CN103734188A - Preparation method and applications of zinc oxide-graphene oxide composite nanomaterial - Google Patents
Preparation method and applications of zinc oxide-graphene oxide composite nanomaterial Download PDFInfo
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Abstract
The invention discloses a preparation method of a zinc oxide-graphene oxide composite nanomaterial, which is implemented through the following steps: by taking soluble divalent zinc ions as a zinc source, taking the soluble divalent zinc ions, graphene oxide and alkali liquor as reactants together, according to a situation that the mass ratio of the zinc ions to the graphene oxide is (1-3): 1, forming a solute composition; by taking alcohol as a solvent, forming a reaction solution mixed system; and after a reaction is performed for 30 min-5 h, purifying a substrate by using centrifugation and washing methods, so that the zinc oxide-graphene oxide composite nanomaterial is obtained. The zinc oxide-graphene oxide composite nanomaterial prepared according to the invention has an effective antibacterial ability at low concentration, and has no obvious toxic action on cells. According to the invention, the operation process is simple, the reaction process has no obvious pollution to the environment, the production cost is low, and the prepared nanomaterial can be applied to the antisepsis of medical apparatuses and instruments, and has a potential in commercial large-scale production.
Description
Technical field
The present invention relates to a kind of nano material preparation and application, particularly relate to a kind of Nano-composite materials and application take graphene oxide as carrier, be applied to nano inorganic material, antibacterial applications and cell toxicology technical field.
Background technology
Day by day serious along with 21 century environmental pollution, pathogenic microorganism becomes one of key factor threatening human health.But some traditional bactericide exist problems such as toxicity is large, resistance, thereby the research of development of new antibacterial green material is extremely urgent.
ZnO itself possesses good antibacterial characteristics, and Gram-negative bacteria and positive bacteria are had to fungistatic effect.When ZnO size drops to nanoscale, its antibacterial activity is enhancing trend.Along with the preparation of nano material and the development of application, nano ZnO material is found to have the performance that is better than conventional ZnO.Nano ZnO material antibacterial effect is better than zinc oxide.Nano-ZnO, owing to being easily adsorbed on bacterium surface, destroys cell wall, affects Growth of Cells; Nano-ZnO discharges zinc ion, causes that free radical increases, and causes bacterium death.In addition, ZnO nano particle can be adsorbed on cell wall surface and cause that wadding is heavy.But the problem of nano-ZnO anti-biotic material is: the damage that also can cause other cells under effective antibacterial concentration is even dead; The ZnO nano material with bigger serface is easily reunited, and weakens its antibacterial ability.
Emerging nano material graphene oxide GO has a large amount of oxy radicals, the feature of large specific surface area, powerful ion-exchange capacity, and these features have been given its good compound ability.Using GO, as the prepared GO composite nano materials of carrier, good stability, dispersiveness and biocompatibility have been demonstrated.Current research shows that GO also can pass through to destroy the growth of anti-bacteria to a certain extent of colibacillary cell membrane, but its fungistatic effect is still not ideal enough.
Summary of the invention
In order to solve zinc oxide bad dispersibility, the unmanageable prior art problem of particle diameter during load on graphene oxide, the object of the invention is to overcome the deficiency that prior art exists, a kind of preparation method and application of zinc oxide-graphene oxide composite nano materials are provided, the two characteristic of combining nano ZnO and GO, prepares novel antibacterial green material ZnO/GO compound.Preparation method of the present invention is easy, with low cost, good anti-bacterial effect, and bio-toxicity is low.The anti-microbial property of composite nano materials and biological safety are verified by the inhibitory action to bacterial growth with to the toxicity of cell respectively, realize safe and effective antibacterial object.
