CN102580716B - Method for synthesizing zinc oxide/graphene composite by solvothermal method - Google Patents
Method for synthesizing zinc oxide/graphene composite by solvothermal method Download PDFInfo
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- CN102580716B CN102580716B CN201210015819.6A CN201210015819A CN102580716B CN 102580716 B CN102580716 B CN 102580716B CN 201210015819 A CN201210015819 A CN 201210015819A CN 102580716 B CN102580716 B CN 102580716B
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Abstract
The invention provides a method for synthesizing a zinc oxide/graphene composite by a solvothermal method, relating to the preparation method of the zinc oxide/graphene composite. The invention aims to solve the following problems in the existing methods for synthesizing the zinc oxide/graphene composites: the methods are more tedious, have poor repeatability and are difficult to realize industrialization; and the obtained zinc oxide/graphene composites have poor dimensional homogeneity. The method comprises the following steps of: 1. mixing graphite oxide, a solvent and a zinc source to obtain a mixed solution; and 2. treating the mixed solution by a solvothermal treatment method and finally vacuum-drying the mixed solution, thus obtaining the zinc oxide/graphene composite. The method has the following advantages that 1. the energy consumption is low and the production cost is lowered; 2. the method is safe to operate; 3. the repeatability is good and the synthesis method is simple; 4. zinc oxide with small dimension is uniformly distributed on graphene and the dimension of the zinc oxide/graphene composite is controllable; and 5. the zinc oxide/graphene composite has excellent photocatalysis. The method is mainly used for preparing the zinc oxide/graphene composite.
Description
Technical field
The present invention relates to a kind of preparation method of zinc oxide/graphene composite material.
Background technology
Zinc oxide/graphene composite material has the advantage of zinc oxide and Graphene.Zinc oxide has excellent electricity, and optics chemical property makes it at photoelectricity, solar cell, and a transmitting, the fields such as air-sensitive have application prospect.Graphene, the two-dimensional structure being comprised of carbon atom, is zero gap semiconductor, makes it have excellent optics, transparency, mechanical elasticity, heat endurance, the performances such as chemical stability.Especially the pi-electron in Graphene, just as relatively without the Di Lake particle of quality, makes it on two-dimensional directional, have excellent electricity conductive performance.
The research that built in the last few years zinc oxide/graphene composite material field is more and more paid attention to, wherein more classical synthetic method be first in substrate growing graphene then utilize excusing from death spray pyrolysis, the various means such as electrochemical deposition and Hydrothermal Synthesis developing zinc oxide on Graphene.But this kind of synthetic method, reactions steps is many, and required instrument and equipment is complicated.And Haixin Chang etc. in < < prepares the high ultraviolet sensitivity device of zinc oxide nano rod/Graphene > > based on a kind of process for thermosynthesizing of situ solvent easily by Zinc oxide quantum dot is mixed with Graphene, prepare Zinc oxide quantum dot/graphene film, then thereby Situ Hydrothermal growing zinc oxide nanorod has made the high ultraviolet sensitivity device of zinc oxide nano rod/Graphene, (this kind of method mixed synthetic zinc oxide seed with Graphene, the method that mix with Graphene in contrast zinc source, the method has reduced both effects of mutually combining, continuous and carry out again Situ Hydrothermal and cause the zinc oxide nano rod that the obtains skewness on Graphene).In the high-performance zinc oxide Graphene complex > > of Er Libao army dyestuff in < < effectively removes water, take graphite oxide and zinc acetate is raw material, uses naoh treatment to make zinc acetate become Zn (OH)
4 2-, more both obtained zinc oxide/graphene composite material with sodium borohydride reduction graphite oxide.In this kind of synthetic method, adopt NaOH alkali treatment, accelerated the hydrolysis rate of zinc acetate, make the zinc oxide size heterogeneity obtaining.
In sum, that the method for existing synthesizing zinc oxide/graphene composite material exists is more loaded down with trivial details, poor repeatability, be difficult to realize industrialization, and the poor problem of the dimensional homogeneity of the zinc oxide/graphene composite material obtaining.
