CN104237339B - A kind of Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex and preparation method thereof - Google Patents
A kind of Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Cobalto-cobaltic oxide zinc oxide/Graphene ternary complex and preparation method thereof.Described complex is by Co (NO3)2·6H2O and graphene oxide water solution mixing, be subsequently adding ammonia spirit and surfactant PVP, in constant temperature reflux heat processing procedure, generates Co (OH)2Nucleus is supported on Graphene；Zn (the NO of follow-up addition3)2·6H2O, adds ammonia again, generates Zn (NH3)4 2+And Zn (OH)2；Last in reactor constant temperature heat treatment process, Co (OH)2And Zn (OH)2Grown by your moral ripening of Oswald as nuclear particle, form nano-cobaltic-cobaltous oxide and nano granular of zinc oxide is supported on Graphene, prepare Cobalto-cobaltic oxide zinc oxide/Graphene ternary complex.Apply the product obtained by this invention to show the air-sensitive performance of excellence, show that it has preferable application prospect in gas sensor field.
Description
Technical field
The present invention relates to the preparation method of a kind of nanometer, particularly a kind of Cobalto-cobaltic oxide-zinc oxide/Graphene three
Unit's complex and preparation method thereof.
Background technology
A kind of important semi-conducting material of n-type semiconductor zinc oxide, due to electricity, the optical characteristics of its uniqueness,
Cause greatly concern in recent years.It is known that air-sensitive performance and the pattern of material, especially with material surface area
Relevant.Nano zinc oxide material has the features such as big, the easily prepared composite of specific surface area, as air-sensitive material
Expect there is a good application prospect in terms of detection poisonous and harmful and imflammable gas, but at selectivity, sensitivity and
The aspects such as operating temperature still have many to need improvements；P-type semiconductor Cobalto-cobaltic oxide has the highest catalysis to live
Property and air-sensitive performance, with zinc oxide composition p-n junction semiconductor compound can improve the response to gas and selection
Property；But due to the small-size effect of nanoparticle, it is susceptible between nanoparticle reunite, affects nanometer micro-
The air-sensitive performance of grain.
Graphene is the allotrope of the carbon that discovered in recent years is new, is the two-dimension nano materials of a kind of uniqueness.Stone
The ink huge specific surface area of alkene and good electric conductivity give the electrochemical behavior of its excellence, receiving different material
Rice grain is supported on graphene sheet layer, can increase its dispersibility because of the existence of Graphene, pass in air-sensitive for it
The research of the microelectric techniques such as sensor and device provides new approaches and new direction.To the multiple performance improving this material
Can play a positive role.
Document 1 (Na, C.W.；Woo,H.S.；Kim,I.D.；Lee,J.H.,Selective detection of NO2
and C2H5OH using a Co3O4-decorated ZnO nanowire network sensor[J].Chemical
Communications2011,47 (18), 5148-50.) report a kind of Cobalto-cobaltic oxide-zinc oxide binary and be combined
The preparation method of thing, this material has good air-sensitive response performance to gases such as ethanol.
Document 2 (Chen, N.；Li,X.；Wang,X.；Yu,J.；Wang,J.；Tang,Z.；Akbar,S.A.,
Enhanced room temperature sensing of Co3O4-intercalated reduced graphene oxide
Based gas sensors [J] .Sensors and Actuators B:Chemical2013,188,902-908.) report
The preparation method of a kind of cobalt oxide/graphene binary complex, this binary material is at room temperature to dioxy
Change nitrogen and there is higher air-sensitive response performance.
Document 3 (Liu, S.；Yu,B.；Zhang,H.；Fei,T.；Zhang,T.,Enhancing NO2gas
sensing performances at room temperature based on reduced graphene oxide-ZnO
Nanoparticleshybrids [J] .Sensors and ActuatorsB:Chemical2014,202,272-278.) report
The road preparation method of a kind of zinc oxide/Graphene binary complex, nitrogen dioxide gas is had very by this material
Fast response and resume speed and higher selectivity.
There is following defect in said method:
(1) small-size effect of nano material causes nanoparticle to be susceptible to reunite, and reduces the performance of material.
