CN104801292A - Preparation method for zinc oxide hollow nanosphere/graphene composite material - Google Patents
Preparation method for zinc oxide hollow nanosphere/graphene composite material Download PDFInfo
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Abstract
The invention relates to a preparation method for a zinc oxide hollow nanosphere/graphene composite material, in particular to a preparation for a graphene composite material, and aims to solve the problems that in the prior art, zinc oxide hollow nanospheres cannot be grown on graphene lamellas according to a one-step hydrothermal method and a nano-scale zinc oxide hollow nanosphere/graphene composite material cannot be prepared. The preparation method for the zinc oxide hollow nanosphere/graphene composite material comprises the following steps: (1) preparing a reacting liquid; (2) carrying out a hydrothermal reaction to prepare a reactant; (3) carrying out washing and drying to obtain the zinc oxide hollow nanosphere/graphene composite material. The zinc oxide hollow nanosphere/graphene composite material prepared according to the one-step hydrothermal method has the advantages that the zinc oxide hollow nanospheres can be uniformly and densely grown on the surface of graphene in an in-situ manner, and have an average particle diameter of 25 nm. According to the preparation method for the zinc oxide hollow nanosphere/graphene composite material, the zinc oxide hollow nanosphere/graphene composite material can be obtained.
Description
Technical field
The present invention relates to a kind of preparation method of graphene composite material.
Background technology
Zinc oxide is a kind of n-type semiconductor, has the advantages such as large exciton bind energy (being 60meV under room temperature), cheap, safety non-toxic, and is extensively used in biology sensor, solar cell, photocatalysis etc.But because zinc oxide energy gap is 3.37eV, when the light only having wavelength to be less than 368nm is radiated at nano-ZnO surface, competence exertion photocatalysis performance.Large quantifier elimination shows, zinc oxide and Graphene recombination energy improve the photocatalysis performance of zinc oxide to a certain extent.Because Graphene is a kind of by carbon atom sp
2the hexangle type of hybridized orbit composition is the flat film of honeycomb lattice shape, it has the advantages such as good optics, electricity and mechanical performance, very high electron mobility and high-specific surface area, thus becomes the multifunctional material of conventional carrier material and electronics or hole-transfer.
Up to now, researchers have successfully prepared the zinc oxide/graphene composite material of different-shape, as zinc-oxide nano point, wire zinc oxide, bar-shaped zinc oxide, flower shape zinc oxide and spherical zinc oxide (being divided into medicine ball and hollow ball) etc.Compared with other patterns, zinc oxide hollow ball has the characteristics such as specific area is large, density is low, surface penetration ability is strong, has wide practical use in photocatalysis, microreactor and light material etc.But large quantifier elimination display, zinc oxide hollow ball/graphene composite material rarely has report, and this is because this kind of pattern is difficult to caused by regulation and control.In the synthetic method of the zinc oxide hollow ball/graphene composite material reported, have with an organic solvent as reaction system, this just increases the danger of reaction and the possibility of contaminated environment.Be exactly also prepare zinc oxide hollow ball/graphene composite material step by step by template in addition, this just makes preparation process consuming time and complicated.And prepared zinc oxide hollow ball is submicron order (0.5 μm ~ 1 μm) or deep-submicron (100nm ~ 0.5 μm), limit its photocatalysis performance because of its size is large, specific area is little characteristic.
Summary of the invention
The object of the invention is to solve and existingly one step hydro thermal method can not be used to make zinc-oxide nano hollow ball growth in situ on graphene sheet layer and the problem of nano level zinc-oxide nano hollow ball/graphene composite material cannot be prepared, and the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material is provided.
A preparation method for zinc-oxide nano hollow ball/graphene composite material, completes according to the following steps:
One, organic zinc salt is joined in deionized water, then low whipping speed is stir 5min ~ 10min under 300r/min ~ 500r/min, obtains organic slat solution; By graphene oxide solution and organic slat solution mixing, low whipping speed is stir 0.5h ~ 1h under 300r/min ~ 500r/min, then adds alkali source solution, then low whipping speed is stirring reaction 0.5h ~ 2h under 300r/min ~ 500r/min, obtains reactant liquor;
The concentration of the organic zinc salt solution described in step one is 0.02mol/L ~ 0.07mol/L;
The concentration of the graphene oxide solution described in step one is 0.1mg/mL ~ 5mg/mL;
The volume ratio of the graphene oxide solution described in step one and organic zinc salt solution is (3 ~ 20): 80;
The concentration of the alkali source solution described in step one is 0.01mol/L ~ 0.5mol/L;
The quality of the organic zinc salt described in step one and the volume ratio of alkali source solution are (0.8g ~ 2.3g): 175mL;
Two, reactant liquor is joined in hydrothermal reaction kettle, be stirring reaction 6h ~ 24h under the condition of 120 DEG C ~ 200 DEG C in temperature, then reactor is naturally cooled to room temperature, obtain reactant;
Three, use deionized water and absolute ethyl alcohol to wash 3 times to reactant respectively, obtain the reactant after cleaning; By the reactant dry 12h ~ 24h at temperature is 40 DEG C ~ 80 DEG C after cleaning, obtain zinc-oxide nano hollow ball/graphene composite material.
