CN102879430A - Graphene/polyaniline hybrid material-based gas sensor and preparation method for same - Google Patents
Graphene/polyaniline hybrid material-based gas sensor and preparation method for same Download PDFInfo
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Abstract
The invention discloses a graphene/polyaniline hybrid material-based gas sensor and a preparation method for the same. The preparation method comprises the following steps of: ultrasonically preparing graphene oxide dispersion, preparing a graphene/manganese dioxide hybrid material, inducing the polymerization of aniline in situ by taking manganese dioxide as an oxidant to replace the manganese dioxide to prepare a graphene/polyaniline hybrid material, and adding obtained graphene/polyaniline hybrid material organic solvent dispersion dropwise to the surface of electrodes, thereby obtaining the graphene/polyaniline hybrid material-based gas sensor. The prepared graphene/polyaniline hybrid material-based gas sensor has high sensitivity to ammonia molecules. The preparation method is simple and suitable for the large-scale preparation of the gas sensor.
Description
Technical field
The invention belongs to sensor technical field, relate to a kind of nano-sensor and preparation method thereof, be specifically related to a kind of gas sensor based on the graphene/polyaniline hybrid material and preparation method thereof.
Background technology
Along with the development of nanometer technology, nano gas sensor has obtained considerable progress.Especially for satisfy commercial production and environment measuring in the urgent need to, metal-oxide semiconductor (MOS) nano particle, carbon nanomaterial and two-dimensional nano film etc. all have been used as sensitive material and have consisted of gas sensor.
Wherein, Graphene is because its unique bi-dimensional cellular structure has the irreplaceable advantage of many conventional sensors materials: the one, and all carbon atoms are fully exposed on its planar structure, have very large specific surface area, a large amount of gas passages are provided, thereby can have greatly improved the sensitivity of device; The 2nd, the two-dimensional structure that it is unique and high-quality lattice are so that Graphene has the signal to noise ratio (S/N ratio) more excellent than carbon nano-tube when gas molecule is responded.Therefore, it has widely development and application prospect at aspects such as biology, chemistry, machinery, aviation, military affairs.
Various preparation methods such as stripping method, chemical gaseous phase deposition method, epitaxial growth method, chemistry or thermal reduction graphite oxide method etc., all can be used for preparing gas response grapheme material.Wherein, the electronation graphene oxide is because it adopts the solwution method preparation, and method is simple, is convenient to extensive preparation, so the electronation graphene oxide has very wide application prospect at sensory field.We write articles and point out that the redox graphene that adopts the p-phenylenediamine (PPD) reduction to prepare has good sensing sensitivity to dimethyl methyl phosphonate (DMMP) gas molecule the 107th page of the 1st phase in 2012 in Sensors and Actuators B:Chemicals.
Although the electronation graphene oxide makes great progress as sensing material, yet there is the bottleneck of sensitvity constraint in Graphene as sensing material.
Therefore, for above-mentioned technical matters, be necessary further research, prepare the Graphene gas sensor that various gas molecules is had selective response, to overcome defects.
Summary of the invention
Still there is the bottleneck of sensitvity constraint in single Graphene as sensing material, be necessary Graphene mutually compoundly with other sensing material, prepare hybrid material, give full play to the advantage of bi-material, the realization material function is integrated, will greatly improve the sensing capabilities of sensor.Polyaniline is as the molecule organic semiconductor of excellent performance, because the advantage such as its material is abundant, cost is low, filming technology is simple, be easy to work with other technical compatibility, is at normal temperatures becoming focus aspect the gas sensor research.Consideration combines Graphene with polyaniline, prepare graphene/polyaniline hybrid material gas sensor, gives full play to the advantage of bi-material performance, has very important significance for the performance that improves sensor.
In view of this, the object of the present invention is to provide a kind of highly sensitive gas sensor based on the graphene/polyaniline hybrid material and preparation method thereof.