For reaching foregoing invention, create object, the present invention adopts following technical proposals:
A kind of preparation method of zinc oxide-graphene oxide composite nano materials, comprise the following steps: take soluble divalent zinc ion as zinc source, with graphene oxide and alkali lye together as reactant, according to the quality proportioning of zinc ion and graphene oxide, be (1～3): 1 quality proportioning forms solute composition, take alcohol as solvent, form reaction solution mixed system, make to carry out one-step method reaction, the OH that the alkali lye in reaction solution mixed system is progressively ionized out between the solute composition of reaction solution mixed system
-with Zn
2+form Zn-OH complex, fully contact with the oxy radical of graphene oxide again, be attached to the surface of graphene oxide, reaction solution mixed system is not under higher than 80 ℃ of conditions, make the dehydrogenation of Zn-OH complex become ZnO, the zinc oxide nucleus uniform load forming is on graphene oxide surface, the one-step method reaction time is 30 min～5 h, after reaction finishes, reaction solution mixed system is cooled to room temperature, to adding in reaction solution mixed system, be equivalent to the more than 2 times n-hexane of reaction solution mixed system volume again, in the environment of 4 ℃, standing sedimentation spends the night, then after abandoning supernatant, with centrifugal, with washing methods, substrate is carried out to purifying, after dry, finally obtain zinc oxide-graphene oxide composite nano materials, the particle diameter that loads on the Zinc oxide nanoparticle on graphene oxide surface is (2～200) nm.
The present invention is preferably by changing each component ratio and the one-step method synthesising reacting time of reactant, realizes the control in the load capacity on graphene oxide surface to Zinc oxide nanoparticle size and zinc oxide.
As the preferred technical scheme of technique scheme of the present invention, adopt Zinc diacetate dihydrate that zinc ion is provided, according to the quality proportioning of Zinc diacetate dihydrate and graphene oxide, be (4～9): 1 quality proportioning forms solute composition, take alcohol as solvent, form reaction solution mixed system.
As the preferred technical scheme of technique scheme of the present invention, after one-step method reaction finishes, reaction solution mixed system is cooled to room temperature, then adds phase n-hexane in reaction solution mixed system, in the environment of 4 ℃, standing sedimentation spends the night.
The present invention also provides a kind of application of the zinc oxide-graphene oxide composite nano materials obtaining by preparation method of the present invention, take soluble divalent zinc ion as zinc source, with graphene oxide and solubility hydroxide together as reactant, according to the quality proportioning according to zinc ion and graphene oxide, be (1～3): 1 quality proportioning forms solute composition proportioning ratio and forms solute composition, take alcohol as solvent, form reaction solution mixed system, reaction solution mixed system is not under higher than 80 ℃ of conditions, carry out one-step method reaction, reaction time is 30 min～5 h, obtain the particle diameter of Zinc oxide nanoparticle for zinc oxide-graphene oxide composite nano materials of (2～200) nm, effectively bacteria growing inhibiting, and cause bacterium death.
The dispersion liquid that adopts above-mentioned zinc oxide-graphene oxide composite nano materials to prepare while being preferably 2.5～10.0 μ g/mL as the dosage of bactericide, can suppressing safely and effectively Escherichia coli Growth, and cause bacterium death in 12 h.
The dispersion liquid that adopts zinc oxide-graphene oxide composite nano materials to prepare while being preferably 7.5～10.0 μ g/mL as the dosage of bactericide, can suppressing safely and effectively Escherichia coli Growth, and cause bacterium death in 18h.
While adopting zinc oxide-graphene oxide composite nano materials to prepare dispersion liquid as bactericide, preferably adopting deionized water is dispersant.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. the invention solves zinc oxide bad dispersibility, the unmanageable problem of particle diameter during load on graphene oxide, in preparation process, utilize static and the complexing of oxy radical on ZnO and GO, in gentle condition, next step has synthesized the ZnO/GO composite nano materials with high antibacterial activity and low cytotoxicity, even if there is efficient antibacterial ability under low concentration, for cell, there is no obvious toxic action simultaneously yet;
2. the present invention is by changing each component ratio and the one-step method synthesising reacting time of reactant, realizes the control in the load capacity on graphene oxide surface to Zinc oxide nanoparticle size and zinc oxide, and industrial being easy to realized;
3. very simple possible of method of operating of the present invention, course of reaction is to environment without obvious pollution, and production cost is low, can be applied to the antibacterial of medicine equipment and equipment, and environmental pollution is little, has commercial size productive potential.