(2) limitation of binary complex, causes it that specific gas response is existed the phenomenon of poor selectivity.
Summary of the invention
It is an object of the invention to provide the preparation of a kind of Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex
Method, is that nano-cobaltic-cobaltous oxide, zinc oxide and Graphene are formed ternary complex, is applied to gas sensing
Device.
The technical solution realizing the object of the invention is:
The preparation method of a kind of Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex, receives in described complex
Rice Cobalto-cobaltic oxide and zinc oxide all uniform loads, on graphene sheet layer surface, are all in granular form；Four described oxygen
Change three cobalts-zinc oxide/Graphene ternary complex to be prepared by the following method:
By Co (NO3)2·6H2O and graphene oxide water solution mixing, be subsequently adding ammonia spirit and lives in surface
Property agent PVP, in constant temperature reflux heat processing procedure, generate Co (OH)2Nucleus is supported on Graphene；Follow-up
Zn (the NO added3)2·6H2O, adds ammonia again, generates Zn (NH3)4 2+And Zn (OH)2；Last instead
Answer in still constant temp. heating processing procedure, Co (OH)2And Zn (OH)2As nuclear particle by Oswald that moral ripening
Growth, forms nano-cobaltic-cobaltous oxide and nano granular of zinc oxide is supported on Graphene, prepares four oxidations
Three cobalts-zinc oxide/Graphene ternary complex.
Wherein, react whole process to carry out under the conditions of continuously stirred；
The concentration of graphene oxide water solution is 0.2～3mg/ml；Co(NO3)2·6H2O and the matter of graphene oxide
Amount ratio is 10:1～125:1；
The NH of the ammonia added3Concentration is 10～28wt%；The PVP mass added is 0.014～0.1g；
Constant temperature reflux heat processes in processing procedure, and reaction temperature is 50～100 DEG C, and the response time is 1～6h.
Zn(NO3)2·6H2O and mass ratio 10:1～43:1 of graphene oxide；The NH of ammonia3Concentration is
10～28wt%；
In reactor constant temperature heat treatment process, reaction temperature is 120～180 DEG C, and the response time is 12～48h.
Principle is explained:
Surface of graphene oxide is electronegative, as Co (NO3)2·6H2When O and graphene oxide mixing, the Co of positively charged2+
Owing to the effect of electrostatic force is adsorbed onto surface of graphene oxide, after adding ammonia spirit, it is formed in situ Co (NH3)6 2+.?
In constant temperature reflux heat processing procedure, generate Co (OH)2Nucleus is supported on Graphene.Zn (the NO of follow-up addition3)2·6H2O
In Zn2+It is adsorbed onto graphenic surface, after adding ammonia, generates Zn (NH3)4 2+And Zn (OH)2.In follow-up reaction
In still constant temp. heating processing procedure, Co (OH)2And Zn (OH)2Grown by your moral ripening of Oswald as nuclear particle, shape
Nano-cobaltic-cobaltous oxide and nano granular of zinc oxide is become to be supported on Graphene.Meanwhile, before graphene oxide passes through twice
Heat treatment be reduced into Graphene, due to nano-cobaltic-cobaltous oxide and the surface adsorption of zinc oxide, graphene sheet layer is not assembled
Collection is to together.Surfactant PVP serves very important effect, significantly affects pattern and the structure of material,
For by nano-cobaltic-cobaltous oxide and zinc oxide uniform load on graphene sheet layer surface, prepare Cobalto-cobaltic oxide-zinc oxide/
Graphene ternary complex.
The present invention has a following remarkable advantage:
(1) described preparation method is prepared by two one-step hydrothermals, and operation is the most convenient.
(2) using PVP is surfactant, for by nano-cobaltic-cobaltous oxide and zinc oxide uniform load at Graphene
Sheet surfaces, significantly affects pattern and the structure of material.
(3) due to nano-cobaltic-cobaltous oxide and the surface adsorption of zinc oxide, the reunion of graphene sheet layer is prevented, for fully
Play its excellent properties and establish solid foundation.
