CN103449504B - Zinc oxide nanodisk/graphene composite material and preparation method thereof - Google Patents
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- CN103449504B CN103449504B CN201310259347.3A CN201310259347A CN103449504B CN 103449504 B CN103449504 B CN 103449504B CN 201310259347 A CN201310259347 A CN 201310259347A CN 103449504 B CN103449504 B CN 103449504B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- 239000002131 composite material Substances 0.000 title abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 14
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004246 zinc acetate Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 8
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 claims description 7
- 239000007900 aqueous suspension Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 3
- -1 Graphene compound Chemical class 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 15
- 239000012153 distilled water Substances 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
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- 229960001296 zinc oxide Drugs 0.000 description 53
- 238000003756 stirring Methods 0.000 description 11
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- 238000006243 chemical reaction Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
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- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
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- 239000012286 potassium permanganate Substances 0.000 description 3
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
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- 206010028980 Neoplasm Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
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- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the field of photocatalytic degradation, and discloses a zinc oxide nanodisk and a preparation method thereof as well as a zinc oxide nanodisk/graphene composite material and a preparation method thereof. The preparation method of the composite material comprises the following steps of mixing the zinc oxide nanodisk with a graphene water solution, carrying out ultrasound treatment for 1-3 hours, and filtering in vacuum so as to obtain the zinc oxide nanodisk/graphene composite material. The zinc oxide nanodisk is synthesized through a hydrothermal method; a precursor solution of the zinc oxide nanodisk comprises dimethyl sulfoxide, zinc acetate and distilled water, wherein the volume ratio of the dimethyl sulfoxide to the distilled water is (60-95):(40-5), and the concentration of zinc acetate is 0.005-1mol/L. The composite material prepared by the method not only has the characteristic of high conductivity of the graphene, but also has the function of high-efficiency photocatalytic degradation.
Description
Technical field
The present invention relates to photocatalytic degradation field, more specifically, relate to a kind of nanometer zinc oxide disc and preparation and a kind of Zinc oxide nanodisk/graphene composite material and preparation method thereof.
Background technology
Industrial expansion makes water resources limited on the earth be subject to day by day serious pollution.In water body, find
Organic chemical pollutant reach kind more than 2000, the carcinogenic substance wherein confirmed in tap water reaches about 20 kinds, suspect carcinogen matter 23 kinds, short cancer material 18 kinds, mutagen 56 kinds.Organic pollutant in waste water with aromatics and heterogeneous ring compound in the majority, more than containing sulfide, nitride, heavy metal and toxic organic compound.Causing toxicity and the stench that distributes of the height of high concentrated organic wastewater has had a strong impact on human health life.
Poisonous, the harmful chemical removed in water has become an important process of field of Environment Protection.Traditional water treatment method mainly can be divided into physico-chemical process and the large class of biological method two.The former is general, and processing cost is higher, and the latter is not high to the processing efficiency of hardly degraded organic substance.Therefore finding water conditioning method that is efficient, low cost, is the vital task that water treatment worker faces.Photocatalyst, as a kind of " green " technology, because its high-level efficiency and widely suitability are that in environment, the elimination completely of toxic chemical substance provides good potentiality.Can degrade under the irradiation of the ultraviolet lamp associated viscera of various organic pollutant of the metal oxide semiconductor of nanostructure is reported.Therefore, recent years, the metal oxide semiconductor nanocatalyst of numerous species, such as Bi
2o
3, Fe
2o
3, TiO
2with ZnO etc., be used to develop into the mankind and created a comfortable environment.
Zinc oxide (ZnO) is a kind of nontoxic broad stopband II-VI compounds of group inorganic semiconductor material.Due to the uniqueness that it has under nanoscale optics, acoustics with the performance of electricity, therefore evoked and studied interest widely.Nano-ZnO has attracted vast researcher with the perfect adaptation of nano material and important conductor oxidate two aspect, emerge many research groups attached most importance to nano-ZnO in the world, many research work about ZnO nano material are carried out, since calendar year 2001, Science publishes report about specific form nano-ZnO continuously.Although during dyestuff in some aqueous solution of photocatalytic degradation, ZnO shows excellent photocatalysis efficiency, but because the bottleneck of the low quantum yield of the quick combination generation in light induced electron and hole, the photocatalysis efficiency strengthening ZnO is a challenge to meet the requirement of real world applications all the time.There is research at present by adopting and there is high-conductivity, carbon material compound compared with bigger serface, effectively improve catching and transportcapacity of light induced electron.But the report of this respect is still less.Graphene is sp
2the carbon atom monoatomic layer of hydridization, has other excellent properties that excellent electric property and two-dimension plane structure material have, as the high-clarity that huge specific surface area, monoatomic thickness are formed.Therefore the compound of ZnO and Graphene, can integrate efficient for ZnO photocatalysis performance and Graphene high-conductivity, effectively prevent the compound in light induced electron and hole, improves the efficiency of photocatalytic degradation further.In addition, the production in enormous quantities of current nano material still limits the development of nano material.