For achieving the above object, the invention provides following technical scheme:
Preparation of the present invention comprises the steps: based on the method for the gas sensor of graphene/polyaniline hybrid material
1, the preparation of graphene oxide dispersion liquid
Graphite oxide is placed water, and the ultrasound wave of 40～100kHz is processed 1～3h, forms the suspending liquid that monolithic disperses.
Described graphite oxide forms by Hummers method, Brodie method or Staudenmaier legal system are standby.
Described graphene oxide dispersion liquid concentration is 0.5～3mg/mL.
2, the preparation of graphene oxide/manganese dioxide hybrid material
In the graphene oxide dispersion liquid of step 1 gained, add four hydration manganous chloride, behind magnetic agitation 4～12h, in 10min～1h, splash into the liquor potassic permanganate of 0.1～1moL/L, magnetic agitation 12～24h, the solid that obtains separates, ethanol is washed, and 60 ℃ of drying 12～24h of vacuum obtain pressed powder.
The mol ratio of described graphene oxide, four hydration manganous chloride and potassium permanganate is 1:1:1.
Described separation is centrifugal or suction filtration, and centrifugation rate is 4500rad/min, and suction filtration filter membrane aperture is 0.22 μ m.
3, the preparation of redox graphene/manganese dioxide hybrid material
The graphene oxide of step 2 gained/manganese dioxide hybrid material is scattered in the N that volume ratio is 1:1, in the mixed solvent of dinethylformamide and water, the ultrasound wave of 40～100kHz is processed 1～3h, add p-phenylenediamine (PPD), place 60～90 ℃ of oil baths, magnetic agitation 12～24h, suction filtration, ethanol is washed, and 60 ℃ of vacuum drying 12～24h obtain pressed powder.
The mass ratio of described graphene oxide/manganese dioxide hybrid material and p-phenylenediamine (PPD) is (1～3): (3～1).
4, the preparation of graphene/polyaniline hybrid material
The redox graphene of step 3 gained/manganese dioxide hybrid material is placed water, processing 1～3h with the ultrasound wave of 40～100kHz disperses, add the 1～2moL/L aniline aqueous sulfuric acid for preparing, stirring at room reaction 12～24h, filter, washing, last 60 ℃ of drying 12～24h of vacuum obtain pressed powder.
The compound method of described aniline aqueous sulfuric acid is add a certain amount of concentrated sulphuric acid in aniline after, dilute with water, ultrasonic several minutes formation clear solutions.
The mass ratio of described redox graphene/manganese dioxide hybrid material and aniline is (1～4): (4～1).
5, the preparation of graphene/polyaniline hybrid material gas sensor
The graphene/polyaniline hybrid material of step 4 gained is dispersed in the organic solvent, form the dispersion liquid of 1～10mg/L, get 0.1～0.5 μ L dispersant liquid drop and be added to electrode surface, 60～150 ℃ of vacuum drying obtain graphene/polyaniline hybrid material gas sensor.
Described organic solvent is selected from one or more in ethanol, acetone, tetrahydrofuran, DMF, DMA, the 1-METHYLPYRROLIDONE.
Described electrode adopts photoetching and the lift-off technology in the micro-processing technology to prepare, and the spacing of positive and negative electrode is 300～800 μ m, and the spacing of adjacent electrode is 10～100 μ m.
Graphene/polyaniline hybrid material gas sensor by the said method preparation has excellent sensing capabilities to the ammonia molecule, and this preparation method's technique is simple, is suitable for a large amount of preparations of gas sensor.
Description of drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the invention, the accompanying drawing of required use was done to introduce simply during the below will describe embodiment, apparently, accompanying drawing relevant of the present invention in the following describes only is some embodiments of the present invention, for those of ordinary skills, under the prerequisite of not paying creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the electrode scanning electron microscope (SEM) photograph based on the gas sensor of graphene/polyaniline hybrid material of the embodiment of the invention 1;
Fig. 2 be the embodiment of the invention 1 based on the gas sensor of the graphene/polyaniline hybrid material response curve to variable concentrations ammonia molecule;
Fig. 3 is that the graphene/polyaniline hybrid material of the embodiment of the invention 1 and conventional pure redox graphene are to the response correlation curve figure of 50ppm ammonia molecule.