Principle of the present invention:
In the present invention, organic salt, graphene oxide and alkali source are uniformly dispersed in aqueous, and due to electrostatic interaction, the metal ion of positively charged and the electronegative functional group of surface of graphene oxide interact, and cause adsorption of metal ions in surface of graphene oxide; In hydro-thermal reaction, along with the rising of reaction temperature, alkali source decomposes, and metal ion generates Zinc oxide nanoparticle gradually and is dispersed in surface of graphene oxide uniformly; Then along with the prolongation in reaction time, graphene oxide is reduced into Graphene, and due to the effect of Ostwald ripening, the Zinc oxide nanoparticle of graphenic surface changes zinc-oxide nano hollow ball gradually into, thus defines zinc-oxide nano hollow ball/graphene composite material.
Advantage of the present invention:
One, the invention provides a kind of simple, effective method to prepare zinc-oxide nano hollow ball/graphene composite material, solve and existingly one step hydro thermal method can not be used to make zinc-oxide nano hollow ball growth in situ on graphene sheet layer and the problem of nano level zinc oxide hollow ball/graphene composite material cannot be prepared;
Two, the present invention adopts one step hydro thermal method to prepare zinc-oxide nano hollow ball/graphene composite material, and the evenly intensive growth in situ of zinc-oxide nano hollow ball is at graphenic surface, and wherein the average grain diameter of zinc-oxide nano hollow ball is only 25nm;
Three, the present invention adopts water to be reaction system, and required reagent is cheap, and safety non-toxic, the hidden danger of nonpollution environment, and the reaction condition of preparation method is gentle, consersion unit used is simple, is conducive to large-scale production;
Four, the present invention adopts simple, safe one step hydro thermal method, has not only effectively prepared undersized zinc-oxide nano hollow ball/graphene composite material, and zinc-oxide nano hollow ball can evenly intensively be dispersed on graphene sheet layer; The visible light activity of the zinc-oxide nano hollow ball/graphene composite material prepared by the present invention is better than business ZnO, to the clearance of methylene blue up to 80%, higher by 32% to the clearance of methylene blue than commercial oxidation zinc; Zinc-oxide nano hollow ball/the graphene composite material of preparation of the present invention has significant effect in visible light photocatalytic degradation methylene blue, has good application prospect in water treatment field such as dye wastewater treatment.
Accompanying drawing explanation
Fig. 1 is the low power transmission electron microscope picture of zinc-oxide nano hollow ball/graphene composite material prepared by test one;
Fig. 2 is the high power transmission electron microscope picture of zinc-oxide nano hollow ball/graphene composite material prepared by test one;
Fig. 3 is the grain size distribution of zinc-oxide nano hollow ball in the zinc-oxide nano hollow ball/graphene composite material of test one preparation;
Fig. 4 is the X-ray diffractogram of zinc-oxide nano hollow ball/graphene composite material prepared by test one;
Fig. 5 is the x-ray photoelectron energy spectrogram of zinc-oxide nano hollow ball/graphene composite material prepared by test one, in Fig. 5,1 is the 3d track absworption peak of Zn, 2 is the 3p track absworption peak of Zn, 3 is the 3s track absworption peak of Zn, 4 is the 1s track absworption peak of C, 5 is the 1s track absworption peak of O, and 6 is the 2p of Zn
3/2track absworption peak, 7 is the 2p of Zn
1/2track absworption peak;
Fig. 6 is the swarming fitted figure of C1s absworption peak in the x-ray photoelectron energy spectrogram of zinc-oxide nano hollow ball/graphene composite material of preparing of test one and graphene oxide, in Fig. 6,1,2 and 3 is the swarming fitted figure of the C1s absworption peak of graphene oxide, and 4,5 and 6 is the swarming fitted figure of the C1s absworption peak of zinc-oxide nano hollow ball/graphene composite material prepared by test one;
Fig. 7 is the curve map of degradation of methylene blue under different condition; In Fig. 7,1 is the curve map of degradation of methylene blue under visible light exposure, the 2 zinc-oxide nano hollow ball/graphene composite materials prepared for test one adsorb the curve map of methylene blue when there is no light irradiation, 3 is the curve map of commercial oxidation zinc degradation of methylene blue under visible light exposure, and 4 is the curve map of zinc-oxide nano hollow ball/graphene composite material photocatalytic degradation methylene blue under visible light exposure prepared by test one.