(4) Graphene has electronic structure, huge specific surface area and the minimum band gap etc. of uniqueness so that Graphene
And the interaction between gas molecule can show many distinctive phenomenons.
(5) inorganic oxide being used as gas sensitive is combined with Graphene, its point can be increased because of the existence of Graphene
Dissipating property, provide new approaches and new direction for it in the research of the microelectric techniques such as gas sensor and device, gained four aoxidizes
Three cobalts-zinc oxide/Graphene ternary complex material list reveals the air-sensitive performance of excellence.
(6) nano-cobaltic-cobaltous oxide in Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex that the present invention prepares
And zinc oxide uniform load is on graphene sheet layer surface, is in granular form form, there is excellent air-sensitive performance, right at 200 DEG C
The sensitivity of 10ppm benzaldehyde reaches as high as 6.6, has preferable application prospect in gas sensor field.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the preparation method of Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex of the present invention.
Fig. 2 is shown by the transmitted electron of embodiment 1 reaction condition gained Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex
Micro mirror (TEM) figure.
Fig. 3 is shown by the transmitted electron of comparative example 1 reaction condition gained Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex
Micro mirror (TEM) figure.
Fig. 4 is by the transmission electron microscope (TEM) of comparative example 2 reaction condition gained Cobalto-cobaltic oxide-zinc oxide composites
Figure.
Detailed description of the invention
In conjunction with Fig. 1, the preparation method of a kind of Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex of the present invention, specifically wrap
Include following steps:
Step one: graphene oxide water solution is carried out supersound process, obtains uniform dispersion liquid；
Step 2: by Co (NO3)2·6H2O joins in the dispersion liquid of step one, obtains mixed liquor a；
Step 3: ammonia, surfactant PVP are joined in the mixed liquor a of step 2, the mixed liquor b obtained；
Step 4: by the mixed liquor b isothermal reaction in reflux in step 3；
Step 5: after back flow reaction terminates, by Zn (NO3)2·6H2O, ammonia mix with step 4 mixed liquor b,
Form reactant liquor；
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor；Product is scrubbed, drying to obtain nano oxygen
Change cobalt-zinc oxide/Graphene ternary complex material.
Above-mentioned reaction is carried out under the conditions of continuously stirred.
In step one, the concentration of graphene oxide water solution is 0.2～3mg/ml, and ultrasonic time is 10～120min；
Co (NO in step 23)2·6H2O is 10:1～125:1 with the mass ratio of the graphene oxide of step one；
The NH of the ammonia added in step 33Concentration is 10～28wt%；The PVP mass added is 0.014～0.1g；
In step 4, back flow reaction temperature is 50～100 DEG C, and the response time is 1～6h.
Zn (NO in step 53)2·6H2Mass ratio 10:1～43:1 of the graphene oxide of O and step one；The NH of ammonia3
Concentration is 10～28wt%；
In step 6, reaction kettle for reaction temperature is 120～180 DEG C, and the response time is 12～48h.
Above-mentioned reaction is carried out under the conditions of continuously stirred.
Below in conjunction with embodiment, comparative example and accompanying drawing, the present invention is further detailed explanation:
Embodiment 1
Step one: 35ml graphene oxide water solution (0.2mg/ml) is carried out supersound process 60min, obtains uniform
Dispersion liquid；
Step 2: by 0.875gCo (NO3)2·6H2O joins in the dispersion liquid of step one, obtains mixed liquor a；
Step 3: 30ml ammonia (concentration is 28wt%), surfactant 0.1gPVP are joined the mixing of step 2
In liquid a, obtain mixed liquor b；
Step 4: by the mixed liquor b isothermal reaction in reflux in step 3, reaction temperature 100 DEG C, during reaction
Between be 6h；
Step 5: after back flow reaction terminates, by 0.301g Zn (NO3)2·6H2O, 5ml ammonia (concentration is 28wt%)
Mix with step 4 mixed liquor b, form reactant liquor；
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor, reaction temperature 180 DEG C, the response time is 18h；
Product is scrubbed, drying to obtain nano-cobaltic-cobaltous oxide-zinc oxide/Graphene ternary complex material.