Accompanying drawing explanation
Fig. 1 is the low power transmission electron microscope TEM photo that utilizes ZnO/GO composite nano materials prepared by the embodiment of the present invention one method.
Fig. 2 is the low power transmission electron microscope TEM photo that utilizes ZnO/GO composite nano materials prepared by the embodiment of the present invention two methods.
Fig. 3 is the high power transmission electron microscope HR-TEM photo figure that utilizes ZnO/GO composite nano materials prepared by the embodiment of the present invention two methods.
Fig. 4 is the X-ray diffractogram that utilizes ZnO/GO composite nano materials prepared by the embodiment of the present invention two methods.
Fig. 5 is the inhibition zone antibacterial experiment comparison diagram that utilizes ZnO/GO composite nano materials variable concentrations prepared by the embodiment of the present invention two methods.
Fig. 6 is the low power transmission electron microscope TEM photo that utilizes the standby ZnO/GO composite nano materials of embodiment of the present invention tripartite legal system.
Fig. 7 is the low power transmission electron microscope TEM photo that utilizes the standby ZnO/GO composite nano materials of embodiment of the present invention four directions legal system.
Fig. 8 is the ZnO/GO composite nano materials variable concentrations of the embodiment of the present invention five and the antibacterial experiment comparison diagram of different time.
Fig. 9 is the ZnO/GO composite nano materials of the embodiment of the present invention six and the colibacillary SEM SEM photo comparison diagram of Escherichia coli effect front and back.
Figure 10 is the cell viability figure after ZnO/GO composite nano materials and the HeLa co-culture of cells of the embodiment of the present invention seven.
Embodiment
Details are as follows for the preferred embodiments of the present invention:
embodiment mono-:
In the present embodiment, the preparation method's of zinc oxide-graphene oxide composite nano materials step is as follows:
Take absolute ethyl alcohol as solvent, form reaction solution mixed system: the Zn (Ac) that takes 0.0025mol
22H
2o is dispersed in 50 mL absolute ethyl alcohols, forms zinc source, vigorous stirring reaction 20 minutes under 80 ℃ of conditions.Meanwhile, adopt Hummer ' s oxidizing process to prepare GO, claim 0.2 g LiOH2H
2o and 60 mg GO, be dispersed in respectively in 20 mL and 30 mL absolute ethyl alcohols, under the state of vigorous stirring, both mixed, and mixed liquor is dropwise added in zinc acetate mixed solution, continues stirring reaction 30 minutes.The OH that LiOH alkali lye in reaction solution mixed system is progressively ionized out
-with Zn
2+form Zn-OH complex, fully contact with the oxy radical of GO again, be attached to the surface of GO, reaction solution mixed system is under 80 ℃ of conditions, make the dehydrogenation of Zn-OH complex become ZnO, the zinc oxide nucleus uniform load forming, on GO surface, by controlling the time of nucleus growth, realizes the synthetic ZnO/GO composite nano materials with high-efficiency antimicrobial characteristic of one-step method.Reaction finishes, and is cooled to after room temperature, adds the n-hexane that is equivalent to mixed liquor two volumes, puts into 4 ℃ of refrigerator standing sedimentations and spends the night.After supernatant discarded, by absolute ethyl alcohol and deionized water, substrate is fully washed 3 times, be placed in 60 ℃ of vacuum drying ovens dry.This material is carried out to structure and performance characterization, referring to Fig. 1, from figure, can clearly see the upper big or small homogeneous of GO, distribution Zinc oxide nanoparticle comparatively uniformly.