Detailed description of the invention
Detailed description of the invention one: present embodiment is that the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material completes according to the following steps:
One, organic zinc salt is joined in deionized water, then low whipping speed is stir 5min ~ 10min under 300r/min ~ 500r/min, obtains organic slat solution; By graphene oxide solution and organic slat solution mixing, low whipping speed is stir 0.5h ~ 1h under 300r/min ~ 500r/min, then adds alkali source solution, then low whipping speed is stirring reaction 0.5h ~ 2h under 300r/min ~ 500r/min, obtains reactant liquor;
The concentration of the organic zinc salt solution described in step one is 0.02mol/L ~ 0.07mol/L;
The concentration of the graphene oxide solution described in step one is 0.1mg/mL ~ 5mg/mL;
The volume ratio of the graphene oxide solution described in step one and organic zinc salt solution is (3 ~ 20): 80;
The concentration of the alkali source solution described in step one is 0.01mol/L ~ 0.5mol/L;
The quality of the organic zinc salt described in step one and the volume ratio of alkali source solution are (0.8g ~ 2.3g): 175mL;
Two, reactant liquor is joined in hydrothermal reaction kettle, be stirring reaction 6h ~ 24h under the condition of 120 DEG C ~ 200 DEG C in temperature, then reactor is naturally cooled to room temperature, obtain reactant;
Three, use deionized water and absolute ethyl alcohol to wash 3 times to reactant respectively, obtain the reactant after cleaning; By the reactant dry 12h ~ 24h at temperature is 40 DEG C ~ 80 DEG C after cleaning, obtain zinc-oxide nano hollow ball/graphene composite material.
Principle of the present invention:
In the present invention, organic salt, graphene oxide and alkali source are uniformly dispersed in aqueous, and due to electrostatic interaction, the metal ion of positively charged and the electronegative functional group of surface of graphene oxide interact, and cause adsorption of metal ions in surface of graphene oxide; In hydro-thermal reaction, along with the rising of reaction temperature, alkali source decomposes, and metal ion generates Zinc oxide nanoparticle gradually and is dispersed in surface of graphene oxide uniformly; Then along with the prolongation in reaction time, graphene oxide is reduced into Graphene, and due to the effect of Ostwald ripening, the Zinc oxide nanoparticle of surface of graphene oxide changes zinc-oxide nano hollow ball gradually into, thus defines zinc-oxide nano hollow ball/graphene composite material.
The advantage of present embodiment:
One, present embodiments provide for a kind of simple, effective method to prepare zinc-oxide nano hollow ball/graphene composite material, solve and existingly one step hydro thermal method can not be used to make zinc-oxide nano hollow ball growth in situ on graphene sheet layer and the problem of nano level zinc oxide hollow ball/graphene composite material cannot be prepared;
Two, present embodiment adopts one step hydro thermal method to prepare zinc-oxide nano hollow ball/graphene composite material, and the evenly intensive growth in situ of zinc-oxide nano hollow ball is at graphenic surface, and wherein the average grain diameter of zinc-oxide nano hollow ball is only 25nm;
Three, present embodiment adopts water to be reaction system, and required reagent is cheap, and safety non-toxic, the hidden danger of nonpollution environment, and the reaction condition of preparation method is gentle, consersion unit used is simple, is conducive to large-scale production;
Four, present embodiment adopts simple, safe one step hydro thermal method, has not only effectively prepared undersized zinc-oxide nano hollow ball/graphene composite material, and zinc-oxide nano hollow ball can evenly intensively be dispersed on graphene sheet layer; The visible light activity of the zinc-oxide nano hollow ball/graphene composite material prepared by present embodiment is better than business ZnO, to the clearance of methylene blue up to 80%, higher by 32% to the clearance of methylene blue than commercial oxidation zinc; Zinc-oxide nano hollow ball/the graphene composite material of the preparation of present embodiment has significant effect in visible light photocatalytic degradation methylene blue, has good application prospect in water treatment field such as dye wastewater treatment.