Embodiment
Preparation of the present invention comprises the steps: based on the method for the gas sensor of graphene/polyaniline hybrid material
1, the preparation of graphene oxide dispersion liquid
Graphite oxide is placed water, and the ultrasound wave of 40～100kHz is processed 1～3h, forms the suspending liquid that monolithic disperses.
Described graphite oxide forms by Hummers method, Brodie method or Staudenmaier legal system are standby.
Described graphene oxide dispersion liquid concentration is 0.5～3mg/mL.
2, the preparation of graphene oxide/manganese dioxide hybrid material
In the graphene oxide dispersion liquid of step 1 gained, add four hydration manganous chloride, behind magnetic agitation 4～12h, in 10min～1h, splash into the liquor potassic permanganate of 0.1～1moL/L, magnetic agitation 12～24h, the solid that obtains separates, ethanol is washed, and 60 ℃ of drying 12～24h of vacuum obtain pressed powder.
The mol ratio of described graphene oxide, four hydration manganous chloride and potassium permanganate is 1:1:1.
Described separation is centrifugal or suction filtration, and centrifugation rate is 4500rad/min, and suction filtration filter membrane aperture is 0.22 μ m.
3, the preparation of redox graphene/manganese dioxide hybrid material
The graphene oxide of step 2 gained/manganese dioxide hybrid material is scattered in the N that volume ratio is 1:1, in the mixed solvent of dinethylformamide and water, the ultrasound wave of 40～100kHz is processed 1～3h, add p-phenylenediamine (PPD), place 60～90 ℃ of oil baths, magnetic agitation 12～24h, suction filtration, ethanol is washed, and 60 ℃ of vacuum drying 12～24h obtain pressed powder.
The mass ratio of described graphene oxide/manganese dioxide hybrid material and p-phenylenediamine (PPD) is (1～3): (3～1).
4, the preparation of graphene/polyaniline hybrid material
The redox graphene of step 3 gained/manganese dioxide hybrid material is placed water, processing 1～3h with the ultrasound wave of 40～100kHz disperses, add the 1～2moL/L aniline aqueous sulfuric acid for preparing, stirring at room reaction 12～24h, filter, washing, last 60 ℃ of drying 12～24h of vacuum obtain pressed powder.
The compound method of described aniline aqueous sulfuric acid is add a certain amount of concentrated sulphuric acid in aniline after, dilute with water, ultrasonic several minutes formation clear solutions.
The mass ratio of described redox graphene/manganese dioxide hybrid material and aniline is (1～4): (4～1).
5, the preparation of graphene/polyaniline hybrid material gas sensor
The graphene/polyaniline hybrid material of step 4 gained is dispersed in the organic solvent, form the dispersion liquid of 1～10mg/L, get 0.1～0.5 μ L dispersant liquid drop and be added to electrode surface, 60～150 ℃ of vacuum drying obtain graphene/polyaniline hybrid material gas sensor.
Described organic solvent is selected from one or more in ethanol, acetone, tetrahydrofuran, DMF, DMA, the 1-METHYLPYRROLIDONE.
Described electrode adopts photoetching and the lift-off technology in the micro-processing technology to prepare, and the spacing of positive and negative electrode is 300～800 μ m, and the spacing of adjacent electrode is 10～100 μ m.
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is described in detail, obviously, described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, the every other embodiment that those of ordinary skills obtain under the prerequisite of not making creative work belongs to the scope of protection of the invention.
Each used raw material of the present invention all can be buied by market.