In the present embodiment, reactant feed adopts analytically pure Zn (Ac)
22H
2o and pass through the GO that Hummer ' s improved method makes.In preparation process, just utilize some simple solvents, therefore prepare resulting materials and have the characteristic of environmental protection.In the ZnO/GO composite nano materials obtaining, the ZnO nano uniform particles being carried on GO distributes.
embodiment bis-:
The present embodiment and embodiment mono-are basic identical, and special feature is:
In the present embodiment, the preparation method's of zinc oxide-graphene oxide composite nano materials step is as follows:
Take the Zn (Ac) of 0.0025mol
22H
2o is dispersed in 50 mL absolute ethyl alcohols, vigorous stirring reaction 20 minutes under 80 ℃ of conditions.Meanwhile, adopt Hummer ' s oxidizing process to prepare GO, claim 0.2 g LiOH2H
2o and 60 mg GO, be dispersed in respectively in 20 mL and 30 mL absolute ethyl alcohols, under the state of vigorous stirring, both mixed, and mixed liquor is dropwise added in zinc acetate mixed solution, continues reaction 1 h.Reaction finishes, and is cooled to after room temperature, adds the n-hexane that is equivalent to mixed liquor two volumes, puts into 4 ℃ of refrigerator standing sedimentations and spends the night.After supernatant discarded, by absolute ethyl alcohol and deionized water, substrate is fully washed 3 times, be placed in 60 ℃ of vacuum drying ovens dry.This material is carried out to structure and performance characterization, referring to Fig. 2, from figure, can clearly see the upper big or small homogeneous of GO, the Zinc oxide nanoparticle being evenly distributed.From Fig. 3, can be clear that load on the GO of the composite nano materials of preparing at the present embodiment ZnO nano particle crystal structure, and the diameter of ZnO nano particle is greatly about 4 nm left and right.X-ray diffraction from Fig. 4 (XRD) figure can be clear that, the ZnO nano particle of load on the GO of the composite nano materials of preparing at the present embodiment belongs to six side's zinc sulfide ore crystal formations, wider diffraction maximum also illustrates that ZnO nano grain diameter is minimum simultaneously, and the particle size obtaining of calculating by Scherrer formula is consistent with HR-TEM analysis result.
In the present embodiment, the ZnO/GO composite nano materials of preparation is scattered in to the suspension that is made into 100 μ g/mL in deionized water, suction filtration makes the antibacterial film that contains ZnO/GO composite nano materials, and the diameter of film is 1.5 centimetres.Prepare two kinds of antibacterial films, contain respectively the ZnO/GO composite nano materials of 2 μ g and 4 μ g, for the test of coated plate anti-microbial property, result as shown in Figure 5.Take blank film and the filter membrane that contains equivalent GO as contrast, can see that the filter membrane that contains ZnO/GO composite nano materials does not have bacterial clump around, and the high filter membrane of ZnO/GO composite nano materials content around inhibition zone is larger.Can draw thus, ZnO/GO composite nano materials, as antibacterial film, has good antibacterial effect, and exists concentration to rely on.
embodiment tri-:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, take the Zn (Ac) of 0.0025mol
22H
2o is dispersed in 50 mL absolute ethyl alcohols, vigorous stirring reaction 20 minutes under 80 ℃ of conditions.Meanwhile, adopt Hummer ' s oxidizing process to prepare GO, claim 0.2 g LiOH2H
2o and 60 mg GO, be dispersed in respectively in 20 mL and 30 mL absolute ethyl alcohols, under the state of vigorous stirring, both mixed, and mixed liquor is dropwise added in zinc acetate mixed solution, continues reaction 5h.Reaction finishes, and is cooled to after room temperature, adds the n-hexane that is equivalent to mixed liquor two volumes, puts into 4 ℃ of refrigerator standing sedimentations and spends the night.After supernatant discarded, by absolute ethyl alcohol and deionized water, substrate is fully washed 3 times, be placed in 60 ℃ of vacuum drying ovens dry.This material is carried out to structure and performance characterization, referring to Fig. 6, from figure, can clearly see the upper big or small homogeneous of GO, the Zinc oxide nanoparticle distributing very evenly.
