CN104237339A - Cobaltosic oxide-zinc oxide/grapheme ternary complex and preparation method thereof - Google Patents
Cobaltosic oxide-zinc oxide/grapheme ternary complex and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cobaltosic oxide- zinc oxide/grapheme ternary complex and a preparation method thereof. The cobaltosic oxide-zinc oxide/grapheme ternary complex is prepared by the following steps: Co(No3)2 6H2O and a graphene oxide water solution are mixed, then an ammonia-water solution and a surface active agent PVP are added, and during a constant temperature backflow heat treatment process, Co(OH)2 loaded on graphene is produced; then, Zn(NO3)2 6H2O is added, then ammonia water is added again, and Zn(NH3)42+ and Zn(OH)2 are generated; finally, during a constant temperature heat treatment process of a reacting kettle, Co(OH)2 and Zn(OH)2 are taken as particles and grow through ostwald ripening, so as to form nanometer cobaltosic oxide and nano-zinc oxide particles loaded on the graphene, and the cobaltosic oxide-zinc oxide/grapheme ternary complex is prepared. The cobaltosic oxide-zinc oxide/grapheme ternary complex prepared according to the preparation method provided by the invention, an excellent gas-sensitive property is shown and the cobaltosic oxide- zinc oxide/grapheme ternary complex has a relatively good application prospect in the field of gas sensors.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer, particularly a kind of cobaltosic oxide-zinc paste/Graphene ternary complex and preparation method thereof.
Background technology
A kind of important semiconductor material of n-type semiconductor zinc paste, due to electricity, the optical characteristics of its uniqueness, causes very big concern in recent years.As everyone knows, the pattern of air-sensitive performance and material, especially relevant with material surface area.Nano zinc oxide material have specific surface area large, be easy to prepare the features such as compound substance, in detection poisonous and harmful and inflammable gas, good application prospect is had as gas sensitive, but in selectivity, the aspect such as sensitivity and working temperature still has and manyly needs improvements; P-type semiconductor cobaltosic oxide has very high catalytic activity and air-sensitive performance, forms p-n junction semiconductor compound can improve response to gas and selectivity with zinc paste; But due to the small-size effect of nanoparticle, easily reunite between nanoparticle, affect the air-sensitive performance of nanoparticle.
Graphene is the allotrope of the carbon that discovered in recent years is new, is a kind of two-dimension nano materials of uniqueness.The specific surface area that Graphene is huge and good electric conductivity give the electrochemical behavior of its excellence, by the nano particle load of different material on graphene sheet layer, can be increased it dispersed, for it provides new approaches and new direction in the research of the microelectric techniques such as gas sensor and device because of the existence of Graphene.Can play a positive role to the multiple performance improving this material.
Document 1 (Na, C.W.; Woo, H.S.; Kim, I.D.; Lee, J.H., Selective detection of NO
2and C
2h
5oH using a Co3O4-decorated ZnO nanowire network sensor [J] .Chemical communications2011,47 (18), 5148-50.) report the preparation method of a kind of cobaltosic oxide-zinc paste binary complex, 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 a kind of preparation method of cobalt oxide/graphene binary complex, this binary material at room temperature has higher air-sensitive response performance to nitrogen dioxide gas.
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 preparation method of a kind of zinc paste/Graphene binary complex, this material has very fast response and recovery speed and higher selectivity to nitrogen dioxide gas.
There is following defect in said method:
(1) small-size effect of nano material causes nano particle easily to reunite, and reduces the performance of material.
(2) limitation of binary complex, causes it to there is the phenomenon of poor selectivity to specific gas response.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of cobaltosic oxide-zinc paste/Graphene ternary complex, be that nano-cobaltic-cobaltous oxide, zinc paste and Graphene are formed ternary complex, be applied to gas sensor.