Detailed description of the invention two: present embodiment and detailed description of the invention one difference are: the organic zinc salt described in step one is zinc acetate, carboxyl acetic acid zinc or zinc acetylacetonate.Other steps are identical with detailed description of the invention one.
Detailed description of the invention three: one of present embodiment and detailed description of the invention one or two difference is: the graphene oxide in the graphene oxide solution described in step one is standby by Hummers legal system.Other steps are identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three difference is: in the alkali source solution described in step one alkali source to be mass fraction be 25% ~ 28% ammoniacal liquor, urea or carbonic hydroammonium.Other steps are identical with detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four difference is: join in hydrothermal reaction kettle by reactant liquor in step 2, be stirring reaction 6h ~ 12h under the condition of 120 DEG C ~ 160 DEG C in temperature, again reactor is naturally cooled to room temperature, obtain reactant.Other steps are identical with detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five difference is: in step 2, reactant liquor is joined in hydrothermal reaction kettle, be stirring reaction 12h ~ 24h under the condition of 160 DEG C ~ 200 DEG C in temperature, again reactor is naturally cooled to room temperature, obtain reactant.Other steps are identical with detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six difference is: the concentration of the organic slat solution described in step one is 0.02mol/L ~ 0.05mol/L.Other steps are identical with detailed description of the invention one to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven difference is: the concentration of the graphene oxide solution described in step one is 1mg/mL ~ 5mg/mL.Other steps are identical with detailed description of the invention one to seven.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight difference is: the volume ratio of the graphene oxide solution described in step one and organic zinc salt solution is (3 ~ 12): 80.Other steps are identical with detailed description of the invention one to eight.
Detailed description of the invention ten: one of present embodiment and detailed description of the invention one to nine difference is: the quality of the organic zinc salt described in step one and the volume ratio of alkali source solution are (1.2g ~ 2.3g): 175mL.Other steps are identical with detailed description of the invention one to nine.
Adopt following verification experimental verification beneficial effect of the present invention:
Test one: a kind of preparation method of zinc-oxide nano hollow ball/graphene composite material, completes according to the following steps:
One, join in deionized water by zinc acetate, low whipping speed is stir 8min under 500r/min, obtains acetic acid zinc solution; By graphene oxide solution and acetic acid zinc solution mixing, low whipping speed is stir 1h under 500r/min, then adds urea liquid, then low whipping speed is stirring reaction 1h under 500r/min, obtains reactant liquor;
The concentration of the organic zinc salt solution described in step one is 0.046mol/L;
The concentration of the graphene oxide solution described in step one is 4mg/mL;
The volume ratio of the graphene oxide solution described in step one and acetic acid zinc solution is 1:8;
The concentration of the alkali source solution described in step one is 0.026mol/L;
The quality of the zinc acetate described in step one and the volume ratio of alkali source solution are 2g:175mL;
Two, reactant liquor is joined in hydrothermal reaction kettle, be stirring reaction 12h under the condition of 160 DEG C in temperature, then reactor is naturally cooled to room temperature, obtain reactant;
Three, use deionized water and absolute ethyl alcohol to wash 3 times to reactant respectively, obtain the reactant after cleaning; By the reactant dry 12h at temperature is 50 DEG C after cleaning, obtain zinc-oxide nano hollow ball/graphene composite material.
Fig. 1 is the low power transmission electron microscope picture of zinc-oxide nano hollow ball/graphene composite material prepared by test one;
Fig. 2 is the high power transmission electron microscope picture of zinc-oxide nano hollow ball/graphene composite material prepared by test one;
Fig. 3 is the grain size distribution of zinc-oxide nano hollow ball in the zinc-oxide nano hollow ball/graphene composite material of test one preparation;
As can be seen from Figure 1, the zinc-oxide nano hollow ball/graphene composite material of test one preparation is two-dimensional sheet structure, and the zinc oxide of preparation is hollow nanosphere, and is evenly intensively dispersed on graphene sheet layer;
As can be seen from Figure 2, the zinc oxide in the zinc-oxide nano hollow ball/graphene composite material of test one preparation is that hollow nanosphere is made up of nano particle, and the spacing of lattice of 0.26nm is for (002) crystal face of zinc oxide;
As can be seen from Figure 3, the zinc-oxide nano hollow ball particle diameter distribution uniform in the zinc-oxide nano hollow ball/graphene composite material of test one preparation, average grain diameter is 25nm;
Fig. 4 is the X-ray diffractogram of zinc-oxide nano hollow ball/graphene composite material prepared by test one;
As can be seen from Figure 4, zinc-oxide nano hollow ball/the graphene composite material of test one preparation has good crystal formation, and its XRD schemes completely corresponding with the standard diagram (PDF No.36-1451) of the ZnO of hexagonal wurtzite structure, illustrates that hollow nanosphere prepared by test one is zinc oxide.