Embodiment 1
1, will with the graphite oxide 0.4g that the Hummers method obtains ultrasonic in water (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in the graphene oxide dispersion liquid, add 0.7859g four hydration manganous chloride, after stirring 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and after potpourri continued magnetic agitation reaction 12h, the reaction product that obtains was with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, and 60 ℃ of dry 12h of vacuum obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h behind the dispersion liquid of formation 1mg/mL, adds the 0.6g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 ℃ of oil baths, the black suspension that obtains is washed with 0.22 μ m teflon membrane filter suction filtration, and ethanol is washed, 60 ℃ of vacuum drying 12h obtain redox graphene/manganese dioxide hybrid material.
4, with redox graphene/manganese dioxide hybrid material ultrasonic in water (45KHz) 1h, form the dispersion liquid of 1mg/mL.Other prepares the aniline aqueous sulfuric acid, and (mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:1, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in the above-mentioned hybrid material aqueous dispersions, room temperature magnetic agitation 12h, with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, 60 ℃ of dry 12h of vacuum obtain the graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in the micro-processing technology to prepare gold electrode, the spacing of control positive and negative electrode is 800 μ m, and the spacing of adjacent electrode is 30 μ m.Get 0.1 μ L graphene/polyaniline hybrid material alcohol dispersion liquid (1mg/L) and be added drop-wise to electrode surface, 80 ℃ of vacuum drying 1h, thus obtaining graphene/polyaniline hybrid material gas sensor, the resistance for preparing device is 1M Ω.
From the electrode scanning electron microscope (SEM) photograph of Fig. 1, can see that polyaniline is distributed in the surface of Graphene, hybrid material forms network structure, is overlapped on and forms the galvanic circle between the interdigital electrode.
From the response curve of the variable concentrations ammonia molecule of Fig. 2, can find out the increase along with the ammonia molecular conecentration, the response of graphene/polyaniline hybrid material gas sensor strengthens gradually.
From the graphene/polyaniline hybrid material of Fig. 3 and the conventional pure redox graphene response comparison diagram to 50ppm ammonia molecule, can find out that hybrid material sensor behind the Polyaniline-modified obviously strengthens the response of ammonia molecule.
Embodiment 2
1, will with the graphite oxide 0.2g that the Hummers method obtains ultrasonic in water (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in the graphene oxide dispersion liquid, add 0.7859g four hydration manganous chloride, after stirring 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and after potpourri continued magnetic agitation reaction 12h, the reaction product that obtains was with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, and 60 ℃ of dry 12h of vacuum obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h behind the dispersion liquid of formation 1mg/mL, adds the 0.6g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 ℃ of oil baths, the black suspension that obtains is washed with 0.22 μ m teflon membrane filter suction filtration, and ethanol is washed, 60 ℃ of vacuum drying 12h obtain redox graphene/manganese dioxide hybrid material.
4, with redox graphene/manganese dioxide hybrid material ultrasonic in water (45KHz) 1h, form the dispersion liquid of 1mg/mL.Other prepares the aniline aqueous sulfuric acid, and (mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:1, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in the above-mentioned hybrid material aqueous dispersions, room temperature magnetic agitation 12h, with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, 60 ℃ of dry 12h of vacuum obtain the graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in the micro-processing technology to prepare gold electrode, the spacing of control positive and negative electrode is 800 μ m, and the spacing of adjacent electrode is 30 μ m.Get 0.1 μ L graphene/polyaniline hybrid material alcohol dispersion liquid (1mg/L) and be added drop-wise to electrode surface, 80 ℃ of vacuum drying 1h, thus obtaining graphene/polyaniline hybrid material gas sensor, the resistance for preparing device is 1.4M Ω.
Embodiment 3
1, will with the graphite oxide 0.4g that the Hummers method obtains ultrasonic in water (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in the graphene oxide dispersion liquid, add 0.7859g four hydration manganous chloride, after stirring 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and after potpourri continued magnetic agitation reaction 12h, the reaction product that obtains was with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, and 60 ℃ of dry 12h of vacuum obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h behind the dispersion liquid of formation 1mg/mL, adds the 0.6g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 ℃ of oil baths, the black suspension that obtains is washed with 0.22 μ m teflon membrane filter suction filtration, and ethanol is washed, 60 ℃ of vacuum drying 12h obtain redox graphene/manganese dioxide hybrid material.
