CN102350337B - Method for preparing ZnO/rectorite/carbon nano tube composite material - Google Patents
Method for preparing ZnO/rectorite/carbon nano tube composite material Download PDFInfo
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- CN102350337B CN102350337B CN 201110218787 CN201110218787A CN102350337B CN 102350337 B CN102350337 B CN 102350337B CN 201110218787 CN201110218787 CN 201110218787 CN 201110218787 A CN201110218787 A CN 201110218787A CN 102350337 B CN102350337 B CN 102350337B
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Abstract
The invention discloses a method for preparing a ZnO/rectorite/carbon nano tube composite material. The method comprises the following steps of: A, preparing zinc oxide sol, namely reacting hydrazine hydrate and zinc acetate at room temperature by taking dimethylbenzene and ethylene glycol as a mixed solvent to prepare ZnO sol; B, loading ZnO by a carbon nano tube and rectorite, namely adding the preprocessed rectorite and the purified carbon nano tube into the ZnO sol, stirring, standing at the room temperature, centrifuging, and separating solid precipitates from a solution; and C, standing, separating, washing and grinding, namely standing at the room temperature, centrifuging, separating the solid precipitates from the solution, washing the precipitates by using absolute ethanol and deionized water, calcining at the temperature of 500 DEG C in a muffle furnace, and grinding uniformly to obtain the composite material. The method has a simple process and is low in cost, process parameters are easy to control, the composite material is high in crystallinity and purity, the loading of nanometer ZnO granules is realized, and the problem of difficulty in separation and recovery in the application process is solved.
Description
Technical field
The present invention relates to absorption and optic catalytic composite material, the preparation method who more specifically relates to a kind of ZnO/ rectorite/carbon nanotube composite photocatalyst material, can be used in absorption and the photocatalytic degradation removal water organic pollutions such as dyestuff, and be expected the processing for actual waste water.
Background technology
Nano zine oxide has obvious skin effect and quantum size effect as a kind of important photochemical catalyst, more is proved to have the TiO of ratio under some experiment condition
2Higher catalytic performance causes people's extensive concern in recent years, compares TiO
2Preparation cost is high, and nano-ZnO is demonstrating better application prospect aspect the pollutant photocatalysis removal.Low for single photocatalytic semiconductor catalytic efficiency, the visible light utilization ratio is low, load and use the characteristics such as difficult separation and recycling, and present technique is had the property modification research of nano-ZnO in mind.
CNT has nanoscale official jargon structure, higher specific area and good heat endurance, chemical stability and good electronic conductivity, so used as catalyst carrier.Rectorite is a kind of special book clay mineral material.Semiconductor catalyst and rectorite are compound, both can realize semi-conductive immobilizedly, can utilize again the good adsorptivity of rectorite, increase contacting of catalyst and organic pollution, improve the efficient of its absorption and photocatalysis.
Summary of the invention
The objective of the invention is to be to provide a kind of preparation method of ZnO/ rectorite/carbon nanotube composite materials, preparation technology is simple, technological parameter is easy to control, cheap, composite good crystallinity, purity height, realized that nano-ZnO is particle loaded, solved the problem of difficult separation and recycling in application process.In order to realize above-mentioned purpose, the present invention adopts following technical measures:
The present invention is based on semiconductor (ZnO), CNT (CNTs) and the good character of rectorite (REC), the nano composite material, absorption and the photocatalytic degradation removal organic pollutants that further prepare semiconductor (ZnO) and CNT and rectorite with sol-gel process.Both improved the visible-range that ZnO uses, and made it under visible light, have higher photocatalytic activity; Can satisfy again it and under specific physicochemical property requirement condition, it evenly is carried on the carrier securely, promote its application in actual waste water is processed.
A kind of preparation method of ZnO/ rectorite/carbon nanotube composite materials the steps include:
1, preparation zinc oxide colloidal sol: under room temperature (20-25 ℃, below identical), take dimethylbenzene and ethylene glycol as mixed solvent, make ZnO colloidal sol through hydrazine hydrate and zinc acetate reaction.In liquid phase, at first form the ZnO nucleus after the reaction, then grow up through gathering and recrystallization.In the nucleation process of nano-ZnO, ethylene glycol has played key effect.Under the room temperature rapid stirring, even the hydration zinc acetate of the identical proportioning of grinding also can't fully be dissolved in the dimethylbenzene, but after adding the ethylene glycol of about 100ml, the very fast clear solution that in mixed solvent, forms of hydration zinc acetate, leave standstill about 2-3min after stopping to stir, can find the droplet that distributing in the solution, infer that just these droplets that formed by ethylene glycol provide the place for forming core and the crystalline growth of ZnO crystal grain in mixed solvent, thereby obtain ZnO colloidal sol.The adding of ethylene glycol has improved the viscosity of solution, and its crystal growth rate is slowed down, and has the sufficient time to generate a lot of nucleus, otherwise only irregular agglomerated particle can occur.