The technical solution realizing the object of the invention is:
A preparation method for cobaltosic oxide-zinc paste/Graphene ternary complex, in described compound, all uniform load is surperficial at graphene sheet layer, all in graininess for nano-cobaltic-cobaltous oxide and zinc paste; Described cobaltosic oxide-zinc paste/Graphene ternary complex is prepared by the following method:
By Co (NO
3)
26H
2o and graphene oxide water solution mixing, then add ammonia spirit and surfactant PVP, in constant temperature reflux heat processing procedure, generates Co (OH)
2nucleus load is on Graphene; Follow-up Zn (the NO added
3)
26H
2o, adds ammoniacal liquor again, generates Zn (NH
3)
4 2+and Zn (OH)
2; Last in reactor constant temperature heat treatment process, Co (OH)
2and Zn (OH)
2grown by your moral slaking of Oswald as nuclear particle, formation nano-cobaltic-cobaltous oxide and nano granular of zinc oxide load, on Graphene, prepare cobaltosic oxide-zinc paste/Graphene ternary complex.
Wherein, react whole process to carry out under Keep agitation condition;
The concentration of graphene oxide water solution is 0.2 ~ 3mg/ml; Co (NO
3)
26H
2the mass ratio of O and graphene oxide is 10:1 ~ 125:1;
The NH of the ammoniacal liquor added
3concentration is 10 ~ 28wt%; The PVP quality added is 0.014 ~ 0.1g;
In constant temperature reflux heat process processing procedure, temperature of reaction is 50 ~ 100 DEG C, and the reaction time is 1 ~ 6h.
Zn (NO
3)
26H
2mass ratio 10:1 ~ the 43:1 of O and graphene oxide; The NH of ammoniacal liquor
3concentration is 10 ~ 28wt%;
In reactor constant temperature heat treatment process, temperature of reaction is 120 ~ 180 DEG C, and the reaction time is 12 ~ 48h.
Principle is explained:
Surface of graphene oxide is electronegative, as Co (NO
3)
26H
2when O and graphene oxide mixing, the Co of positively charged
2+because the effect of electrostatic force is adsorbed onto surface of graphene oxide, after adding ammonia spirit, original position forms Co (NH
3)
6 2+.In constant temperature reflux heat processing procedure, generate Co (OH)
2nucleus load is on Graphene.Follow-up Zn (the NO added
3)
26H
2zn in O
2+be adsorbed onto graphenic surface, after adding ammoniacal liquor, generate Zn (NH
3)
4 2+and Zn (OH)
2.In follow-up reactor constant temperature heat treatment process, Co (OH)
2and Zn (OH)
2grown by your moral slaking of Oswald as nuclear particle, formation nano-cobaltic-cobaltous oxide and nano granular of zinc oxide load are on Graphene.Meanwhile, graphene oxide is reduced into Graphene by the thermal treatment before twice, and due to the adsorption of nano-cobaltic-cobaltous oxide and zinc paste, graphene sheet layer can not be brought together.Surfactant PVP serves very important effect, significantly affects pattern and the structure of material, for by nano-cobaltic-cobaltous oxide and zinc paste uniform load on graphene sheet layer surface, prepare cobaltosic oxide-zinc paste/Graphene ternary complex.
The present invention has following remarkable advantage:
(1) described preparation method is by two one-step hydrothermal preparations, and operation facilitates continuously.
(2) adopt PVP to be surfactant, for by nano-cobaltic-cobaltous oxide and zinc paste uniform load on graphene sheet layer surface, significantly affects pattern and the structure of material.
(3) due to the adsorption of nano-cobaltic-cobaltous oxide and zinc paste, preventing the reunion of graphene sheet layer, having established solid foundation for giving full play to its excellent properties.
(4) Graphene has unique electronic structure, huge specific surface area and minimum band gap etc., makes the interaction between Graphene and gas molecule can show many distinctive phenomenons.
(5) inorganic oxide and the Graphene compound of gas sensitive will be used as, can be increased it dispersed because of the existence of Graphene, for it provides new approaches and new direction in the research of the microelectric techniques such as gas sensor and device, gained cobaltosic oxide-zinc paste/Graphene ternary complex material list reveals excellent air-sensitive performance.
(6) in cobaltosic oxide-zinc paste/Graphene ternary complex of preparing of the present invention nano-cobaltic-cobaltous oxide and zinc paste uniform load on graphene sheet layer surface, in particulate form, there is excellent air-sensitive performance, at 200 DEG C, 6.6 are reached as high as to the sensitivity of 10ppm benzaldehyde, in gas sensor field, there is good application prospect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the preparation method of cobaltosic oxide-zinc paste/Graphene ternary complex of the present invention.