Summary of the invention
Technical problem to be solved by this invention is, can not produce in enormous quantities and the deficiency of the easy compound of photo-generate electron-hole in Photocatalytic Degradation Process, providing a kind of nanometer zinc oxide disc with photo-catalysis capability to overcome in prior art.
Another object of the present invention is to provide a kind of Zinc oxide nanodisk/graphene composite material with excellent photocatalytic degradation capability.
Another technical problem to be solved by this invention provides a kind of preparation method of Zinc oxide nanodisk/graphene composite material.
Technical problem to be solved by this invention is solved by the following technical programs:
Invention provide firstly a kind of nanometer zinc oxide disc, and it is characterized in that being obtained by water heat transfer by precursor solution by following, the precursor solution preparing nanometer zinc oxide disc is made up of dimethyl sulfoxide (DMSO), zinc acetate and water; Wherein the volume ratio of dimethyl sulfoxide (DMSO) and water is 60 ~ 95:40 ~ 5; Acetic acid zinc concentration is 0.005 ~ 1mol/L.
Preferably, the volume ratio of dimethyl sulfoxide (DMSO) and water is 60 ~ 90:40 ~ 10; Acetic acid zinc concentration is 0.01 ~ 1mol/L.
Preferably, the volume ratio of dimethyl sulfoxide (DMSO) and water is 90:10; Acetic acid zinc concentration is 0.01mol/L.
Preferably, described hydrothermal temperature is 60 ~ 90 DEG C; Reaction times is 0.5 ~ 2h.Preferred hydrothermal temperature is 70 ~ 80 DEG C, and the reaction times is 1 ~ 2h.
Invention provides a kind of nanometer zinc oxide disc matrix material simultaneously, it is characterized in that being composited by above-mentioned nanometer zinc oxide disc and Graphene.
Preferably, the mass ratio of nanometer zinc oxide disc and Graphene is 1:0.1 ~ 2.
The preparation method of matrix material as claimed in claims 6 or 7, is characterized in that, by zinc oxide
Nanometer plate mixes with Graphene aqueous suspension, ultrasonic 1 ~ 3h, suction filtration and get final product.
Preferably, the mass ratio of nanometer zinc oxide disc and Graphene is 1:1.
Preferably, in described graphene aqueous solution, the concentration of Graphene is 2 ~ 5mg/ml.
Invention provides a kind of preparation method of Zinc oxide nanodisk/graphene composite material simultaneously, and the method is: mixed with Graphene water suspension solution by nanometer zinc oxide disc, ultrasonic 1 ~ 3h, suction filtration and get final product;
Described nanometer zinc oxide disc is obtained by water heat transfer by precursor solution, and the precursor solution preparing nanometer zinc oxide disc is made up of dimethyl sulfoxide (DMSO), zinc acetate and water; Wherein the volume ratio of dimethyl sulfoxide (DMSO) and water is 60 ~ 95:40 ~ 5; Acetic acid zinc concentration is 0.005 ~ 1mol/L.
Above-mentioned inorganic salt are mainly used to provide metallic zinc ion.In order to control the pattern of obtained zinc oxide, the aqueous solution of dimethyl sulfoxide (DMSO) (DMSO) is used to make solvent.In addition, DMSO can be used to provide OH in hydrolytic process
-.The matrix material that the present invention prepares, both has the feature of Graphene high conductance, simultaneously the function of combining efficient rate photocatalytic degradation again.
As a kind of preferred version, the volume ratio of described dimethyl sulfoxide (DMSO) and water is 60 ~ 90:40 ~ 10; Acetic acid zinc concentration is 0.01 ~ 1mol/L.
