CN101342486B - Metallic oxide nano-material - Google Patents
Metallic oxide nano-material Download PDFInfo
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- CN101342486B CN101342486B CN2008100423246A CN200810042324A CN101342486B CN 101342486 B CN101342486 B CN 101342486B CN 2008100423246 A CN2008100423246 A CN 2008100423246A CN 200810042324 A CN200810042324 A CN 200810042324A CN 101342486 B CN101342486 B CN 101342486B
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- zinc oxide
- oxide
- nanophase material
- tin dioxide
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Abstract
The invention provides a metal-oxide nanophase material, pertaining to the fields of nanophase material preparation and application. Zinc-oxide nanophase material and tin dioxide nanophase material are mixed by a proper mass ratio, the mass fraction of zinc oxide in the mixture is 10-50 percent, the mixture achieved has high-efficient photochemical performance; the mixture comprises zinc oxide and tin dioxide micron spheres; the micron sphere diameter drops within 0.2-3 microns; the micron sphere is composed of nanometer sticks (diameter: 10-100) and/or nanometer particles (diameter: 5-50); the photocatalysis performance is much higher than the photocatalysis activity of single-constituent zinc-oxide nanophase material or tin dioxide nanophase material, and also much higher than the photocatalysis activity of the mixture of commercial zinc oxide and commercial tin dioxide. The zinc oxide nanophase material and the tin dioxide nanophase material are prepared by microwave auxiliary heating, and have the advantages of simple technique, rapidness, high production efficiency, etc.
Description
Technical field
The present invention relates to metal oxide nano-material, belong to nano material preparation and application.
Technical background
Photochemical catalyst can utilize luminous energy as a kind of catalysis material, and degradation of organic substances under illumination reaches the purpose of environment purification.In recent years, along with the constant growth of productivity, the energy and environmental problem are also more and more serious, and the research of photochemical catalyst also becomes the focus of research.Prepared multiple photochemical catalyst at present, mainly contained oxide (like titanium dioxide, zinc oxide, tin ash etc.), sulfide (like zinc sulphide, cadmium sulfide etc.), multivariant oxide (like Bi
2WO
6, ZnSnO
3, BiVO
4Deng) and compound.
Improve the activity of photochemical catalyst, thereby mainly be to improve catalyst the absorptivity of photon and the utilization rate that reduces the compound raising photon of electron hole pair.At present, the method for utilization mainly is to realize through methods such as doping, surface modification and different materials are compound, and wherein using the widest is composite methods.Compound through several kinds of different materials, the coupling between the different materials can so that the electronics that optical excitation produces and hole to separating, thereby the photocatalytic activity of the utilization rate raising catalyst of raising photon.Prepared multiple composite photo-catalyst at present, like TiO
2/ C, ZnO/SnO
2Deng.But preparation technology's relative complex of composite, cost is higher, and this has also limited its application.
Along with the development of nanoscale science and technology, the research of nano material is also more and more deep.Nano material has big specific area, and more activity site can be provided, and has broad application prospects at catalytic field.At present prepared multiple photochemical catalyst with nanostructured, nano-photocatalyst has shown and has been much higher than the normal optical activity of such catalysts.
Summary of the invention
Photochemical catalyst of the present invention is that nano zinc oxide material and stannic oxide nanometer material are mixed with mass ratio; The mass fraction of zinc oxide is 10%-50% in the mixture; The mixture that obtains has photocatalysis performance efficiently; Mixture is made up of zinc oxide and tin ash micron ball, and the diameter of micron ball is 0.2 to 3 micron, and the micron ball is assembled by diameter 10-100 nanometer rods and/or diameter 5-50 nano particle.
Preparation method of the present invention be mixed liquor with water and a kind of low-grade monobasic alcohol (like methyl alcohol, ethanol, isopropyl alcohol etc.) as solvent, the volume fraction of alcohol is 20%-60% in the said mixed solvent.Choosing a kind of surfactant (like softex kw, polyethylene glycol or polyvinylpyrrolidone etc.) is dispersant, and its concentration is 0.01-1 mol; Soluble metallic salt (like halide, nitrate, sulfate and acetate etc.) and highly basic (hydroxide of alkali metal and alkaline-earth metal is NaOH and potassium hydroxide for example) with zinc and tin are raw material, at room temperature form uniform clear solution.The concentration of solubility amphoteric metal salt is 0.01-1 mol, and the concentration of highly basic is 0.5-5 mol.And then as reactant, its concentration is 0.5-5 mol to choose a kind of organic monoacid ester (like ethyl acetate, methyl acetate, Ethyl formate or methyl formate etc.).With the organic monoacid ester with change in the agitated reactor after above-mentioned clear solution mixes, under 60-220 ℃, carry out microwave solvent heat treatment, the processing time is 5-120 minute.After microwave solvent heat treatment finishes, to product centrifugalize, water or absolute ethanol washing, then under room temperature to 100 ℃ temperature, drying can obtain corresponding oxide-based nanomaterial under the air atmosphere.
