CN104098088A - Preparation method for nano-zinc oxide modified graphene hybrid material - Google Patents
Preparation method for nano-zinc oxide modified graphene hybrid material Download PDFInfo
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Abstract
The invention discloses a preparation method for a nano-zinc oxide modified graphene hybrid material. The method includes: preparing a graphene oxide suspension solution; dissolving a zinc salt in water, adding the solution into the graphene oxide suspension solution, conducting ultrasonic treatment, adding an alkali reagent dropwise to obtain a zinc hydroxide graphene oxide suspension solution; under ultraviolet light irradiation, performing static aging to obtain a zinc hydroxide-graphene oxide gel, adding an excessive reducing agent, carrying out reaction, using water and ethanol to conduct repeated washing, and performing drying to obtain a zinc hydroxide-graphene dry gel; placing the gel in a muffle furnace, and conducting treatment at high temperature to obtain the gray nano-zinc oxide modified graphene hybrid material. The nano-zinc oxide obtained by the invention has a large specific surface area, can effectively promote vulcanization crosslinking, greatly reduces the using amount of zinc oxide, and is of great importance to full utilization of zinc resources and ecological economy. At the same time, without affecting the performance of graphene, the method is in favor of further expanding the potential application scope of graphene.
Description
Technical field
The present invention relates to a kind of preparation method of Graphene hybrid material, be specifically related to the preparation method of the grapheme modified hybrid material of a kind of nano zine oxide.
Background technology
Since utilizing adhesive tape micromechanics, peel off after highly oriented pyrolytic graphite prepares Graphene British scientist Andrew Geim in 2004 etc., Graphene is as a kind of novel Nano filling, due to its excellent mechanical property, electrical property and heat conductivility etc., caused that people study interest extremely widely.So far, owing to can preparing in a large number Graphene, oxidation reduction process is to prepare the main method of Graphene.But due to stronger interlayer Van der Waals force, redox graphene lamella is easily reunited, and causes the forfeiture of Graphene excellent properties.
As everyone knows, zinc oxide has the performances such as outstanding catalytic efficiency, tinctorial property, preservative activity, ultraviolet screener ability, biological antibiotic due to it, be widely used in chemical industry, rubber industry, coating, health care and food service industry etc.But European Union delimit zinc oxide for severe poisonous chemicals, and the necessary strict use of controlling zinc oxide of macromolecule product process is being prepared in statement.Meanwhile, U.S. environment protection is organized and is also assert that zinc oxide has very large toxic action to waterplant.Therefore it is imperative, reducing the consumption of zinc oxide in macromolecule product.And be compared to common zinc oxide, and nano zine oxide has larger specific surface area, and reactive behavior is higher.In reaction process, can greatly increase contacting of nano zine oxide and other reaction promoters, further promote the carrying out of reaction.
The present invention prepares the method for the grapheme modified matrix material of a kind of nano zine oxide.Prepare at present the grapheme modified research of nano zine oxide less, being applied to does not have relevant report in elastomeric material.Chinese patent CN101857222A, adopts hydrothermal method to prepare Graphene/zinc oxide composite, and proposes to be applied to the application prospect of the aspects such as sensor, solar cell and novel nano device.Meanwhile, Chinese patent CN102654474A, adopts simple method of mixing, and Graphene and zinc oxide are scattered in solvent, further prepares Graphene/zinc-oxide film, and is applied to detected gas.Chinese patent CN103199126A adopts sol-gel method to prepare zinc oxide-transparent graphene conductive film in addition, and proposes to apply to solar film battery etc. as transparent conducting glass.But these preparation methods exist a common problem, can not, in preparing Graphene-zinc oxide composite process, effectively control the reunion of Graphene exactly.Meanwhile, the application of preparation-obtained Graphene/zinc oxide composite is only confined to the research of photoelectric material aspect.
Therefore, by preparation, nano zine oxide is modified to Graphene surface, slackened the Van der Waals force of graphene film interlayer, reach and hinder the object of reuniting.Meanwhile, the nano zine oxide obtaining has very large specific surface area, can effectively promote vulcanization crosslinking, greatly reduces the consumption of zinc oxide, to zinc resource make full use of and the ecological economy has important effect.Do not affecting under the performance prerequisite of Graphene, be conducive to further expand the potential range of application of Graphene simultaneously.