Fig. 2 is by transmission electron microscope (TEM) figure of embodiment 1 reaction conditions gained cobaltosic oxide-zinc paste/Graphene ternary complex.
Fig. 3 is by transmission electron microscope (TEM) figure of comparative example 1 reaction conditions gained cobaltosic oxide-zinc paste/Graphene ternary complex.
Fig. 4 is by transmission electron microscope (TEM) figure of comparative example 2 reaction conditions gained cobaltosic oxide-zinc oxide composites.
Embodiment
Composition graphs 1, the preparation method of a kind of cobaltosic oxide-zinc paste/Graphene ternary complex of the present invention, specifically comprises the following steps:
Step one: graphene oxide water solution is carried out ultrasonic process, obtains uniform dispersion liquid;
Step 2: by Co (NO
3)
26H
2o joins in the dispersion liquid of step one, obtains mixed liquor a;
Step 3: ammoniacal liquor, 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 (NO
3)
26H
2o, ammoniacal liquor mix with step 4 mixed liquor b, forming reactions liquid;
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor; Product is through washing, being drying to obtain nanometer cobalt oxide-zinc paste/Graphene ternary complex material.
Above-mentioned reaction is carried out under Keep agitation condition.
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 2
3)
26H
2the mass ratio of the graphene oxide of O and step one is 10:1 ~ 125:1;
The NH of the ammoniacal liquor added in step 3
3concentration is 10 ~ 28wt%; The PVP quality added is 0.014 ~ 0.1g;
In step 4, back flow reaction temperature is 50 ~ 100 DEG C, and the reaction time is 1 ~ 6h.
Zn (NO in step 5
3)
26H
2mass ratio 10:1 ~ the 43:1 of the graphene oxide of O and step one; The NH of ammoniacal liquor
3concentration is 10 ~ 28wt%;
In step 6, reaction kettle for reaction temperature is 120 ~ 180 DEG C, and the reaction time is 12 ~ 48h.
Above-mentioned reaction is carried out under Keep agitation condition.
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 ultrasonic process 60min, obtains uniform dispersion liquid;
Step 2: by 0.875gCo (NO
3)
26H
2o joins in the dispersion liquid of step one, obtains mixed liquor a;
Step 3: 30ml ammoniacal liquor (concentration is 28wt%), surfactant 0.1gPVP are joined in the mixed liquor a of step 2, obtains mixed liquor b;
Step 4: by the mixed liquor b isothermal reaction in reflux in step 3, temperature of reaction 100 DEG C, the reaction time is 6h;
Step 5: after back flow reaction terminates, by 0.301g Zn (NO
3)
26H
2o, 5ml ammoniacal liquor (concentration is 28wt%) mixes with step 4 mixed liquor b, forming reactions liquid;
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor, temperature of reaction 180 DEG C, the reaction time is 18h; Product is through washing, being drying to obtain nano-cobaltic-cobaltous oxide-zinc paste/Graphene ternary complex material.
As shown in Figure 2, nano-cobaltic-cobaltous oxide and the uniform load of zinc paste, on graphene sheet layer surface, are graininess, and produce without extensive agglomeration transmission electron microscope (TEM) photo of products therefrom.By air-sensitive measuring and calculation, be 6.6 to the sensitivity of 10ppm benzaldehyde at nano-cobaltic-cobaltous oxide-zinc paste that this example obtains/Graphene ternary complex material 200 DEG C.
Embodiment 2
Step one: 35ml graphene oxide water solution (1.5mg/ml) is carried out ultrasonic process 10min, obtains uniform dispersion liquid;
Step 2: by 0.525gCo (NO
3)
26H
2o joins in the dispersion liquid of step one, obtains mixed liquor a;
Step 3: 30ml ammoniacal liquor (concentration is 20wt%), surfactant 0.014gPVP are joined in the mixed liquor a of step 2, obtains mixed liquor b;
Step 4: by the mixed liquor b isothermal reaction in reflux in step 3, temperature of reaction 80 DEG C, the reaction time is 3h;
Step 5: after back flow reaction terminates, by 1.3125gZn (NO
3)
26H
2o, 5ml ammoniacal liquor (concentration is 20wt%) mixes with step 4 mixed liquor b, forming reactions liquid;
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor, temperature of reaction 150 DEG C, the reaction time is 48h; Product is through washing, being drying to obtain nano-cobaltic-cobaltous oxide-zinc paste/Graphene ternary complex material.