The photocatalysis performance of photochemical catalyst of the present invention is much higher than the zinc oxide of independent component or the photocatalytic activity of tin ash, also is much higher than simultaneously the photocatalytic activity of mixture of tin ash of zinc oxide and the commodity of commodity.
The present invention also has following advantage:
1. the preparation method is simple, just can obtain through simple method of mixing.
2. nano zinc oxide material and stannic oxide nanometer material adopt the mode of heating using microwave to prepare, and can shorten the reaction time greatly, enhance productivity.
3. low in raw material cost is easy to get, and is easy to operate, and preparation technology is simple, and productive rate is high, does not need cost and complex equipment, is easy to realize suitability for industrialized production.
Description of drawings
The electron scanning micrograph of the ZnO micron ball that is assembled into by nanometer rods that 0 ℃ of microwave solvent of Figure 116 heat obtained in 30 minutes: the diameter of ball is the 1-2 micron.
The SnO that is assembled into by nano particle that 60 ℃ of microwave solvents of Figure 21 heat obtained in 30 minutes
2The electron scanning micrograph of nanosphere: the diameter of ball is the 200-300 nanometer.
ZnO micron ball, the SnO of Fig. 3 preparation
2Nanosphere and both mix the photocatalytic degradation curve of back to methyl orange with the 1:3 mass ratio.
The ZnO of Fig. 4 commodity, SnO
2And both mix the photocatalytic degradation curve of back to methyl orange with the 1:3 mass ratio.
The specific embodiment
Further specify embodiment and effect with detail description embodiment.
Embodiment 1
The photochemical catalyst that obtains after the mass ratio mixing of nano zinc oxide material and stannic oxide nanometer material with 1:3.The zinc oxide micrometer ball is made up of about 50 nanometer rods of diameter, and the diameter of micron ball is at the 1-2 micron; The stannic oxide nanometer ball is assembled less than 10 nano particles by diameter, and the diameter of micron ball is in the 200-300 nanometer.
Above-mentioned nano zinc oxide material and stannic oxide nanometer preparation methods are:
1mmol Zinc diacetate dihydrate (perhaps Tin tetrachloride pentahydrate), 0.5 gram softex kw and 1.2 are restrained the mixed solution that NaOH are dissolved in 20ml deionized water and 10ml methyl alcohol, and the back that stirs adds 2.75ml ethyl acetate.Change this reactant liquor in the agitated reactor (the liner capacity is 60 milliliters), sealing.Agitated reactor is put into the microwave solvent thermal reaction apparatus, be incubated 30 minutes down at 160 ℃.After reaction system naturally cools to room temperature, take out product, use the centrifugal process separated product, the product of separation is with absolute ethanol washing 3 times, 60 ℃ of air dryings.Analysis shows that the product that obtains is zinc oxide micrometer ball or tin ash micron ball.Zinc oxide micrometer is asked by the rod of about 50 nanometers of diameter and is formed, and the diameter of ball is at the 1-2 micron; Tin ash micron ball is assembled by the particle of diameter 10 nanometers, and the diameter of ball is in the 200-300 nanometer.
Is the mixed of 1:3 with the nano zinc oxide material and the stannic oxide nanometer material of above-prepared with the mass ratio, obtains novel colleges and universities' photochemical catalyst.
Above-mentioned photochemical catalyst is suspended in the methyl orange aqueous solution, again this suspension is placed irradiation under the ultraviolet light,, obtain the speed of photocatalytic degradation methyl orange with measurement of ultraviolet-visible spectrophotometer methyl orange solution concentration curve over time.Experimental result shows that under the effect of the mixture photochemical catalyst that obtains, through 40 minutes ultraviolet irradiation, the methyl orange in the solution can all be degraded.