Summary of the invention
The present invention overcomes above-mentioned technological deficiency, and the preparation method of the grapheme modified hybrid material of a kind of nano zine oxide is provided; First graphite oxide is prepared to finely dispersed graphene oxide suspension at water or organic solvent for ultrasonic, then adopt sol-gel method to prepare zinc hydroxide-graphene oxide collosol and gel, after ageing, adopt strong reductant further to reduce and obtain zinc hydroxide-Graphene gel, final high temperature is processed and is prepared the grapheme modified hybrid material of nano zine oxide.
The present invention is first under ul-trasonic irradiation, the graphite oxide that effects on surface has a large amount of oxy radical (hydroxyl, carboxyl, carbonyl etc.) carries out supersound process, ultrasonic energy can overcome Van der Waals force and the pi-pi bond reactive force of sheet interlayer, realization is peeled off oxidized graphite flake layer, prepares finely dispersed graphene oxide suspension.Secondly, zinc salt is added in suspension, adopt sol-gel method, first prepare zinc hydroxide-graphene oxide colloidal sol.In order to prevent that Graphene is reunited in reduction process, by room temperature further ageing of colloidal sol, form the comparatively perfect zinc hydroxide gel of network structure, graphene oxide sheet is further isolated, confined.Then adopt reductive agent effectively to remove a large amount of oxy radical of sheet surfaces, obtain zinc hydroxide-Graphene gel.Finally, the xerogel that purification process is obtained carries out pyroprocessing, and under zinc hydroxide high temperature, dehydration generates nano zine oxide, and is adsorbed on the graphene sheet layer that specific surface area is very large, has further stoped the reunion of graphene sheet layer.
This programme object realizes by following scheme:
A preparation method for nano zine oxide Graphene hybrid material, comprises the following steps:
(1) prepare graphene oxide suspension: get graphite oxide and be scattered in water or organic solvent, after ultrasonic 0.5～2.5h, the centrifugal brown color graphene oxide suspension that obtains;
(2) prepare zinc hydroxide-graphene oxide colloidal sol: zinc salt is dissolved in to the zinc salt solution of making clarification in distilled water, and is added in the graphene oxide suspension that step (1) prepares and mixes, obtain mixing solutions; Under lasting ultrasonic environment, bases reagent is dropwise dropped in mixing solutions, after ultrasonic 0.5～1.5h, obtain the zinc hydroxide graphene oxide suspension of brown color;
(3) prepare zinc hydroxide-Graphene gel: the zinc hydroxide graphene oxide suspension preparing in step (2) is irradiated under UV-light, at room temperature static ageing, obtain zinc hydroxide-graphene oxide gel of certain denseness, then, add excessive reductive agent in gel, under 80～90 ℃ of constant temperature, react after 6～24h, adopt water and ethanol repetitive scrubbing, vacuum-drying 12～36h at 50 ℃～70 ℃, obtains zinc hydroxide-Graphene xerogel of black;
(4) prepare nano zine oxide-Graphene hybrid material: the zinc hydroxide-Graphene xerogel obtaining in step (3) is placed in to retort furnace, after at high temperature processing, obtains the grapheme modified hybrid material of nano zine oxide of grey.
In aforesaid method, described organic solvent is a kind of in methyl alcohol, ethanol, acetone, acetonitrile, tetrahydrofuran (THF), DMF or N-Methyl pyrrolidone.
In aforesaid method, described zinc salt is a kind of in zinc sulfate, zinc nitrate, zinc acetate, zinc chloride, zinc sulphide or zinc cyanide.
In aforesaid method, the mass ratio of described graphite oxide and zinc salt is 0.5:3～8.
In aforesaid method, described bases reagent is a kind of in ammoniacal liquor, urea, quadrol, trolamine, tri-isopropanolamine or vulkacit H.
In aforesaid method, the quality mol ratio of described zinc salt and alkaline reagents is 3:2.2～6.2.
In aforesaid method, the energy of described uviolizing is 5～10 joules/cm
2, the UV-irradiation time is 10～60min.
In aforesaid method, described digestion time is 12～24h.
In aforesaid method, described reductive agent is a kind of in tea-polyphenol, Trisodium Citrate, Cys, vitamins C or Resorcinol.
In aforesaid method, described pyroprocessing condition is that treatment temp is 400～600 ℃, and the treatment time is 0.5～4h.