By air-sensitive measuring and calculation, be 3.6 to the sensitivity of 10ppm benzaldehyde at nano-cobaltic-cobaltous oxide-zinc paste that this example obtains/Graphene ternary complex material 200 DEG C.
Embodiment 3
Step one: 35ml graphene oxide water solution (2mg/ml) is carried out ultrasonic process 120min, obtains uniform dispersion liquid;
Step 2: by 0.7gCo (NO
3)
26H
2o joins in the dispersion liquid of step one, obtains mixed liquor a;
Step 3: 30ml ammoniacal liquor (concentration is 10wt%), surfactant 0.05gPVP are joined in the mixed liquor a of step 2, obtains mixed liquor b;
Step 4: by the mixed liquor b isothermal reaction in reflux in step 3, temperature of reaction 50 DEG C, the reaction time is 1h;
Step 5: after back flow reaction terminates, by 0.7gZn (NO
3)
26H
2o, 5ml ammoniacal liquor (concentration is 10wt%) mixes with step 4 mixed liquor b, forming reactions liquid;
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor, temperature of reaction 120 DEG C, the reaction time is 12h; Product is through washing, being drying to obtain nano-cobaltic-cobaltous oxide-zinc paste/Graphene ternary complex material.
By air-sensitive measuring and calculation, be 2.3 to the sensitivity of 10ppm benzaldehyde at nano-cobaltic-cobaltous oxide-zinc paste that this example obtains/Graphene ternary complex material 200 DEG C.
Embodiment 4
Step one: 35ml graphene oxide water solution (3mg/ml) is carried out ultrasonic process 60min, obtains uniform dispersion liquid;
Step 2: by 2.1gCo (NO
3)
26H
2o joins in the dispersion liquid of step one, obtains mixed liquor a;
Step 3: 30ml ammoniacal liquor (concentration is 28wt%), surfactant 0.1gPVP are joined in the mixed liquor a of step 2, obtains mixed liquor b;
Step 4: by the mixed liquor b isothermal reaction in reflux in step 3, temperature of reaction 100 DEG C, the reaction time is 4h;
Step 5: after back flow reaction terminates, by 2.1gZn (NO
3)
26H
2o, 5ml ammoniacal liquor (concentration is 28wt%) mixes with step 4 mixed liquor b, forming reactions liquid;
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor, temperature of reaction 150 DEG C, the reaction time is 20h; Product is through washing, being drying to obtain nano-cobaltic-cobaltous oxide-zinc paste/Graphene ternary complex material.
By air-sensitive measuring and calculation, be 3.3 to the sensitivity of 10ppm benzaldehyde at nano-cobaltic-cobaltous oxide-zinc paste that this example obtains/Graphene ternary complex material 200 DEG C.
Comparative example 1
Step one: 35ml graphene oxide water solution (0.2mg/ml) is carried out ultrasonic process 60min, obtains uniform dispersion liquid;
Step 2: by 0.875gCo (NO
3)
26H
2o joins in the dispersion liquid of step one, obtains mixed liquor a;
Step 3: 30ml ammoniacal liquor (concentration is 28wt%) is joined in the mixed liquor a of step 2, obtains mixed liquor b;
Step 4: by the mixed liquor b isothermal reaction in reflux in step 3, temperature of reaction 100 DEG C, the reaction time is 6h;
Step 5: after back flow reaction terminates, by 0.301gZn (NO
3)
26H
2o, 5ml ammoniacal liquor (concentration is 28wt%) mixes with step 4 mixed liquor b, forming reactions liquid;
Step 6: by the isothermal reaction in closed reactor of above-mentioned reactant liquor, temperature of reaction 180 DEG C, the reaction time is 18h; Product is through washing, being drying to obtain nano-cobaltic-cobaltous oxide-zinc paste/Graphene ternary complex material.