Transmission electron microscope (TEM) photo of products therefrom is as in figure 2 it is shown, nano-cobaltic-cobaltous oxide and zinc oxide are equal
Even is supported on graphene sheet layer surface, is graininess, and produces without extensive agglomeration.By air-sensitive measuring and calculation,
To 10ppm benzaldehyde at nano-cobaltic-cobaltous oxide-zinc oxide that this example obtains/Graphene ternary complex material 200 DEG C
Sensitivity be 6.6.
Embodiment 2
Step one: 35ml graphene oxide water solution (1.5mg/ml) is carried out supersound process 10min, obtains uniform
Dispersion liquid；
Step 2: by 0.525gCo (NO3)2·6H2O joins in the dispersion liquid of step one, obtains mixed liquor a；
Step 3: 30ml ammonia (concentration is 20wt%), surfactant 0.014gPVP are joined the mixed of step 2
Close in liquid a, obtain mixed liquor b；
Step 4: by the mixed liquor b isothermal reaction in reflux in step 3, reaction temperature 80 DEG C, during reaction
Between be 3h；
Step 5: after back flow reaction terminates, by 1.3125gZn (NO3)2·6H2O, 5ml ammonia (concentration is 20wt%)
Mix with step 4 mixed liquor b, form reactant liquor；
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor, reaction temperature 150 DEG C, the response time is 48h；
Product is scrubbed, drying to obtain nano-cobaltic-cobaltous oxide-zinc oxide/Graphene ternary complex material.
By air-sensitive measuring and calculation, nano-cobaltic-cobaltous oxide-zinc oxide that this example obtains/Graphene ternary complex material
At 200 DEG C, the sensitivity to 10ppm benzaldehyde is 3.6.
Embodiment 3
Step one: 35ml graphene oxide water solution (2mg/ml) is carried out supersound process 120min, obtains uniform
Dispersion liquid；
Step 2: by 0.7gCo (NO3)2·6H2O joins in the dispersion liquid of step one, obtains mixed liquor a；
Step 3: 30ml ammonia (concentration is 10wt%), surfactant 0.05gPVP are joined the mixing of step 2
In liquid a, obtain mixed liquor b；
Step 4: by the mixed liquor b isothermal reaction in reflux in step 3, reaction temperature 50 DEG C, during reaction
Between be 1h；
Step 5: after back flow reaction terminates, by 0.7gZn (NO3)2·6H2O, 5ml ammonia (concentration is 10wt%) with
Step 4 mixed liquor b mixes, and forms reactant liquor；
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor, reaction temperature 120 DEG C, the response time is 12h；
Product is scrubbed, drying to obtain nano-cobaltic-cobaltous oxide-zinc oxide/Graphene ternary complex material.
By air-sensitive measuring and calculation, nano-cobaltic-cobaltous oxide-zinc oxide that this example obtains/Graphene ternary complex material
At 200 DEG C, the sensitivity to 10ppm benzaldehyde is 2.3.
Embodiment 4
Step one: 35ml graphene oxide water solution (3mg/ml) is carried out supersound process 60min, obtains uniform
Dispersion liquid；
Step 2: by 2.1gCo (NO3)2·6H2O joins in the dispersion liquid of step one, obtains mixed liquor a；
Step 3: 30ml ammonia (concentration is 28wt%), surfactant 0.1gPVP are joined the mixing of step 2
In liquid a, obtain mixed liquor b；
Step 4: by the mixed liquor b isothermal reaction in reflux in step 3, reaction temperature 100 DEG C, during reaction
Between be 4h；
Step 5: after back flow reaction terminates, by 2.1gZn (NO3)2·6H2O, 5ml ammonia (concentration is 28wt%) with
Step 4 mixed liquor b mixes, and forms reactant liquor；
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor, reaction temperature 150 DEG C, the response time is 20h；
Product is scrubbed, drying to obtain nano-cobaltic-cobaltous oxide-zinc oxide/Graphene ternary complex material.