Compared with prior art, advantage of the present invention is:
(1) technique is simple, and synthesis condition is gentle, and actually operating is convenient, safety, and equipment requirements is low, can big area generate;
(2) originally with low cost, energy consumption is low, and Operating parameters can be good at;
(3) the grapheme modified hybrid material of prepared nano zine oxide shows continuously and stacking provisions, and dispersions of mutually promoting under both effects of zinc oxide and Graphene, suppresses reunion and overlapping.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1 sample;
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 2 samples;
Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment 3 samples;
Fig. 4 is the scanning electron microscope (SEM) photograph of embodiment 4 samples;
Fig. 5 is the scanning electron microscope (SEM) photograph of embodiment 5 samples;
Fig. 6 is the X-ray diffractogram of embodiment 1～5 sample.
Embodiment
Embodiment 1:
(1) prepare graphene oxide suspension: get 0.5g graphite oxide and be scattered in water, after ultrasonic 1h, the centrifugal brown color graphene oxide suspension that obtains.
(2) prepare zinc hydroxide-graphene oxide colloidal sol: the zinc sulfate of 3.0g (0.01mol) is dissolved in to the zinc sulfate solution of making clarification in distilled water, and is added in the graphene oxide suspension that step (1) prepares and mixes.Afterwards, 0.735g (0.021mol) ammoniacal liquor dropwise to mixing solutions, and is constantly stirred to ultrasonic 0.5h, obtain brown color zinc hydroxide graphene oxide suspension.
(3) prepare zinc hydroxide-Graphene gel: the zinc hydroxide-graphene oxide suspension preparing in step (2) is irradiated to 20min under the exposure intensity of 10 joules/cm2, then ageing 12h at room temperature, obtains zinc hydroxide-graphene oxide gel of certain denseness.Then, excessive tea-polyphenol is added in gel, under 80 ℃ of constant temperature, reacts after 12h, adopt water and ethanol repetitive scrubbing several times, vacuum-drying 12h at 50 ℃, obtains zinc hydroxide-Graphene xerogel of black.
(4) prepare nano zine oxide-Graphene hybrid material: the zinc hydroxide-Graphene xerogel obtaining in step (3) is placed in to retort furnace, at 600 ℃, process 1h, the grapheme modified hybrid material of nano zine oxide that obtains grey, its surface topography as shown in Figure 1.Graphene sheet layer is embedded in white zinc oxide granule interior and forms mixture.The effect of inhibition is played in this reunion to Graphene, has promoted the dispersion in rubber matrix.By XRD test result, show, as Fig. 6 can find out crystalline diffraction peak (100), (002), (101), (102), (110), (103), (112), (200), (112) and (201) crystal face of zinc oxide, and do not have impurity peaks, simultaneously, the diffraction peak of (001) of graphite does not occur, illustrates that agglomeration does not occur Graphene.
The grapheme modified hybrid material of the nano zine oxide of synthesized in (4), the productive rate that binding isotherm zinc oxide Mass Calculation goes out zinc oxide is 52.94%.(4) mass percent that middle Graphene accounts for the grapheme modified hybrid material of nano zine oxide is 25.12%.
Embodiment 2:
(1) prepare graphene oxide suspension: get 0.5g graphite oxide and be scattered in water, after ultrasonic 1h, the centrifugal brown color graphene oxide suspension that obtains.
(2) prepare zinc hydroxide-graphene oxide colloidal sol: the zinc sulfate of 5.0g (0.0174mol) is dissolved in to the zinc sulfate solution of making clarification in distilled water, and is added in the graphene oxide suspension that step (1) prepares and mixes.Afterwards, 1.3706g (0.03916mol) ammoniacal liquor dropwise to mixing solutions, and is constantly stirred to ultrasonic 0.5h, obtain brown color zinc hydroxide graphene oxide suspension.
(3) prepare zinc hydroxide-Graphene gel: the zinc hydroxide-graphene oxide suspension preparing in step (2) is irradiated to 20min under the exposure intensity of 10 joules/cm2, then ageing 12h under room temperature, obtains zinc hydroxide-graphene oxide gel of certain denseness.Then, excessive tea-polyphenol is added in gel, after 80 ℃ of isothermal reaction 6h, adopts water and ethanol repetitive scrubbing several times, vacuum-drying 12h at 50 ℃, obtains zinc hydroxide-Graphene xerogel of black.