By air-sensitive measuring and calculation, be 3.4 to the sensitivity of 10ppm benzaldehyde at nano-cobaltic-cobaltous oxide-zinc paste that this example obtains/Graphene ternary complex material 200 DEG C.
Comparative example 2
Step one: by 0.875gCo (NO
3)
26H
2o joins in the dispersion liquid of step one, obtains mixed liquor a;
Step 2: 30ml ammoniacal liquor (concentration is 28wt%), surfactant 0.1gPVP are joined in the mixed liquor a that step one obtains;
Step 3: by the isothermal reaction in reflux of the mixed liquor in step 2, temperature of reaction 100 DEG C, the reaction time is 6h, obtains mixed liquor b;
Step 4: after back flow reaction terminates, by 0.301g Zn (NO
3)
26H
2o, 5ml ammoniacal liquor (concentration is 28wt%) mixes with step 3 mixed liquor b, forming reactions liquid;
Step 5: by the isothermal reaction in closed reactor of the reactant liquor in step 4, temperature of reaction 180 DEG C, the reaction time is 18h; Product is through washing, being drying to obtain nano-cobaltic-cobaltous oxide-zinc paste/Graphene ternary complex material.
By air-sensitive measuring and calculation, be 3.0 to the sensitivity of 10ppm benzaldehyde at nano-cobaltic-cobaltous oxide-zinc paste that this example obtains/Graphene ternary complex material 200 DEG C.
Conclusion: transmission electron microscope (TEM) figure of composition graphs 2 and Fig. 3, when there is no surfactant PVP, the size of graphenic surface nanoparticle cannot be well controlled, there is phenomenon not of uniform size (particle diameter 50nm ~ 200nm not etc.), and there is reunion to a certain degree to occur, cause the specific surface area of nano material entirety to decline, air-sensitive performance is had an impact.Transmission electron microscope (TEM) figure of composition graphs 2 and Fig. 4, when there is no Graphene, there is not too large change in the particle diameter of nanoparticle and pattern, but there is obvious agglomeration, cause the specific surface area of nano material entirety to decline, illustrate that the existence of Graphene can play effective effect to nanoparticle dispersion.As Fig. 2, when there is Graphene and PVP, cobaltosic oxide and Zinc oxide nanoparticle about mean grain size 20nm, favorable dispersibility, occurs without extensive agglomeration.Simultaneously, obvious transparent graphite platelet structure has been there is in figure, cobaltosic oxide and the uniform load of ZnO nanoparticle are on the fold of the border of Graphene and similar silk shape, through air-sensitive performance test, best to the sensitivity of 10ppm benzaldehyde at nano-cobaltic-cobaltous oxide-zinc paste/Graphene ternary complex material 200 DEG C.
Claims (10)
1. cobaltosic oxide-zinc paste/Graphene ternary complex, is characterized in that: described compound is by Co (NO
3)
26H
2o and graphene oxide water solution mixing, then add ammonia spirit and surfactant PVP, in constant temperature reflux heat processing procedure, generates Co (OH)
2nucleus load is on Graphene; Follow-up Zn (the NO added
3)
26H
2o, adds ammoniacal liquor again, generates Zn (NH
3)
4 2+and Zn (OH)
2; Last in reactor constant temperature heat treatment process, Co (OH)
2and Zn (OH)
2grown by your moral slaking of Oswald as nuclear particle, formation nano-cobaltic-cobaltous oxide and nano granular of zinc oxide load, on Graphene, prepare cobaltosic oxide-zinc paste/Graphene ternary complex.
2. cobaltosic oxide-zinc paste/Graphene ternary complex according to claim 1, is characterized in that: react whole process and carry out under Keep agitation condition.
3. cobaltosic oxide-zinc paste/Graphene ternary complex according to claim 1, is characterized in that: the concentration of graphene oxide water solution is 0.2 ~ 3mg/ml.
4. cobaltosic oxide-zinc paste/Graphene ternary complex according to claim 1, is characterized in that: Co (NO
3)
26H
2the mass ratio of O and graphene oxide is 10:1 ~ 125:1.