By air-sensitive measuring and calculation, nano-cobaltic-cobaltous oxide-zinc oxide that this example obtains/Graphene ternary complex material
At 200 DEG C, the sensitivity to 10ppm benzaldehyde is 3.3.
Comparative example 1
Step one: 35ml graphene oxide water solution (0.2mg/ml) is carried out supersound process 60min, obtains uniform
Dispersion liquid；
Step 2: by 0.875gCo (NO3)2·6H2O joins in the dispersion liquid of step one, obtains mixed liquor a；
Step 3: 30ml ammonia (concentration is 28wt%) is joined in the mixed liquor a of step 2, obtain mixed liquor b；
Step 4: by the mixed liquor b isothermal reaction in reflux in step 3, reaction temperature 100 DEG C, during reaction
Between be 6h；
Step 5: after back flow reaction terminates, by 0.301gZn (NO3)2·6H2O, 5ml ammonia (concentration is 28wt%)
Mix with step 4 mixed liquor b, form reactant liquor；
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor, reaction temperature 180 DEG C, the response time is 18h；
Product is scrubbed, drying to obtain nano-cobaltic-cobaltous oxide-zinc oxide/Graphene ternary complex material.
By air-sensitive measuring and calculation, nano-cobaltic-cobaltous oxide-zinc oxide that this example obtains/Graphene ternary complex material
At 200 DEG C, the sensitivity to 10ppm benzaldehyde is 3.4.
Comparative example 2
Step one: by 0.875gCo (NO3)2·6H2O joins in the dispersion liquid of step one, obtains mixed liquor a；
Step 2: 30ml ammonia (concentration is 28wt%), surfactant 0.1gPVP are joined what step one obtained
In mixed liquor a；
Step 3: by the isothermal reaction in reflux of the mixed liquor in step 2, reaction temperature 100 DEG C, response time
For 6h, obtain mixed liquor b；
Step 4: after back flow reaction terminates, by 0.301g Zn (NO3)2·6H2O, 5ml ammonia (concentration is 28wt%)
Mix with step 3 mixed liquor b, form reactant liquor；
Step 5: by the isothermal reaction in closed reactor of the reactant liquor in step 4, reaction temperature 180 DEG C, during reaction
Between be 18h；Product is scrubbed, drying to obtain nano-cobaltic-cobaltous oxide-zinc oxide/Graphene ternary complex material.
By air-sensitive measuring and calculation, nano-cobaltic-cobaltous oxide-zinc oxide that this example obtains/Graphene ternary complex material
At 200 DEG C, the sensitivity to 10ppm benzaldehyde is 3.0.
Conclusion: combine transmission electron microscope (TEM) figure of Fig. 2 and Fig. 3, when not having surfactant PVP, stone
The size of ink alkene nano surface microgranule cannot be well controlled, and occurs in that phenomenon (particle diameter 50nm～200 not of uniform size
Nm), and having a certain degree of reunion to occur, the specific surface area causing nano material overall declines, to gas sensing property
Impact can be produced.In conjunction with transmission electron microscope (TEM) figure of Fig. 2 and Fig. 4, when not having Graphene, nanometer is micro-
There is not the biggest change in particle diameter and the pattern of grain, but occurs in that obvious agglomeration, causes the ratio that nano material is overall
Surface area declines, and illustrates that nanoparticle dispersion can be played effective effect by the existence of Graphene.Such as Fig. 2, work as existence
In the case of Graphene and PVP, about Cobalto-cobaltic oxide and Zinc oxide nanoparticle mean diameter 20nm, dispersibility
Well, occur without extensive agglomeration.Meanwhile, figure occurs in that the most transparent graphite platelet structure, four oxidations
Three cobalts be supported on uniformly with ZnO nanoparticle the border of Graphene with on the fold of similar silk shape, through air-sensitive
Performance test, to 10ppm benzaldehyde at nano-cobaltic-cobaltous oxide-zinc oxide/Graphene ternary complex material 200 DEG C
Sensitivity is optimal.