(4) prepare nano zine oxide-Graphene hybrid material: the zinc hydroxide-Graphene xerogel obtaining in step (3) is placed in to retort furnace, at 600 ℃, process 1h, the grapheme modified hybrid material of nano zine oxide that obtains grey, its surface topography as shown in Figure 2.Nano granular of zinc oxide and graphene film surface are bonded together, and form complicated, continuous mixture, both dispersion of having mutually promoted.XRD test result shows, as Fig. 6, has only occurred the crystalline diffraction peak of zinc oxide, and there is no other impurity peaks, meanwhile, does not also occur the diffraction peak of (001) face of graphite, illustrates that Graphene exists with the state of disarray of monolithic layer.
The grapheme modified hybrid material of the nano zine oxide of synthesized in (4), the productive rate that binding isotherm zinc oxide Mass Calculation goes out zinc oxide is 58.76%.(4) mass percent that middle Graphene accounts for the grapheme modified hybrid material of nano zine oxide is 15.34%.
Embodiment 3:
(1) prepare graphene oxide suspension: get 0.5g graphite oxide and be scattered in water, after ultrasonic 1h, the centrifugal brown color graphene oxide suspension that obtains.
(2) prepare zinc hydroxide-graphene oxide colloidal sol: the zinc sulfate of 8.0g (0.0279mol) is dissolved in to the zinc sulfate solution of making clarification in distilled water, and is added in the graphene oxide suspension that step (1) prepares and mixes.Afterwards, 2.2460g (0.06417mol) ammoniacal liquor dropwise to mixing solutions, and is constantly stirred to ultrasonic 0.5h, obtain brown color zinc hydroxide graphene oxide suspension.
(3) prepare zinc hydroxide-Graphene gel: the zinc hydroxide-graphene oxide suspension preparing in step (2) is irradiated to 20min under the exposure intensity of 10 joules/cm2, then ageing 12h under room temperature, obtains zinc hydroxide-graphene oxide gel of certain denseness.Then, excessive tea-polyphenol is added in gel, under 80 ℃ of constant temperature, reacts after 12h, adopt water and ethanol repetitive scrubbing several times, vacuum-drying 12h at 50 ℃, obtains zinc hydroxide-Graphene xerogel of black.
(4) prepare nano zine oxide-Graphene hybrid material: the zinc hydroxide-Graphene xerogel obtaining in step (3) is placed in to retort furnace, at 600 ℃, process 1h, the grapheme modified hybrid material of nano zine oxide that obtains grey, its surface topography as shown in Figure 3.Nano granular of zinc oxide is adsorbed on the surface of graphene sheet layer, has alleviated nano zine oxide and has occurred serious agglomeration.Meanwhile, the diffraction peak of (001) face of graphite does not exist and has illustrated in system that nano zine oxide has suppressed Graphene and occurred being stacked yet.
The grapheme modified hybrid material of the nano zine oxide of synthesized in (4), the productive rate that binding isotherm zinc oxide Mass Calculation goes out zinc oxide is 61.6%.(4) mass percent that middle Graphene accounts for the grapheme modified hybrid material of nano zine oxide is 7.9%.
Embodiment 4:
(1) prepare graphene oxide suspension: get 0.5g graphite oxide and be scattered in water, after ultrasonic 1h, the centrifugal brown color graphene oxide suspension that obtains.
(2) prepare zinc hydroxide-graphene oxide colloidal sol: the zinc nitrate of 3.0g (0.012mol) is dissolved in to the zinc nitrate aqueous solution of making clarification in distilled water, and is added in the graphene oxide suspension that step (1) prepares and mixes.Afterwards, 0.792g (0.0132mol) quadrol dropwise to mixing solutions, and is constantly stirred to ultrasonic 0.5h, obtain brown color zinc hydroxide graphene oxide suspension.
(3) prepare zinc hydroxide-Graphene gel: by the zinc hydroxide-graphene oxide suspension preparing in step (2) at 10 joules/cm
2exposure intensity under irradiate 20min, ageing 18h under room temperature then, obtains zinc hydroxide-graphene oxide gel of certain denseness.Then, excessive tea-polyphenol is added in gel, under 80 ℃ of constant temperature, reacts after 12h, adopt water and ethanol repetitive scrubbing several times, vacuum-drying 12h at 50 ℃, obtains zinc hydroxide-Graphene xerogel of black.