Fig. 5 is the x-ray photoelectron energy spectrogram of zinc-oxide nano hollow ball/graphene composite material prepared by test one, in Fig. 5,1 is the 3d track absworption peak of Zn, 2 is the 3p track absworption peak of Zn, 3 is the 3s track absworption peak of Zn, 4 is the 1s track absworption peak of C, 5 is the 1s track absworption peak of O, and 6 is the 2p of Zn
3/2track absworption peak, 7 is the 2p of Zn
1/2track absworption peak;
Obviously can find the absworption peak of C element, O element and Zn element in Figure 5, illustrate that the material that test one step 3 obtains is zinc-oxide nano hollow ball/graphene composite material.
Fig. 6 is the swarming fitted figure of C1s absworption peak in the x-ray photoelectron energy spectrogram of zinc-oxide nano hollow ball/graphene composite material of preparing of test one and graphene oxide, in Fig. 6,1,2 and 3 is the swarming fitted figure of the C1s absworption peak of graphene oxide, and 4,5 and 6 is the swarming fitted figure of the C1s absworption peak of zinc-oxide nano hollow ball/graphene composite material prepared by test one;
The corresponding C-C functional group in the peak of 1 and 4 in Fig. 6, the corresponding O-C/C=O functional group in peak of 2 and 5, the corresponding O-C=O functional group in peak of 3 and 6; Can obviously find out in figure 6, compared with the swarming fitted figure of the C1s absworption peak of graphene oxide, in zinc-oxide nano hollow ball/graphene composite material, C-C peak increases by force, and O-C/C=O and O-C=O peak reduces by force, illustrate that graphene oxide is in preparation process, be reduced into Graphene.
Test two: the method for degradation of methylene blue under visible light exposure, specifically completes according to the following steps:
This test adopt light source to be the xenon lamp edge filter of 400nm (configuration) of 300W, concrete steps are: be after the 50mL methylene blue solution of 30mg/L in the dark stirs 30min by concentration, open xenon lamp again, carry out photochemical reaction, take out the sample of 1mL every 20min, after filtration, dilution, measure the methylene blue concentration under the different light time.
Test three: the method for zinc-oxide nano hollow ball/graphene composite material absorption methylene blue prepared by service test one specifically completes according to the following steps:
Under dark condition, it is stir 30min in the 50mL methylene blue solution of 30mg/L that the zinc-oxide nano hollow ball/graphene composite material of 10mg test one preparation is added to concentration, take out the sample of 1mL again every 20min, after filtration, dilution, measure the methylene blue concentration under the different light time.
Test four: use the method for commercial oxidation zinc degradation of methylene blue under visible light exposure specifically to complete according to the following steps:
This test adopt light source to be the xenon lamp edge filter of 400nm (configuration) of 300W, concrete steps are: 10mg business ZnO being added to concentration is in the 50mL methylene blue solution of 30mg/L, first in the dark stir 30min, make business ZnO reach adsorption-desorption balance; Open xenon lamp again, carry out photochemical reaction, take out the sample of 1mL every 20min, after filtration, dilution, measure the methylene blue concentration under the different light time.
Test five: the method for zinc-oxide nano hollow ball/graphene composite material degradation of methylene blue under visible light exposure prepared by service test one completes according to the following steps:
This test adopt light source to be the xenon lamp edge filter of 400nm (configuration) of 300W, concrete steps are: it is in the 50mL methylene blue solution of 30mg/L that the zinc-oxide nano hollow ball/graphene composite material of 10mg test one preparation is added to concentration, first in the dark stir 30min, make composite reach adsorption-desorption balance; Open xenon lamp again, carry out photochemical reaction, take out the sample of 1mL every 20min, after filtration, dilution, measure the methylene blue absorbance under the different light time.