Claims (10)
1. Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex, it is characterised in that: described complex
It is by Co (NO3)2·6H2O and graphene oxide water solution mixing, be subsequently adding ammonia spirit and surfactant
PVP, in constant temperature reflux heat processing procedure, generates Co (OH)2Nucleus is supported on Graphene；Follow-up addition
Zn(NO3)2·6H2O, adds ammonia again, generates Zn (NH3)4 2+And Zn (OH)2；Last at reactor constant temperature
In heat treatment process, Co (OH)2And Zn (OH)2Grown by your moral ripening of Oswald as nuclear particle, formed
Nano-cobaltic-cobaltous oxide and nano granular of zinc oxide are supported on Graphene, prepare Cobalto-cobaltic oxide-oxidation
Zinc/Graphene ternary complex.
Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex the most according to claim 1, its feature
It is: react whole process and carry out under the conditions of continuously stirred.
Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex the most according to claim 1, its feature
It is: the concentration of graphene oxide water solution is 0.2～3mg/ml.
Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex the most according to claim 1, its feature
It is: Co (NO3)2·6H2O is 10:1～125:1 with the mass ratio of graphene oxide.
Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex the most according to claim 1, its feature
It is: the NH of the ammonia of addition3Concentration is 10～28wt%；The PVP mass added is 0.014～0.1g.
Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex the most according to claim 1, its feature
It is: constant temperature reflux heat processes in processing procedure, and reaction temperature is 50～100 DEG C, and the response time is 1～6h.
Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex the most according to claim 1, its feature
It is: Zn (NO3)2·6H2O and mass ratio 10:1～43:1 of graphene oxide；The NH of ammonia3Concentration is
10～28wt%.
Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex the most according to claim 1, its feature
Being: in reactor constant temperature heat treatment process, reaction temperature is 120～180 DEG C, and the response time is 12～48h.
9. the preparation method of Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex, it is characterised in that bag
Include following steps:
Step one, by Co (NO3)2·6H2O and graphene oxide water solution mixing, be subsequently adding ammonia spirit and
Surfactant PVP, in constant temperature reflux heat processing procedure, generates Co (OH)2Nucleus is supported on Graphene；
Step 2, follow-up addition Zn (NO3)2·6H2O, adds ammonia again, generates Zn (NH3)4 2+And Zn (OH)2；
Step 3, finally in reactor constant temperature heat treatment process, Co (OH)2And Zn (OH)2As nuclear particle
Grown by your moral ripening of Oswald, form nano-cobaltic-cobaltous oxide and nano granular of zinc oxide is supported on Graphene
On, prepare Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex.
The preparation method of Cobalto-cobaltic oxide-zinc oxide/Graphene ternary complex the most according to claim 9,
It is characterized in that:
React whole process to carry out under the conditions of continuously stirred；
The concentration of graphene oxide water solution is 0.2～3mg/ml；Co(NO3)2·6H2O and the matter of graphene oxide
Amount ratio is 10:1～125:1；
The NH of the ammonia added3Concentration is 10～28wt%；The PVP mass added is 0.014～0.1g；
Constant temperature reflux heat processes in processing procedure, and reaction temperature is 50～100 DEG C, and the response time is 1～6h；
Zn(NO3)2·6H2O and mass ratio 10:1～43:1 of graphene oxide；The NH of ammonia3Concentration is
10～28wt%；
In reactor constant temperature heat treatment process, reaction temperature is 120～180 DEG C, and the response time is 12～48h.
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| CN104849324B (en) * | 2015-05-25 | 2017-05-31 | 吉林大学 | A kind of resistor-type gas sensor and preparation method based on Graphene/multi-walled carbon nano-tubes/zinc oxide composite |
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Inventor after: Zhu Junwu Inventor after: Cai Shuqi Inventor after: Wang Chao Inventor after: Wang Xin Inventor after: Bi Huiping Inventor after: Liang Shiming Inventor after: Ding Jing Inventor after: Meng Xiaoqian Inventor after: Zhang Zhongqiang Inventor before: Zhu Junwu Inventor before: Wang Chao Inventor before: Wang Xin Inventor before: Bi Huiping Inventor before: Liang Shiming Inventor before: Ding Jing Inventor before: Meng Xiaoqian Inventor before: Zhang Zhongqiang |