(4) prepare nano zine oxide-Graphene hybrid material: the zinc hydroxide-Graphene xerogel obtaining in step (3) is placed in to retort furnace, at 600 ℃, process 2h, the grapheme modified hybrid material of nano zine oxide that obtains grey, its surface topography as shown in Figure 4.White nano granular of zinc oxide covers graphene film surface equably, and the lamellar spacing of mixture obviously increases, and illustrates that effect is between the two more intense, has promoted dispersion each other.And the graphite characteristic diffraction peak of (001) face do not occur yet, further illustrate dispersions of mutually promoting between nano zine oxide Graphene, suppress reunion.
The grapheme modified hybrid material of the nano zine oxide of synthesized in (4), the productive rate that binding isotherm zinc oxide Mass Calculation goes out zinc oxide is 56.40%.(4) mass percent that middle Graphene accounts for the grapheme modified hybrid material of nano zine oxide is 21.7%.
Embodiment 5:
(1) prepare graphene oxide suspension: get 0.5g graphite oxide and be scattered in water, after ultrasonic 1h, the centrifugal brown color graphene oxide suspension that obtains.
(2) prepare zinc hydroxide-graphene oxide colloidal sol: the zinc nitrate of 5.0g (0.02mol) is dissolved in to the zinc nitrate aqueous solution of making clarification in distilled water, and is added in the graphene oxide suspension that step (1) prepares and mixes.Afterwards, 1.44g (0.024mol) quadrol dropwise to mixing solutions, and is constantly stirred to ultrasonic 0.5h, obtain brown color zinc hydroxide graphene oxide suspension.
(3) prepare zinc hydroxide-Graphene gel: the zinc hydroxide-graphene oxide suspension preparing in step (2) is irradiated to 20min under the exposure intensity of 10 joules/cm2, then ageing 18h under room temperature, obtains zinc hydroxide-graphene oxide gel of certain denseness.Then, excessive tea-polyphenol is added in gel, under 80 ℃ of constant temperature, reacts after 12h, adopt water and ethanol repetitive scrubbing several times, vacuum-drying 12h at 50 ℃, obtains zinc hydroxide-Graphene xerogel of black.
(4) prepare nano zine oxide-Graphene hybrid material: the zinc hydroxide-Graphene xerogel obtaining in step (3) is placed in to retort furnace, at 600 ℃, process 2h, the grapheme modified hybrid material of nano zine oxide that obtains grey, its surface topography as shown in Figure 5.Nano zine oxide and Graphene form the compound system that big area is complicated, continuous, and Zinc oxide particles is evenly dispersed in the surface of graphene film.Simultaneously, (001) face diffraction peak of Graphene appears at 2 θ=23.8 °, ° less than normal than the characteristic diffraction peak of graphite 2 θ=26.6, illustrate that nano zine oxide is dispersed in the building-up process that graphene film surface can prevent hybrid material and occurs further reuniting.
The grapheme modified hybrid material of the nano zine oxide of synthesized in (4), the productive rate that binding isotherm zinc oxide Mass Calculation goes out zinc oxide is 58.42%.(4) mass percent that middle Graphene accounts for the grapheme modified hybrid material of nano zine oxide is 13.9%.
Press the basic rubber compounding shown in table 1, respectively with the mixing legal system of routine for native rubber composite material, and with add matrix material prepared by 5 parts of common zinc oxides and contrast.Wherein preparation technology's flow process is: natural rubber (NR) → plasticate → carbon black (N330) → zinc oxide (the grapheme modified hybrid material of nano zine oxide), stearic acid → accelerant CZ, altax → antioxidant 4010NA → sulphur (S); The NR composite materials property obtaining is as shown in table 2.
Table 1. rubber test basic recipe
The mechanical property of table 2.NR matrix material
Note: blank 1 sample is to add 5 parts of matrix materials prepared by common zinc oxide; Embodiment 1～5 has added respectively 1.5 parts of NR matrix materials prepared by the grapheme modified hybrid material of prepared nano zine oxide.