As a comparison, with the photochemical catalyst that obtains after zinc oxide and of the mass ratio mixing of tin ash commodity powder with 1:3.Above-mentioned photochemical catalyst is suspended in the methyl orange aqueous solution, again this suspension is placed irradiation under the ultraviolet light,, obtain the speed of photocatalytic degradation methyl orange with measurement of ultraviolet-visible spectrophotometer methyl orange solution concentration curve over time.Experimental result shows that under the effect of this photochemical catalyst, through 40 minutes ultraviolet irradiation, the methyl orange in the solution only degraded about 45%.
The photochemical catalyst that obtains after the mass ratio mixing of nano zinc oxide material and stannic oxide nanometer material with 1:2.The zinc oxide micrometer ball is made up of about 20 nanometer rods of diameter, and the diameter of micron ball is at 3 microns; The stannic oxide nanometer ball is assembled by diameter 20 nano particles, and the diameter of micron ball is in 0.5 nanometer.
The preparation method is with embodiment 1.
Embodiment 3
The photochemical catalyst that obtains after the mass ratio mixing of nano zinc oxide material and stannic oxide nanometer material with 1:4.The zinc oxide micrometer ball is made up of about 20 nanometer rods of diameter, and the diameter of micron ball is at 3 microns; The stannic oxide nanometer ball is assembled by diameter 10 nano particles, and the diameter of micron ball is in the 200-300 nanometer.
The preparation method is with embodiment 1.
Claims (3)
1. metal oxide nano-material; It is characterized in that it being with nano zinc oxide material and stannic oxide nanometer material mixing; Wherein the structure of zinc oxide and tin ash is the micron ball; The diameter of micron ball is 0.2 to 3 micron, and the micron ball is that 10-100 nanometer rods and/or diameter 5-50 nano particle assemble by diameter.
2. by the described metal oxide nano-material of claim 1, the mass fraction that it is characterized in that zinc oxide is 10%-50%.
3. be used for the photochemical catalyst field by claim 1 or 2 described metal oxide nano-materials.
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| CN2008100423246A CN101342486B (en) | 2008-08-29 | 2008-08-29 | Metallic oxide nano-material |
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| CN2008100423246A CN101342486B (en) | 2008-08-29 | 2008-08-29 | Metallic oxide nano-material |
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| CN101342486B true CN101342486B (en) | 2012-05-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102489293B (en) * | 2011-11-18 | 2013-03-13 | 陕西科技大学 | Preparation method of tin dioxide/bismuth tungstate composite photocatalyst |
| CN104744909B (en) * | 2013-12-31 | 2019-01-11 | 比亚迪股份有限公司 | Polymer product and printing ink composition and surface selective metallization method |
| CN107216043A (en) * | 2017-06-26 | 2017-09-29 | 陈霞 | A kind of preparation method of high-strength armoured-glass |
| CN112993234B (en) * | 2019-12-12 | 2022-06-03 | 中国科学院大连化学物理研究所 | Niobium-based oxide material, preparation method and application thereof |
| CN116510719A (en) * | 2023-04-16 | 2023-08-01 | 大连理工大学 | Core-shell material ZnO/SnO 2 Preparation method and application of (C) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1460544A (en) * | 2003-05-26 | 2003-12-10 | 中国科学院广州地球化学研究所 | Preparation method of nano ZnO-SnO2 composite oxide photo-catalyst |
| CN1140480C (en) * | 2002-02-05 | 2004-03-03 | 中国科学院理化技术研究所 | Spherical and microporous composite zine oxide-SiO2 particles and preparing process and usage thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1140480C (en) * | 2002-02-05 | 2004-03-03 | 中国科学院理化技术研究所 | Spherical and microporous composite zine oxide-SiO2 particles and preparing process and usage thereof |
| CN1460544A (en) * | 2003-05-26 | 2003-12-10 | 中国科学院广州地球化学研究所 | Preparation method of nano ZnO-SnO2 composite oxide photo-catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 杨洪伟等.氧化锌纳米棒微球的水热制备及其气敏性质研究.《材料工程》.2007,(第2期),第4页左栏第2段至右栏第2段. * |
| 郭宏飞等.纳米氧化锌的制备方法对合成碳酸二甲酯性能的影响.《山东化工》.2007,第36卷(第8期),第2页左栏第2段至右栏第2段. * |
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