As one most preferably scheme, the volume ratio of described dimethyl sulfoxide (DMSO) and water is 90:10; Acetic acid zinc concentration is 0.01mol/L.
As a kind of preferred version, described water is distilled water.
As a kind of preferred version, described hydrothermal temperature is 60 ~ 90 DEG C; Reaction times is 0.5 ~ 2h.
As the further preferred version of one, described hydrothermal temperature is 70 ~ 80 DEG C, and the reaction times is
1~2h。
As one most preferably scheme, described hydrothermal temperature is 70 DEG C, and the reaction times is 1h.
As a kind of preferred version, described hydro-thermal reaction is carried out in oil bath.
As a kind of preferred version, the mass ratio of nanometer zinc oxide disc and Graphene is 1:0.1 ~ 2.
As one most preferably scheme, the mass ratio of nanometer zinc oxide disc and Graphene is 1:1.
As a kind of preferred version, in described Graphene aqueous suspension, the concentration of Graphene is 2 ~ 5mg/ml.
As one most preferably scheme, in described Graphene aqueous suspension, the concentration of Graphene is 3mg/ml.
As a kind of preferred version, described graphene solution is obtained by improvement Hummer ' s method.By 15mL concentrated nitric acid, the 60mL vitriol oil and 1.5g Graphite Powder 99 mixing and stirring in ice-water bath situation.Add 9g potassium permanganate and maintain the temperature at about 20 DEG C 5min.Then remove ice-water bath be heated to 35 DEG C and keep 2h.Then add 420mL water, add 3 ~ 4mL hydrogen peroxide and obtain brown solution.Hydrochloric acid soln eccentric cleaning with 20% twice.Then centrifugal gained powder is made into suspension liquid, then ultrasonic 2h.Then by 10 mg/mL vitamins Cs, gained solution reduction is become Graphene suspension liquid, regulate pH to be 6 ~ 7 with 1mol/L sodium hydroxide solution.
A kind of Zinc oxide nanodisk/graphene composite material prepared by above-mentioned preparation method.
The structure of described Zinc oxide nanodisk/graphene composite material is the nanometer zinc oxide disc matrix material of flake graphite alkene parcel.
Described Zinc oxide nanodisk/graphene composite material combines the high light catalytic performance of nano zinc oxide material and the advantage of Graphene high conductance.
Compared with prior art, the present invention has following beneficial effect:
(1) preparation method's mild condition of described Zinc oxide nanodisk/graphene composite material, operation steps is simple, reaction required time is short, is applicable to industrialization scale operation;
(2) current found nano zinc oxide material, has higher catalytic efficiency in Photocatalytic Degradation Process, but in catalytic process, a large amount of compounds in light induced electron and hole imply that the catalytic performance of nano zinc oxide material has greatly improved space.To Graphene and the nanometer zinc oxide disc compound of high conductance be had in the present invention, and by the excellent electric conductivity of Graphene, as the transmission path of light induced electron, greatly reduce the compound with hole, thus increase effectively the photocatalysis performance to organic dye.
Compared with the nanometer zinc oxide disc that in the present invention prepared by obtained nanometer zinc oxide disc and ordinary method, there is following gain effect:
Through slaking mechanism, in the present invention, zinc-oxide nano disk is made up of the crystal grain of diameter 10-20 nm, and the vesicular structure between crystal grain considerably increases the contact area of tropeolin-D and zinc oxide, further increases its photocatalytic activity.
Accompanying drawing explanation
X-ray diffraction (XRD) spectrogram that Fig. 1 (a) is nanometer zinc oxide disc, scanning electron microscope (SEM) picture that (b, c, d) is nanometer zinc oxide disc under different multiples.
(a) low power (b) high power SEM picture of Fig. 2 Zinc oxide nanodisk/graphene composite material.
Photocatalytic degradation capability to the 100mL 50mg/L methyl orange solution contrast of Fig. 3 20mg nanometer zinc oxide disc/Graphene and nanometer zinc oxide disc.
Embodiment
Explain the present invention further below in conjunction with specific embodiment, but embodiment does not limit in any form to the present invention.