Table 2 is the mechanical properties of having added the prepared NR matrix material of the nano zine oxide grapheme modified hybrid material of 1.5 parts of embodiment, 1～5 preparation, by more blank sample (adding 5 parts of matrix materials prepared by common zinc oxide), can find, added after the grapheme modified hybrid material of nano zine oxide of 1.5 parts, there is obvious raising in the mechanical property of NR matrix material, enhancing in various degree all appears in tensile strength, tensile yield, 300% stress at definite elongation and tear strength.This is that particle diameter due to common zinc oxide reaches micron level, in sulfidation, lower with the surface in contact of promotor, vulcanizing agent etc., causes the activation efficiency of zinc oxide lower.And the prepared grapheme modified hybrid material of nano zine oxide of example 1～5, as the hybrid material of example 3 preparation, because zinc oxide reaches Nano grade, particle diameter is little, surface-area is very large, larger with promotor, vulcanizing agent contact surface in system, catalytic activity is very large, has further promoted the vulcanization crosslinking of system, thereby improving appears in the mechanical property of matrix material, meanwhile, the graphene uniform of Nano grade is dispersed in the middle of rubber matrix, plays the effect of nanometer reinforcement.Therefore, the grapheme modified hybrid material of a small amount of nano zine oxide can significantly improve the mechanical property of matrix material.
Claims (10)
1. a preparation method for the grapheme modified hybrid material of nano zine oxide, is characterized in that, comprises the following steps:
(1) prepare graphene oxide suspension: get graphite oxide and be scattered in water or organic solvent, after ultrasonic 0.5～2.5 h, the centrifugal brown color graphene oxide suspension that obtains;
(2) prepare zinc hydroxide-graphene oxide colloidal sol: zinc salt is dissolved in to the zinc salt solution of making clarification in distilled water, and is added in the graphene oxide suspension that step (1) prepares and mixes, obtain mixing solutions; Under lasting ultrasonic environment, bases reagent is dropwise dropped in mixing solutions, after ultrasonic 0.5～1.5 h, obtain the zinc hydroxide graphene oxide suspension of brown color;
(3) prepare zinc hydroxide-Graphene gel: the zinc hydroxide graphene oxide suspension preparing in step (2) is irradiated under UV-light, at room temperature static ageing, obtain zinc hydroxide-graphene oxide gel of certain denseness, then, add excessive reductive agent in gel, under 80～90 ℃ of constant temperature, react after 6～24h, adopt water and ethanol repetitive scrubbing, vacuum-drying 12～36h at 50 ℃～70 ℃, obtains zinc hydroxide-Graphene xerogel of black;
(4) prepare nano zine oxide-Graphene hybrid material: the zinc hydroxide-Graphene xerogel obtaining in step (3) is placed in to retort furnace, after at high temperature processing, obtains the grapheme modified hybrid material of nano zine oxide of grey.
2. the preparation method of the grapheme modified hybrid material of a kind of nano zine oxide as claimed in claim 1, it is characterized in that: described organic solvent is a kind of in methyl alcohol, ethanol, acetone, acetonitrile, tetrahydrofuran (THF), DMF or N-Methyl pyrrolidone.
3. the preparation method of the grapheme modified hybrid material of a kind of nano zine oxide as claimed in claim 1, is characterized in that: described zinc salt is a kind of in zinc sulfate, zinc nitrate, zinc acetate, zinc chloride, zinc sulphide or zinc cyanide.
4. the preparation method of the grapheme modified hybrid material of a kind of nano zine oxide as claimed in claim 1, is characterized in that: the mass ratio of described graphite oxide and zinc salt is 0.5:3～8.
5. the preparation method of the grapheme modified hybrid material of a kind of nano zine oxide as claimed in claim 1, is characterized in that: described bases reagent is a kind of in ammoniacal liquor, urea, quadrol, trolamine, tri-isopropanolamine or vulkacit H.
6. the preparation method of the grapheme modified hybrid material of a kind of nano zine oxide as claimed in claim 1, is characterized in that: the quality mol ratio of described zinc salt and alkaline reagents is 3:2.2～6.2.
7. the preparation method of the grapheme modified hybrid material of a kind of nano zine oxide as claimed in claim 1, is characterized in that: the energy of described uviolizing is 5～10 joules/cm
2, the UV-irradiation time is 10～60min.
8. the preparation method of the grapheme modified hybrid material of a kind of nano zine oxide as claimed in claim 1, is characterized in that: described digestion time is 12～24h.
9. the preparation method of the grapheme modified hybrid material of a kind of nano zine oxide as claimed in claim 1, is characterized in that: described reductive agent is a kind of in tea-polyphenol, Trisodium Citrate, Cys, vitamins C or Resorcinol.
10. the preparation method of the grapheme modified hybrid material of a kind of nano zine oxide as claimed in claim 1, is characterized in that: described pyroprocessing condition is that treatment temp is 400～600 ℃, and the treatment time is 0.5～4h.
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