embodiment tetra-:
The present embodiment and previous embodiment are basic identical, and special feature is:
In the present embodiment, take the Zn (Ac) of 0.00125mol
22H
2o is dispersed in 50 mL absolute ethyl alcohols, vigorous stirring reaction 20 minutes under 80 ℃ of conditions.Meanwhile, adopt Hummer ' s oxidizing process to prepare GO, claim 0.2 g LiOH2H
2o and 60 mg GO, be dispersed in respectively in 20 mL and 30 mL absolute ethyl alcohols, under the state of vigorous stirring, both mixed, and mixed liquor is dropwise added in zinc acetate mixed solution, continues reaction 1h.Reaction finishes, and is cooled to after room temperature, adds the n-hexane that is equivalent to mixed liquor two volumes, puts into 4 ℃ of refrigerator standing sedimentations and spends the night.After supernatant discarded, by absolute ethyl alcohol and deionized water, substrate is fully washed 3 times, be placed in 60 ℃ of vacuum drying ovens dry.This material is carried out to structure and performance characterization, referring to Fig. 7, from figure, can clearly see the upper big or small homogeneous of GO, distribution Zinc oxide nanoparticle comparatively uniformly.
embodiment five:
In the present embodiment, the ZnO/GO composite nano materials that utilizes the embodiment of the present invention two methods to prepare is scattered in and in certain quantity of fluid medium, is made into different dispersion liquids, ultra violet lamp sterilizing.Ultrasonic dispersion 15 minutes before using.Get the frozen bacterium liquid of 400 μ L to the conical flask that contains 100 mL LB medium, 37 ℃ of concussions are cultivated approximately 3 hours.Light absorption value with measurement of ultraviolet-visible spectrophotometer culture fluid at 600 nm places, medium is made reference, OD
600value should be 0.2 left and right.Choose the Escherichia coli in logarithmic growth logarithmic phase
e.colicarry out the antibacterial experiment of variable concentrations ZnO/GO sample, poisoning dosage is respectively 2.5,5.0,7.5,10.0 μ g/mL, sample blank group adds isodose ZnO/GO composite nano materials, and blank group adds equivalent liquid nutrient medium, and each sample does three Duplicate Samples.After contamination, under 37 ℃ of environment, 200 rpm concussions are cultivated, and then with vortex blender, bacterium are disperseed.Bacterium liquid in each conical flask samples three times as Duplicate Samples, in the time of 0,4,8,12,16,20,24 hour, gets respectively the mixed bacteria liquid of 200 μ L, adds in 96 orifice plates, detects the light absorption value at 600 nm places by microplate reader.Under the condition that the ZnO/GO composite nano materials of variable concentrations exists,
e.coligrowth curve as shown in Figure 8.In Fig. 8, during as the applying dosage and be 2.5,5.0,7.5,10.0 μ g/mL of the ZnO/GO composite nano materials dispersion liquid of bactericide, respectively in 12 h, in 13h, in 18h, in 24h, can suppress safely and effectively Escherichia coli Growth, and cause bacterium death.Compared with blank group, when 2.5 μ g/mL, ZnO/GO composite nano materials has shown the ability of bacteria growing inhibiting; Along with the increase of ZnO/GO concentration,
e.coligrowing multiplication speed is obviously postponed, and when the maximum dose level 10 .0 μ g/mL of our use, fungistatic effect is particularly evident.Composite nano materials can affect
e.coligrowth, and there is concentration effect and time effect.