Summary of the invention
That the method that the present invention will solve existing synthesizing zinc oxide/graphene composite material exists is more loaded down with trivial details, poor repeatability, be difficult to realize industrialization, and the problem that the dimensional homogeneity of the zinc oxide/graphene composite material obtaining is poor, and a kind of method of solvent-thermal method synthesizing zinc oxide/graphene composite material.
A kind of method of solvent-thermal method synthesizing zinc oxide/graphene composite material, specifically complete according to the following steps: one, mix: under the condition that first low whipping speed is 100r/min～300r/mim, graphite oxide is scattered in solvent, then add zinc source and mix, obtaining mixed solution; Two, forming processes: the mixed solution first under 60 ℃～180 ℃ conditions, step 1 being obtained carries out solvent heat treatment 1h～16h, then adopt distilled water washing 2～4 times, finally vacuum drying 2h～8h under 60 ℃～80 ℃ conditions, had both obtained zinc oxide/graphene composite material; The mass ratio of the graphite oxide described in step 1 and solvent is 1:(500～1500); The mass ratio in the graphite oxide described in step 1 and zinc source is 1:(1～20).
Advantage of the present invention: one, preparation flow of the present invention is simple, and the zinc source that the present invention adopts cheap with graphite oxide, be easy to buy to synthesize, operating process adopts solvent heat to synthesize, and consumes energy low, reduces production costs; Two, the present invention is controlled at reaction temperature below 200 ℃, has guaranteed security; Three, favorable reproducibility of the present invention, and synthetic method is simple, therefore can be for large-scale production; Four, the zinc oxide/graphene composite material that adopts scanning electron microscopic observation the present invention to prepare can see that undersized zinc oxide distributes uniformly on Graphene, the present invention is by controlling solvent, He Xin source, zinc source and the graphite oxide ratio use, and realization regulates and controls zinc oxide/graphene composite material size when reaction temperature and reaction; Five, zinc oxide/graphene composite material that prepared by the present invention is that light induced electron and the hole that pure zinc oxide produces in photocatalytic process is easy to compound, suppressed its photocatalysis performance, Graphene can be used as effective electron carrier, thereby promoted the separated of light induced electron and hole, improved photocatalytic activity.
Accompanying drawing explanation
Fig. 1 is 25000 times of TEM figure that zinc oxide/graphene composite material is prepared in test one; Fig. 2 is 110000 times of TEM figure that zinc oxide/graphene composite material is prepared in test one.
The specific embodiment
The specific embodiment one: present embodiment is a kind of method of solvent-thermal method synthesizing zinc oxide/graphene composite material, specifically completes according to the following steps:
One, mix: under the condition that first low whipping speed is 100r/min～300r/mim, graphite oxide is scattered in solvent, then adds zinc source and mix, obtain mixed solution; Two, forming processes: the mixed solution first under 60 ℃～180 ℃ conditions, step 1 being obtained carries out solvent heat treatment 1h～16h, then adopt distilled water washing 2～4 times, finally vacuum drying 2h～8h under 60 ℃～80 ℃ conditions, had both obtained zinc oxide/graphene composite material.
The mass ratio of the graphite oxide described in present embodiment step 1 and solvent is 1:(500～1500).
The mass ratio in the graphite oxide described in present embodiment step 1 and zinc source is 1:(1～20).
In present embodiment process, first carry out the mix and blend of zinc source and graphite oxide, because the sufficient negative electricity function group in graphite oxide surface can occur effectively to interact with zinc ion, continuous and carry out again solvent thermal reaction, in course of reaction, graphite oxide is reduced into Graphene in high-temperature solvent heat treatment process, zinc source can occur to be slowly hydrolyzed and original position generation zinc oxide in solvent (ethanol etc.) simultaneously, finally obtains zinc oxide/graphene composite material.
Present embodiment preparation flow is simple, and the zinc source that the present invention adopts cheap with graphite oxide, be easy to buy to synthesize, operating process adopts solvent heat to synthesize, and consumes energy low, reduces production costs.