5. cobaltosic oxide-zinc paste/Graphene ternary complex according to claim 1, is characterized in that: the NH of the ammoniacal liquor added
3concentration is 10 ~ 28wt%; The PVP quality added is 0.014 ~ 0.1g.
6. cobaltosic oxide-zinc paste/Graphene ternary complex according to claim 1, is characterized in that: in constant temperature reflux heat process processing procedure, temperature of reaction is 50 ~ 100 DEG C, and the reaction time is 1 ~ 6h.
7. cobaltosic oxide-zinc paste/Graphene ternary complex according to claim 1, is characterized in that: Zn (NO
3)
26H
2mass ratio 10:1 ~ the 43:1 of O and graphene oxide; The NH of ammoniacal liquor
3concentration is 10 ~ 28wt%.
8. cobaltosic oxide-zinc paste/Graphene ternary complex according to claim 1, is characterized in that: in reactor constant temperature heat treatment process, and temperature of reaction is 120 ~ 180 DEG C, and the reaction time is 12 ~ 48h.
9. a preparation method for cobaltosic oxide-zinc paste/Graphene ternary complex, is characterized in that comprising the following steps:
Step one, by Co (NO
3)
26H
2o and graphene oxide water solution mixing, then add ammonia spirit and surfactant PVP, in constant temperature reflux heat processing procedure, generates Co (OH)
2nucleus load is on Graphene;
Step 2, the follow-up Zn (NO added
3)
26H
2o, adds ammoniacal liquor again, generates Zn (NH
3)
4 2+and Zn (OH)
2;
Step 3, finally in reactor constant temperature heat treatment process, Co (OH)
2and Zn (OH)
2grown by your moral slaking of Oswald as nuclear particle, formation nano-cobaltic-cobaltous oxide and nano granular of zinc oxide load, on Graphene, prepare cobaltosic oxide-zinc paste/Graphene ternary complex.
10. the preparation method of cobaltosic oxide-zinc paste/Graphene ternary complex according to claim 9, is characterized in that:
React whole process to carry out under Keep agitation condition;
The concentration of graphene oxide water solution is 0.2 ~ 3mg/ml; Co (NO
3)
26H
2the mass ratio of O and graphene oxide is 10:1 ~ 125:1;
The NH of the ammoniacal liquor added
3concentration is 10 ~ 28wt%; The PVP quality added is 0.014 ~ 0.1g;
In constant temperature reflux heat process processing procedure, temperature of reaction is 50 ~ 100 DEG C, and the reaction time is 1 ~ 6h.
Zn (NO
3)
26H
2mass ratio 10:1 ~ the 43:1 of O and graphene oxide; The NH of ammoniacal liquor
3concentration is 10 ~ 28wt%; In reactor constant temperature heat treatment process, temperature of reaction is 120 ~ 180 DEG C, and the reaction time is 12 ~ 48h.
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| CN104713914A (en) * | 2015-02-02 | 2015-06-17 | 华中科技大学 | Semiconductor resistance gas sensor and production method thereof |
| CN104849324A (en) * | 2015-05-25 | 2015-08-19 | 吉林大学 | Resistance-type gas sensor based on graphene/multi-walled carbon nano-tube/zinc oxide composite material, and manufacturing method of resistance-type gas sensor |
| CN105158303A (en) * | 2015-09-09 | 2015-12-16 | 安徽工程大学 | Precious metal/base metal oxide/graphene ternary composite gas sensitive material and preparation method thereof |
| CN106450235A (en) * | 2016-12-07 | 2017-02-22 | 华南师范大学 | Preparation method and application of self-assembled nano flaky porous structure tricobalt tetraoxide-zinc oxide composite material |
| CN106841326A (en) * | 2017-03-13 | 2017-06-13 | 中国石油大学(华东) | A kind of zinc oxide cobalt hollow nano polyhedron film to alcohol sensible |
| CN110749628A (en) * | 2019-10-25 | 2020-02-04 | 中国石油大学(华东) | Acetone-sensitive cobaltosic oxide/zinc oxide nano-meter rice heterojunction thin film |
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