embodiment six:
The present embodiment is with the special feature that embodiment five compares:
In the present embodiment, it is 10 μ g/mL dispersion liquids that the ZnO/GO composite nano materials that utilizes the embodiment of the present invention two methods to prepare is prepared into concentration, by ZnO/GO composite nano materials dispersion liquid with
e.coli after co-incubation 24 hours, 6000 g are supernatant discarded after centrifugal 8 minutes, and substrate, with after PBS buffer solution washed twice, is dispersed in ultra-pure water again.Suspension, after polycarbonate membrane filtration, takes off filter membrane, under 4 ° of C, with glutaraldehyde solution, fixes 2 hours.Use afterwards cacodylic acid sodium-hydrochloric acid buffer solution rinsing 3 times, pre-fix 1 hour with somuum oxide.Complete after above-mentioned steps, with ultra-pure water rinsing three times, then use 50% ethanol dehydration 30 minutes, then use respectively 75%, 85% and 95% ethanol dehydration 10 minutes, finally with absolute ethyl alcohol dehydration 2 times.Sample is put into critical point drying case dry thoroughly to remove ethanol.After removing from drying box, sticked on silicon chip, metal spraying, carries out sem test.As shown in Figure 9, compare with blank group, after cultivating altogether with ZnO/GO composite nano materials
e.coli, from shaft-like, become round shape, the bacterial cell film rupture after some and material close contact, the materials such as cytoplasm leak, and cell appearance is shrivelled shape.Find out that thus ZnO/GO composite nano materials and bacterium close contact can cause cyto-architectural variation, and then cause bacterium death.In the present embodiment, ZnO/GO composite nano materials has excellent antibacterial activity, its efficient antibacterial activity derives from the synergy of ZnO nano particle and GO, be GO as the Filament Wound Composite of carrier in bacterium surface, make bacterium more close with contacting of ZnO nano particle, cause the local zinc ion concentration of bacterium surface to increase, the permeability of cell membrane strengthens, thereby causes bacterium death.
embodiment seven:
The present embodiment is with the special feature that embodiment five and embodiment six compare:
In the present embodiment, choosing 24 hours is time point, uses the CCK-8 kit of Japanese colleague's chemistry institute exploitation to detect the cytotoxicity of ZnO/GO composite nano materials.HeLa cell is inoculated in to 96 orifice plates, every hole approximately 5 × 10
3individual cell, 200 μ L medium, respectively 37
°in C constant incubator, cultivate 24 h.The GO and the ZnO/GO that introduce afterwards variable concentrations are respectively 5,10 with ultimate density, and 50 μ g/mL are as experimental group, and the cell that does not add any material is control group.Cultivate respectively after 24 hours, absorb medium, wash cell with D-Hanks buffer solution.Every hole adds the CCK-8 solution of 200 μ L medium dilutions, only contains the not celliferous hole of CCK-8 solution as blank group, is placed in 37
°in C incubator, hatch 24 h.Centrifugal 5 min of 4000 rpm, are transferred to 96 new orifice plates by 100 μ L supernatants, measure the light absorption value at 450 nm places, i.e. OD value by microplate reader.Calculate as follows cell viability: cell viability=(the OD value of the OD value-blank well of test hole)/(the OD value of the OD value-blank well of control wells) × 100 %.Be CCK-8 testing result as shown in figure 10, GO and ZnO/GO act on respectively the cell viability contrast of 24 h under variable concentrations with HeLa cell.For the cell of ZnO/GO composite nano materials effect 24 h, the vigor of cell shows certain dose effect, and cell viability reduces with the rising of ZnO/GO concentration.When 10 μ g/mL, cell still keeps more than 90% cell viability.Visible, under the concentration of high-efficiency antimicrobial, ZnO/GO composite nano materials does not show obvious cytotoxicity to HeLa cell, illustrates that ZnO/GO composite nano materials has low cytotoxicity and good biological safety as antibacterial agent.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; can also make multiple variation according to the object of innovation and creation of the present invention; the change made under all Spirit Essences according to technical solution of the present invention and principle, modification, substitute, combination, simplify; all should be equivalent substitute mode; as long as goal of the invention according to the invention; only otherwise deviate from the preparation method of zinc oxide-graphene oxide composite nano materials of the present invention and know-why and the inventive concept of application, all belong to protection scope of the present invention.