Present embodiment is controlled at reaction temperature below 200 ℃, has guaranteed security.
The favorable reproducibility of present embodiment, and synthetic method is simple, and therefore can be for large-scale production.
Present embodiment is by controlling solvent, He Xin source, zinc source and the graphite oxide ratio use, and realization regulates and controls zinc oxide/graphene composite material size when reaction temperature and reaction.
Zinc oxide/graphene composite material prepared by present embodiment is that light induced electron and the hole that pure zinc oxide produces in photocatalytic process is easy to compound, suppressed its photocatalysis performance, Graphene can be used as effective electron carrier, thereby promoted the separated of light induced electron and hole, improved photocatalytic activity.
The specific embodiment two: the difference of present embodiment and the specific embodiment one is: the solvent described in step 1 is ethanol, ethylene glycol or diethylene glycol.Other is identical with the specific embodiment one.
The specific embodiment three: present embodiment and one of the specific embodiment one or two difference are: the zinc source described in step 1 is Zn (Ac)
2, ZnCl
2or Zn (NO
3)
2.Other is identical with the specific embodiment one or two.
The specific embodiment four: one of present embodiment and specific embodiment one to three difference is: the graphite oxide described in step 1 adopts Hummer method to be prepared from, concrete steps are as follows: 1. first native graphite and sodium nitrate are added in the concentrated sulfuric acid, and low whipping speed is 100r/min～300r/mim, temperature is at-1 ℃～1 ℃, to add potassium permanganate, then temperature is warming up to 34 ℃～36 ℃ from-1 ℃～1 ℃, and low whipping speed is 100r/min～300r/mim, temperature is to react 18h～30h at 34 ℃～36 ℃, obtain initial action product, 2. to initial action product, dropwise add deionized water, then be cooled to 20 ℃～30 ℃, and low whipping speed is 100r/min～300r/mim, temperature is 20 ℃～30 ℃ reaction 10min～60min, obtain the suspension of brownish black, then dropwise adding mass concentration is 20%～40% H
2o
2the aqueous solution, till becoming brown color to the color of brownish black suspension, then under centrifugal speed 3000r/min～4000r/min, separation obtains brown color solid, then adopt the salt acid elution 3～5 times of 0.5mol/L～1.5mol/L, finally in temperature, be 50 ℃～70 ℃ and dry to constant weight, obtain graphite oxide.Other is identical with the specific embodiment one to three.
Adopt following verification experimental verification effect of the present invention:
Test one: plant the method for solvent-thermal method synthesizing zinc oxide/graphene composite material, specifically complete according to the following steps:
One, mix: under the condition that first low whipping speed is 200r/mim, graphite oxide is scattered in ethanol, then adds Zn (Ac)
2and mix, obtain mixed solution; Two, forming processes: the mixed solution first under 150 ℃ of conditions, step 1 being obtained carries out solvent heat treatment 8h, then adopts distilled water washing 3 times, and finally vacuum drying 6h under 70 ℃ of conditions, had both obtained zinc oxide/graphene composite material.
The mass ratio of the graphite oxide described in present embodiment step 1 and ethanol is 1:1000.
Graphite oxide described in present embodiment step 1 and Zn (Ac)
2mass ratio be 1:5.
Graphite oxide described in present embodiment step 1 adopts Hummer method to be prepared from, concrete steps are as follows: 1. first native graphite and sodium nitrate are added in the concentrated sulfuric acid, and low whipping speed is 200r/mim, temperature is to add potassium permanganate at 0 ℃, then temperature is warming up to 35 ℃ from 0 ℃, and low whipping speed is 200r/mim, temperature is to react 24h at 35 ℃, obtain initial action product, 2. to initial action product, dropwise add deionized water, then be cooled to 25 ℃, and low whipping speed is 200r/mim, temperature is 25 ℃ of reaction 15min, obtain the suspension of brownish black, then dropwise adding mass concentration is 30% H
2o
2the aqueous solution, till becoming brown color to the color of brownish black suspension, then under centrifugal speed 3500r/min, separation obtains brown color solid, then adopts the salt acid elution 4 times of 1mol/L, finally in temperature, is 60 ℃ and dries to constant weight, obtains graphite oxide.