2. CNT and rectorite loading ZnO:
CNT behind rectorite after pretreatment (rectorite, REC) and the purifying (CNTs) adds in the ZnO colloidal sol, and rapid stirring 4-6h leaves standstill rear centrifugally under the room temperature, solids of sedimentation is separated from solution; After the CNT behind the purifying and pretreated rectorite are distributed to ZnO colloidal sol, because physics and chemistry suction-operated, the ZnO colloidal particles load on the CNT outer wall, and insert the interlamination region of the stratiform rectorite with two-dimensional space structure, become new nuclearing centre.Owing to reduced the reaction system energy, thereby the ZnO particle is grown up gradually after the load.Nanocrystalline pattern and size are determined by the internal structure of crystal, also are subject to the impact of external condition simultaneously, and the growth of the ZnO after the nucleation more is subject to the impact of reaction condition (temperature, solvent property).At first to have anisotropy in the particle growth process, just may obtain the nanometer short column.EG is as solvent, increased on the one hand the viscosity of reaction system, the mutual fusion that makes nucleus a little less than, form easily independently short cylinder crystal; On the other hand, in the ZnO crystal growth course, the EG segregation has suppressed the growth of these crystal faces on some crystal face of ZnO crystal, thus make ZnO crystal one party to growth generate the nanometer short column much larger than other direction.
3, standing separation, washing is ground:
Leave standstill behind the 3-5h centrifugally under the room temperature, solids of sedimentation is separated from solution; To precipitate wash each 2-4 time with absolute ethyl alcohol and deionized water respectively after, 500 ℃ of lower roasting 4-6h in Muffle furnace, grinding evenly can this composite.
In described ZnO/ rectorite/carbon nanotube composite materials, the mass ratio of ZnO, rectorite, CNT is 2:1:0.1.
The present invention compared with prior art has the following advantages and effect:
1. prepared the ZnO/ rectorite/absorption of CNT composite Nano and photochemical catalyst
2. the most of source of raw materials is abundant, cheap; Though the CNT price is more expensive, addition less (mass fraction is no more than 3.23%), little to overall cost impact.
3. preparation technology is simple, the gentle (common zinc acetate (Zn (CH of reaction condition
3COO)
22H
2O) thermal decomposition is that the temperature of ZnO is 350 ℃, and in this experiment, this reaction is then at room temperature carried out, and need not the heating that heats up), technological parameter (mass ratio 2:1:0.1, reaction time 4 ~ 5h, 500 ℃ of sintering temperatures, roasting time 5h) easy to control.
4. this composite good crystallinity, purity are high, and average grain diameter is 18.96nm.Realized that simultaneously nano-ZnO is particle loaded, solved the problem of difficult separation and recycling in application process.
5. this composite has good adsorption capacity (saturated extent of adsorption is 34.72mg/g, the ZnO/ rectorite composite adsorption and the photochemical catalyst that are higher than the same procedure preparation), and under visible light to water in the organic pollution such as dyestuff higher photocatalysis removal effect is arranged (in the methylene blue solution at 5mg/L, when this composite catalyst consumption is 500mg/L, behind the illumination 60min, the methylene blue clearance can reach more than 90%.）。
The specific embodiment
Below by embodiment, further illustrate outstanding feature of the present invention, only be the present invention is described and never limit the present invention.
Embodiment 1:
A kind of preparation method of ZnO/ rectorite/carbon nanotube composite materials the steps include:
A, preparation zinc oxide colloidal sol: under the room temperature, take dimethylbenzene and ethylene glycol as mixed solvent, through hydrazine hydrate and zinc acetate reaction gained.
Take by weighing the 2.1950 hydration zinc acetates that restrain with precision balance, join in the dimethylbenzene and 0.04mol ethylene glycol mixed solvent of 100ml.After rapid stirring is even, dropwise add the ethanolic solution of an amount of 0.04mol hydrazine hydrate, dropwise rear continuation and stir l h, solution becomes milky, obtains ZnO colloidal sol;
B, the CNT that takes by weighing behind the pretreated rectorite powder of 0.4050g and the 0.0405g purifying respectively add in the ZnO colloidal sol, rapid stirring 5h, leave standstill under the room temperature 34 or 5h after centrifugal, solids of sedimentation is separated from solution;
C, will precipitate respectively with after absolute ethyl alcohol and the deionized water washing each 3 times, 500 ℃ of lower roastings 4 or 5 or 6h in Muffle furnace, grinding evenly can this composite.
Embodiment 2:
A kind of preparation method of ZnO/ rectorite/carbon nanotube composite materials the steps include:
1, preparation zinc oxide colloidal sol: under the room temperature, take dimethylbenzene and ethylene glycol as mixed solvent, through hydrazine hydrate and zinc acetate reaction gained.
Take by weighing the hydration zinc acetate of 4.3902g with precision balance, join in the dimethylbenzene and 2.23ml ethylene glycol mixed solvent of 100ml.After rapid stirring is even, dropwise add ethanol (100ml) solution of 1.94ml hydrazine hydrate, dropwise rear continuation and stir l h, solution becomes milky, obtains ZnO colloidal sol.