Embodiment 1
Under normal temperature, 0.1mol/L zinc acetate aqueous solution 10mL and 90mLDMSO is mixed to join in 100mL beaker, stirring reaction 1h under 70 DEG C of oil baths.Centrifugal after taking out solution left standstill half an hour, respectively with ethanol, distilled water cleaning, gained powder is nanometer zinc oxide disc.Get nanometer zinc oxide disc 20mg in the methyl orange solution of 100mL 50mg/L, stirring reaction 20min in dark enclosed space, to guarantee that physical adsorption reaches capacity.Then, under ultra violet lamp, 2min, 10min, 20min, 30min, 60min, 90min, 120min take out 3mL solution respectively in black sample pipe from solution.Gained solution 10000 is left heart 5min, gets supernatant liquor test ultra-violet absorption spectrum.Obtained nanometer zinc oxide disc is in 99.7% of 120min photocatalytic degradation total amount.
Embodiment 2
Under normal temperature, 0.01mol/L zinc acetate aqueous solution 10mL and 90mL DMSO is mixed to join in 100mL beaker, stirring reaction 1h under 90 DEG C of oil baths.Centrifugal after taking out solution left standstill half an hour, respectively with ethanol, distilled water cleaning, gained powder is Zinc oxide nanoparticle.Get Zinc oxide nanoparticle 20mg in the methyl orange solution of 100mL 50mg/L, stirring reaction 20min in dark enclosed space, to guarantee that physical adsorption reaches capacity.Then, under ultra violet lamp, 2min, 10min, 20min, 30min, 60min, 90min, 120min take out 3mL solution respectively in black sample pipe from solution.Gained solution 10000 is left heart 5min, gets supernatant liquor test ultra-violet absorption spectrum.Obtained Zinc oxide nanoparticle is in 89% of 120min photocatalytic degradation total amount.
Embodiment 3
By 15mL concentrated nitric acid, the 60mL vitriol oil and 1.5g Graphite Powder 99 mixing and stirring in ice-water bath situation.Add 9g potassium permanganate and maintain the temperature at about 20 DEG C 5min.Then remove ice-water bath be heated to 35 DEG C and keep 2h.Then add 420mL water, add 3 ~ 4mL hydrogen peroxide and obtain brown solution.Hydrochloric acid soln eccentric cleaning with 20% twice.Then centrifugal gained powder is made into the aqueous solution, then ultrasonic 2h.Then by 10 mg/mL vitamins Cs, gained solution reduction is become graphene solution, regulate pH to be 6 ~ 7 with 1mol/L sodium hydroxide solution.Graphene solution concentration is regulated to be 3mg/mL.
Under normal temperature, 0.1mol/L zinc acetate aqueous solution 10mL and 90mLDMSO is mixed to join in 100mL beaker, stirring reaction 1h under 70 DEG C of oil baths.Centrifugal after taking out solution left standstill half an hour, respectively with ethanol, distilled water cleaning, gained powder is nanometer zinc oxide disc (as shown in Figure 1).Obtained powder 30mg is joined in 10mL graphene solution, ultrasonic 2h, use the filtering membrane suction filtration of 0.2 μm subsequently.
By aforesaid method, obtain Zinc oxide nanodisk/graphene composite material (as shown in Figure 2).Get matrix material 20mg in the methyl orange solution of 100mL 50mg/L, stirring reaction 20min in dark enclosed space, to guarantee that physical adsorption reaches capacity.Then, under ultra violet lamp, 2min, 10min, 20min, 30min, 60min, 90min, 120min take out 3mL solution respectively in black sample pipe from solution.Gained solution 10000 is left heart 5min, gets supernatant liquor test ultra-violet absorption spectrum.As a comparison, 20mg zinc-oxide nano disk carries out photochemical catalysis test under the same conditions.Result as shown in Figure 3, significantly, obtained Zinc oxide nanodisk/graphene composite material 20min photo-catalytic degradation of methyl-orange 99%, 30min time complete catalyzed degradation.Greatly improve in 120min photocatalytic degradation 99.7% catalytic efficiency compared to nanometer zinc oxide disc.
Embodiment 4
By 15mL concentrated nitric acid, the 60mL vitriol oil and 1.5g Graphite Powder 99 mixing and stirring in ice-water bath situation.Add 9g potassium permanganate and maintain the temperature at about 20 DEG C 5min.Then remove ice-water bath be heated to 35 DEG C and keep 2h.Then add 420mL water, add 3 ~ 4mL hydrogen peroxide and obtain brown solution.Hydrochloric acid soln eccentric cleaning with 20% twice.Then centrifugal gained powder is made into the aqueous solution, then ultrasonic 2h.Then by 10 mg/mL vitamins Cs, gained solution reduction is become graphene solution, regulate pH to be 6 ~ 7 with 1mol/L sodium hydroxide solution.Graphene solution concentration is regulated to be 1mg/mL.