Adopt the zinc oxide/graphene composite material of this test of electron microscope observation preparation, as depicted in figs. 1 and 2, as can be seen from Figure 1 zinc oxide/the graphene composite material of this test preparation is to using the zinc oxide nano-particle of Graphene as base material growth high dispersive, and can see that zinc oxide nano-particle distributes uniformly on Graphene, the size of zinc oxide nano-particle is about 10nm, Graphene size is about 4 μ m, as can be seen from Figure 1 the transparency of the zinc oxide/graphene composite material of this test preparation can prove that the Graphene obtaining is very thin, zinc oxide/graphene composite material edge to this test preparation amplifies as shown in Figure 2, from Fig. 2, proved the generation of thin layer graphite alkene, thickness is about 10nm.
Claims (1)
1. a method for solvent-thermal method synthesizing zinc oxide/graphene composite material, the method that it is characterized in that solvent-thermal method synthesizing zinc oxide/graphene composite material is to complete according to the following steps:
One, mix: under the condition that first low whipping speed is 200r/min, graphite oxide is scattered in ethanol, then adds Zn (Ac)
2and mix, obtain mixed solution; Two, forming processes: the mixed solution first under 150 ℃ of conditions, step 1 being obtained carries out solvent heat treatment 8h, then adopts distilled water washing 3 times, and finally vacuum drying 6h under 70 ℃ of conditions, obtains zinc oxide/graphene composite material;
The mass ratio of the graphite oxide described in step 1 and ethanol is 1:1000;
Graphite oxide described in step 1 and Zn (Ac)
2mass ratio be 1:5;
Graphite oxide described in step 1 adopts Hummer method to be prepared from, concrete steps are as follows: 1. first native graphite and sodium nitrate are added in the concentrated sulfuric acid, and low whipping speed is 200r/min, temperature is to add potassium permanganate at 0 ℃, then temperature is warming up to 35 ℃ from 0 ℃, and low whipping speed is 200r/min, temperature is to react 24h at 35 ℃, obtain initial action product, 2. to initial action product, dropwise add deionized water, then be cooled to 25 ℃, and low whipping speed is 200r/min, temperature is 25 ℃ of reaction 15min, obtain the suspension of brownish black, then dropwise adding mass concentration is 30% H
2o
2the aqueous solution, till becoming brown color to the color of brownish black suspension, then under centrifugal speed 3500r/min, separation obtains brown color solid, then adopts the salt acid elution 4 times of 1mol/L, finally in temperature, is 60 ℃ and dries to constant weight, obtains graphite oxide.
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| CN104069807A (en) * | 2014-06-19 | 2014-10-01 | 北京师范大学 | Preparation method and application of ZnO nano particle/graphene oxide composite material |
| CN104475076A (en) * | 2014-12-11 | 2015-04-01 | 上海烟草集团有限责任公司 | Preparation method of graphene-nano zinc oxide composite photocatalytical material for adsorbing and degrading nitrosamine |
| CN104667902B (en) * | 2015-03-02 | 2017-03-29 | 哈尔滨理工大学 | The method that sol method prepares ZnO exfoliated-graphite composites |
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| CN105749896A (en) * | 2016-02-15 | 2016-07-13 | 东南大学 | Zinc oxide/reduced graphene oxide aerogel and preparation method of zinc oxide/reduced graphene oxide aerogel |
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| CN107362803A (en) * | 2017-07-08 | 2017-11-21 | 蚌埠学院 | A kind of preparation method of magnetic graphite alkenyl zinc oxide nanometer composite material |
| CN110152603A (en) * | 2018-04-12 | 2019-08-23 | 济南开发区星火科学技术研究院 | A kind of graphene adsorbent for gasoline desulfurization |
| CN109399616A (en) * | 2018-12-11 | 2019-03-01 | 四川省安德盖姆石墨烯科技有限公司 | A kind of graphene organic material and its application in gas sensor |
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