps:
(1) with the polyvinylpyrrolidone of two water zinc acetates and molecular weight 2～60,000, be dissolved in the ethylene glycol, mix then, wherein the weight ratio of two water zinc acetates and polyvinylpyrrolidone is 0.2～4: 1, and the weight ratio of ethylene glycol and two water zinc acetates is 300～50: 1;
(2) stir heating down by the prepared mixed liquor to 140 of step (1)～200 ℃, behind condensing reflux 1～5h, the sediment suction filtration is separated, absolute ethanol washing, drying 300～700 ℃ of calcination process, obtain having the Zinc oxide catalytic of visible light activity.
2, the preparation method of Zinc oxide catalytic according to claim 1, the weight ratio that it is characterized in that two water zinc acetates and polyvinylpyrrolidone is 0.5～2: 1, the weight ratio of ethylene glycol and two water zinc acetates is 200～100: 1, be heated to 160～195 ℃ under stirring, behind condensing reflux 3～5h, the sediment suction filtration is separated, and absolute ethanol washing, drying are 400～600 ℃ of calcination process.
3, the preparation method of Zinc oxide catalytic according to claim 1 and 2 is characterized in that described polyvinylpyrrolidonemolecules molecules amount is 3～50,000.
4, the Zinc oxide catalytic of the described method preparation of claim 1.
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| CN 200410077519 CN1285405C (en) | 2004-12-22 | 2004-12-22 | Photocatalyst of zinc oxide possessing visible light activity and preparation method |
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| CN 200410077519 CN1285405C (en) | 2004-12-22 | 2004-12-22 | Photocatalyst of zinc oxide possessing visible light activity and preparation method |
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| CN1285405C true CN1285405C (en) | 2006-11-22 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100420632C (en) * | 2007-01-22 | 2008-09-24 | 南京大学 | Method for synthesizing zinc oxide nano micro pin |
| CN102294246A (en) * | 2011-06-11 | 2011-12-28 | 西南交通大学 | Preparation method for Cu2O/ZnO heterojunction |
| CN103831093B (en) * | 2014-03-06 | 2015-12-30 | 浙江师范大学 | A kind of Zinc oxide-base composite photocatalyst nano material and preparation method thereof |
| CN108568295B (en) * | 2017-03-07 | 2021-05-25 | 中国科学院上海硅酸盐研究所 | Inkstone-shaped ZnO/graphene composite photocatalyst and preparation method thereof |
| CN107416889A (en) * | 2017-05-15 | 2017-12-01 | 上海电机学院 | A kind of preparation method of Co doping ZnO quantum dot |
| CN108184898B (en) * | 2018-01-05 | 2019-06-21 | 烟台鲁量新材料科技有限公司 | A kind of preparation method of inorganic complex antimicrobials |
| CN109201029B (en) * | 2018-09-17 | 2021-04-06 | 绍兴文理学院 | Preparation method of efficient porous composite photocatalytic material |
| CN109316920A (en) * | 2018-10-17 | 2019-02-12 | 厦门大学 | A kind of catalyst of transition metal oxide, preparation method and applications |
| CN112777626B (en) * | 2021-01-11 | 2022-04-12 | 大连理工大学 | Highly uniform zinc oxide submicron spheres with controllable particle size and preparation method thereof |
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Assignee: Zhongshan Zifang Environmental Protection Technology Co., Ltd. Assignor: South China University of Technology Contract fulfillment period: 2007.8.12 to 2012.8.12 contract change Contract record no.: 2008440000491 Denomination of invention: Photocatalyst of zinc oxide possessing visible light activity and preparation method Granted publication date: 20061122 License type: Exclusive license Record date: 20081211 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.8.12 TO 2012.8.12; CHANGE OF CONTRACT Name of requester: ZHONGSHAN CITY ZIFANG ENVIRONMENT PROTECTION TECHN Effective date: 20081211 |
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