Claims (8)
1. the preparation method of zinc oxide-graphene oxide composite nano materials, it is characterized in that, comprise the following steps: take soluble divalent zinc ion as zinc source, with graphene oxide and alkali lye together as reactant, according to the quality proportioning of zinc ion and graphene oxide, be (1～3): 1 quality proportioning forms solute composition, take alcohol as solvent, form reaction solution mixed system, make to carry out one-step method reaction, the OH that the alkali lye in reaction solution mixed system is progressively ionized out between the solute composition of reaction solution mixed system
-with Zn
2+form Zn-OH complex, fully contact with the oxy radical of graphene oxide again, be attached to the surface of graphene oxide, reaction solution mixed system is not under higher than 80 ℃ of conditions, make the dehydrogenation of Zn-OH complex become ZnO, the zinc oxide nucleus uniform load forming is on graphene oxide surface, the one-step method reaction time is 30 min～5 h, after reaction finishes, reaction solution mixed system is cooled to room temperature, to adding in reaction solution mixed system, be equivalent to the more than 2 times n-hexane of reaction solution mixed system volume again, in the environment that is greater than 0 ℃, standing sedimentation spends the night, then after abandoning supernatant, with centrifugal, with washing methods, substrate is carried out to purifying, after dry, finally obtain zinc oxide-graphene oxide composite nano materials, the particle diameter that loads on the Zinc oxide nanoparticle on graphene oxide surface is (2～200) nm.
2. the preparation method of zinc oxide-graphene oxide composite nano materials according to claim 1, it is characterized in that: by changing each component ratio and the one-step method synthesising reacting time of reactant, realize the control in the load capacity on graphene oxide surface to Zinc oxide nanoparticle size and zinc oxide.
3. according to the preparation method of zinc oxide-graphene oxide composite nano materials described in claim 1 or 2, it is characterized in that: adopt Zinc diacetate dihydrate that zinc ion is provided, according to the quality proportioning of Zinc diacetate dihydrate and graphene oxide, be (4～9): 1 quality proportioning forms solute composition, take alcohol as solvent, form reaction solution mixed system.
4. according to the preparation method of zinc oxide-graphene oxide composite nano materials described in claim 1 or 2, it is characterized in that: after one-step method reaction finishes, reaction solution mixed system is cooled to room temperature, in reaction solution mixed system, add phase n-hexane again, in the environment of 4 ℃, standing sedimentation spends the night.
5. one kind is utilized the application of zinc oxide-graphene oxide composite nano materials that the preparation method of zinc oxide-graphene oxide composite nano materials obtains described in claim 1, it is characterized in that: take soluble divalent zinc ion as zinc source, with graphene oxide and solubility hydroxide together as reactant, according to the quality proportioning of zinc ion and graphene oxide, be (1～3): 1 quality proportioning forms solute composition, take alcohol as solvent, form reaction solution mixed system, reaction solution mixed system is not under higher than 80 ℃ of conditions, carry out one-step method reaction, changing the reaction time is 30 min～5 h, obtain the particle diameter of Zinc oxide nanoparticle for zinc oxide-graphene oxide composite nano materials of (2～200) nm, effectively bacteria growing inhibiting, and cause bacterium death.
6. the application of zinc oxide-graphene oxide composite nano materials according to claim 5, it is characterized in that: the dispersion liquid that adopts zinc oxide-graphene oxide composite nano materials to prepare, while being 2.5～10.0 μ g/mL as the dosage of bactericide, in 12 h, can suppress safely and effectively Escherichia coli Growth, and cause bacterium death.
7. the application of zinc oxide-graphene oxide composite nano materials according to claim 6, it is characterized in that: the dispersion liquid that adopts zinc oxide-graphene oxide composite nano materials to prepare, while being 7.5～10.0 μ g/mL as the dosage of bactericide, in 18h, can suppress safely and effectively Escherichia coli Growth, and cause bacterium death.
8. according to the application of zinc oxide-graphene oxide composite nano materials described in any one in claim 5～7, it is characterized in that: while adopting zinc oxide-graphene oxide composite nano materials to prepare dispersion liquid as bactericide, take deionized water as dispersant.
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