Under normal temperature, 0.01mol/L zinc acetate aqueous solution 10mL and 90mLDMSO is mixed to join in 100mL beaker, stirring reaction 1h under 90 DEG C of oil baths.Centrifugal after taking out solution left standstill half an hour, respectively with ethanol, distilled water cleaning, gained powder is Zinc oxide nanoparticle.Obtained powder 30mg is joined in 10mL graphene solution, ultrasonic 3h, use the filtering membrane suction filtration of 0.2 μm subsequently.
By aforesaid method, obtain Zinc oxide nanoparticle/graphene composite material.Get matrix material 20mg in the methyl orange solution of 100mL 50mg/L, stirring reaction 20min in dark enclosed space, to guarantee that physical adsorption reaches capacity.Then, under ultra violet lamp, 2min, 10min, 20min, 30min, 60min, 90min, 120min take out 3mL solution respectively in black sample pipe from solution.Gained solution 10000 is left heart 5min, gets supernatant liquor test ultra-violet absorption spectrum.As a comparison, 20mg Zinc oxide nanoparticle carries out photochemical catalysis test under the same conditions.Obtained Zinc oxide nanodisk/graphene composite material is at 120min photo-catalytic degradation of methyl-orange 93%.
Claims (2)
1. a nanometer zinc oxide disc matrix material, is characterized in that, is composited by nanometer zinc oxide disc and Graphene;
Described nanometer zinc oxide disc is obtained by water heat transfer by precursor solution, and the precursor solution preparing nanometer zinc oxide disc is made up of dimethyl sulfoxide (DMSO), zinc acetate and water; Wherein the volume ratio of dimethyl sulfoxide (DMSO) and water is 60 ~ 95:40 ~ 5; Acetic acid zinc concentration is 0.005 ~ 1mol/L;
The method of nanometer zinc oxide disc and Graphene compound is mixed with Graphene aqueous suspension by nanometer zinc oxide disc, ultrasonic 1 ~ 3h, suction filtration and get final product;
The mass ratio of nanometer zinc oxide disc and Graphene is 1:0.1 ~ 2;
In described graphene aqueous solution, the concentration of Graphene is 2 ~ 5mg/mL.
2. nanometer zinc oxide disc matrix material according to claim 1, it is characterized in that, the mass ratio of nanometer zinc oxide disc and Graphene is 1:1.
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| CN104229777B (en) * | 2014-05-28 | 2016-06-15 | 淮海工学院 | A kind of green reducing preparation method of self-supporting oxidation graphene film |
| 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 |
| CN105129778A (en) * | 2015-07-22 | 2015-12-09 | 上海工程技术大学 | Preparation method of nano ZnO/graphene composite material |
| CN105369341A (en) * | 2015-12-15 | 2016-03-02 | 淮北师范大学 | Method used for preparing uniform large single-orientation ZnO hexagonal micro disk |
| CN105645458B (en) * | 2016-01-12 | 2018-05-04 | 浙江师范大学 | Single dispersing ZnO micro Nano materials and its preparation method and application |
| CN106135203A (en) * | 2016-06-23 | 2016-11-23 | 温州生物材料与工程研究所 | A kind of Graphene parcel nano zine oxide hetero-junctions anti-biotic material and preparation method thereof |
| CN106925296A (en) * | 2017-03-28 | 2017-07-07 | 青岛科技大学 | A kind of nano composite material and its preparation method and application |
| CN108993467A (en) * | 2018-08-15 | 2018-12-14 | 江苏仁净环保科技有限公司 | A kind of nano-photocatalyst and preparation method and application for sewage treatment |
| CN109806857A (en) * | 2019-02-21 | 2019-05-28 | 重庆大学 | A kind of nano zinc oxide photocatalysis composite material and preparation method |
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| Controllable synthesis of hierarchical ZnO nanodisks for highly photocatalytic activity;Teng Zhai et al.;《CrystEngComm》;20120110;第14卷;第1850-1855页 * |
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