2, the CNT that takes by weighing respectively behind the pretreated rectorite powder of 0.8139g and the 0.0814g purifying adds in the ZnO colloidal sol, rapid stirring 5h, leave standstill under the room temperature 34 or 5h after centrifugal, solids of sedimentation is separated from solution.
3, will precipitate respectively with after absolute ethyl alcohol and the deionized water washing each 3 times, 500 ℃ of lower roasting 5h in Muffle furnace, grinding evenly can this composite.
Embodiment 3:
A kind of preparation method of ZnO/ rectorite/carbon nanotube composite materials the steps include:
1, preparation zinc oxide colloidal sol: under the room temperature, take dimethylbenzene and ethylene glycol as mixed solvent, through hydrazine hydrate and zinc acetate reaction gained.
Take by weighing the hydration zinc acetate of 6.6003g with precision balance, join in the dimethylbenzene and 4.46ml ethylene glycol (EG) mixed solvent of 100ml.After rapid stirring is even, dropwise add ethanol (100ml) solution of an amount of 3.88ml hydrazine hydrate, dropwise rear continuation and stir l h, solution becomes milky, obtains ZnO colloidal sol.
2. the CNT that takes by weighing respectively behind the pretreated rectorite powder of 1.2237g and the 0.1224g purifying adds in the ZnO colloidal sol, rapid stirring 5h, leave standstill under the room temperature 34 or 5h after centrifugal, solids of sedimentation is separated from solution.
3. will precipitate respectively with after absolute ethyl alcohol and the deionized water washing each 3 times, 500 ℃ of lower roasting 5h in Muffle furnace, grinding evenly can this composite.
This composite has good adsorption capacity, saturated extent of adsorption is 34.72mg/g, the ZnO/ rectorite composite adsorption and the photochemical catalyst that are higher than the same procedure preparation, and under visible light to water in the organic pollution such as dyestuff higher photocatalysis removal effect is arranged, in the methylene blue solution of 5mg/L, when this composite catalyst consumption was 500mg/L, behind the illumination 60min, the methylene blue clearance can reach more than 90%.
Claims (1)
1. the preparation method of a ZnO/ rectorite/carbon nanotube composite materials the steps include:
A, preparation zinc oxide colloidal sol: at room temperature, take dimethylbenzene and ethylene glycol as mixed solvent, make ZnO colloidal sol through hydrazine hydrate and zinc acetate reaction, in liquid phase, at first form the ZnO nucleus after the reaction, then through assembling and recrystallization is grown up;
B, CNT and rectorite loading ZnO: the CNT behind pretreated rectorite and the purifying adds in the ZnO colloidal sol, stirs 4-6h;
C, standing separation, washing is ground: leave standstill behind the 3-5h centrifugally under the room temperature, solids of sedimentation is separated from solution; To precipitate wash each 2-4 time with absolute ethyl alcohol and deionized water respectively after, 500 ℃ of lower roasting 4-6h in Muffle furnace, grinding evenly can this composite;
In described ZnO/ rectorite/carbon nanotube composite materials, the mass ratio of ZnO, rectorite, CNT is 2:1:0.1.
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| CN106390918A (en) * | 2016-12-01 | 2017-02-15 | 武汉大学 | Preparation method of rectorite/zinc oxide/ferroferric oxide nano composite material |
| CN110318252B (en) * | 2019-08-16 | 2021-09-28 | 四川轻化工大学 | Composite material with spiral carbon nanofiber surface loaded with zinc oxide particles and preparation method and application thereof |
| CN111297708B (en) * | 2019-11-06 | 2022-08-05 | 成都理工大学 | Talc-loaded nano ZnO composite anti-ultraviolet agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1669642A (en) * | 2004-12-24 | 2005-09-21 | 中国科学院上海硅酸盐研究所 | Carbon nano tube/zinc oxide composite powder with photocatalysis performance and method for preparing the same |
| CN101423678A (en) * | 2008-10-29 | 2009-05-06 | 国家纳米科学中心 | Light curing nano composite coating |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1669642A (en) * | 2004-12-24 | 2005-09-21 | 中国科学院上海硅酸盐研究所 | Carbon nano tube/zinc oxide composite powder with photocatalysis performance and method for preparing the same |
| CN101423678A (en) * | 2008-10-29 | 2009-05-06 | 国家纳米科学中心 | Light curing nano composite coating |
Non-Patent Citations (4)
| Title |
|---|
| Facile synthesis and photocatalytic property of bicrystalline TiO2/rectorite composites;Yalei Zhanga et al.;《Colloids and Surfaces A: Physicochemical and Engineering Aspects》;20110326;第384卷;page 137-144 * |
| Yalei Zhanga et al..Facile synthesis and photocatalytic property of bicrystalline TiO2/rectorite composites.《Colloids and Surfaces A: Physicochemical and Engineering Aspects》.2011,第384卷page 137-144. |
| ZnO-CNTs纳米复合材料的制备及性能表征;朱路平等;《物理化学学报》;20061031;第22卷(第10期);第1175-1180页 * |
| 朱路平等.ZnO-CNTs纳米复合材料的制备及性能表征.《物理化学学报》.2006,第22卷(第10期),第1175-1180页. |
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