Fig. 7 is the curve map of degradation of methylene blue under different condition; In Fig. 7,1 is the curve map of degradation of methylene blue under visible light exposure, the curve map of the 2 zinc-oxide nano hollow ball prepared for test one/graphene composite material absorption methylene blue, 3 is the curve map of commercial oxidation zinc degradation of methylene blue under visible light exposure, and 4 is the curve map of zinc-oxide nano hollow ball/graphene composite material photocatalytic degradation methylene blue under visible light exposure prepared by test one.
As can be seen from Figure 7, zinc-oxide nano hollow ball/the graphene composite material of test one preparation is obviously better than the degradation effect under other conditions under visible light to the degradation effect of methylene blue, zinc-oxide nano hollow ball/graphene composite material of preparing of service test one under visible light to methylene blue clearance can up to 80%, improve 22%, 55% and 32% than the clearance of the Visible Light Induced Photocatalytic of business ZnO, separately light degradation and dark place absorption separately respectively.
Claims (10)
1. a preparation method for zinc-oxide nano hollow ball/graphene composite material, is characterized in that the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material completes according to the following steps:
One, join in deionized water by organic zinc salt, low whipping speed is stir 5min ~ 10min under 300r/min ~ 500r/min, obtains organic slat solution; By graphene oxide solution and organic slat solution mixing, low whipping speed is stir 0.5h ~ 1h under 300r/min ~ 500r/min, then adds alkali source solution, then low whipping speed is stirring reaction 0.5h ~ 2h under 300r/min ~ 500r/min, obtains reactant liquor;
The concentration of the organic slat solution described in step one is 0.02mol/L ~ 0.07mol/L;
The concentration of the graphene oxide solution described in step one is 0.1mg/mL ~ 5mg/mL;
The volume ratio of the graphene oxide solution described in step one and organic zinc salt solution is (3 ~ 20): 80;
The concentration of the alkali source solution described in step one is 0.01mol/L ~ 0.5mol/L;
The quality of the organic zinc salt described in step one and the volume ratio of alkali source solution are (0.8g ~ 2.3g): 175mL;
Two, reactant liquor is joined in hydrothermal reaction kettle, be stirring reaction 6h ~ 24h under the condition of 120 DEG C ~ 200 DEG C in temperature, then reactor is naturally cooled to room temperature, obtain reactant;
Three, use deionized water and absolute ethyl alcohol to wash 3 times to reactant respectively, obtain the reactant after cleaning; By the reactant dry 12h ~ 24h at temperature is 40 DEG C ~ 80 DEG C after cleaning, obtain zinc-oxide nano hollow ball/graphene composite material.
2. the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material according to claim 1, is characterized in that the organic zinc salt described in step one is zinc acetate, carboxyl acetic acid zinc or zinc acetylacetonate.
3. the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material according to claim 1, is characterized in that the graphene oxide in the graphene oxide solution described in step one is standby by Hummers legal system.
4. the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material according to claim 1, is characterized in that alkali source in the alkali source solution described in step one to be mass fraction is the ammoniacal liquor of 25% ~ 28%, urea or carbonic hydroammonium.
5. the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material according to claim 1, it is characterized in that in step 2, reactant liquor being joined in hydrothermal reaction kettle, be stirring reaction 6h ~ 12h under the condition of 120 DEG C ~ 160 DEG C in temperature, again reactor is naturally cooled to room temperature, obtain reactant.
6. the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material according to claim 1, it is characterized in that in step 2, reactant liquor being joined in hydrothermal reaction kettle, be stirring reaction 12h ~ 24h under the condition of 160 DEG C ~ 200 DEG C in temperature, again reactor is naturally cooled to room temperature, obtain reactant.
7. the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material according to claim 1, is characterized in that the concentration of the organic slat solution described in step one is 0.02mol/L ~ 0.05mol/L.
8. the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material according to claim 1, is characterized in that the concentration of the graphene oxide solution described in step one is 1mg/mL ~ 5mg/mL.
9. the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material according to claim 1, is characterized in that the volume ratio of the graphene oxide solution described in step one and organic zinc salt solution is for (3 ~ 12): 80.
10. the preparation method of a kind of zinc-oxide nano hollow ball/graphene composite material according to claim 1, is characterized in that the quality of the organic zinc salt described in step one and the volume ratio of alkali source solution are (1.2g ~ 2.3g): 175mL.
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