4, with redox graphene/manganese dioxide hybrid material ultrasonic in water (45KHz) 1h, form the dispersion liquid of 1mg/mL.Other prepares the aniline aqueous sulfuric acid, and (mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:1, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in the above-mentioned hybrid material aqueous dispersions, room temperature magnetic agitation 12h, with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, 60 ℃ of dry 12h of vacuum obtain the graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in the micro-processing technology to prepare gold electrode, the spacing of control positive and negative electrode is 800 μ m, and the spacing of adjacent electrode is 30 μ m.Get 0.1 μ L graphene/polyaniline hybrid material alcohol dispersion liquid (10mg/L) and be added drop-wise to electrode surface, 80 ℃ of vacuum drying 1h, thus obtaining graphene/polyaniline hybrid material gas sensor, the resistance for preparing device is 0.5M Ω.
Embodiment 4
1, will with the graphite oxide 0.4g that the Hummers method obtains ultrasonic in water (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in the graphene oxide dispersion liquid, add 0.7859g four hydration manganous chloride, after stirring 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and after potpourri continued magnetic agitation reaction 12h, the reaction product that obtains was with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, and 60 ℃ of dry 12h of vacuum obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h behind the dispersion liquid of formation 1mg/mL, adds the 0.6g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 ℃ of oil baths, the black suspension that obtains is washed with 0.22 μ m teflon membrane filter suction filtration, and ethanol is washed, 60 ℃ of vacuum drying 12h obtain redox graphene/manganese dioxide hybrid material.
4, with redox graphene/manganese dioxide hybrid material ultrasonic in water (45KHz) 1h, form the dispersion liquid of 1mg/mL.Other prepares the aniline aqueous sulfuric acid, and (mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:0.5, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in the above-mentioned hybrid material aqueous dispersions, room temperature magnetic agitation 12h, with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, 60 ℃ of dry 12h of vacuum obtain the graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in the micro-processing technology to prepare gold electrode, the spacing of control positive and negative electrode is 800 μ m, and the spacing of adjacent electrode is 30 μ m.Get 0.1 μ L graphene/polyaniline hybrid material alcohol dispersion liquid (1mg/L) and be added drop-wise to electrode surface, 80 ℃ of vacuum drying 1h, thus obtaining graphene/polyaniline hybrid material gas sensor, the resistance for preparing device is 0.7M Ω.
Embodiment 5
1, will with the graphite oxide 0.4g that the Hummers method obtains ultrasonic in water (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in the graphene oxide dispersion liquid, add 0.7859g four hydration manganous chloride, after stirring 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and after potpourri continued magnetic agitation reaction 12h, the reaction product that obtains was with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, and 60 ℃ of dry 12h of vacuum obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h behind the dispersion liquid of formation 1mg/mL, adds the 1.2g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 ℃ of oil baths, the black suspension that obtains is washed with 0.22 μ m teflon membrane filter suction filtration, and ethanol is washed, 60 ℃ of vacuum drying 12h obtain redox graphene/manganese dioxide hybrid material.
4, with redox graphene/manganese dioxide hybrid material ultrasonic in water (45KHz) 1h, form the dispersion liquid of 1mg/mL.Other prepares the aniline aqueous sulfuric acid, and (mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:1, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in the above-mentioned hybrid material aqueous dispersions, room temperature magnetic agitation 12h, with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, 60 ℃ of dry 12h of vacuum obtain the graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in the micro-processing technology to prepare gold electrode, the spacing of control positive and negative electrode is 800 μ m, and the spacing of adjacent electrode is 30 μ m.Get 0.1 μ L graphene/polyaniline hybrid material alcohol dispersion liquid (1mg/L) and be added drop-wise to electrode surface, 80 ℃ of vacuum drying 1h, thus obtaining graphene/polyaniline hybrid material gas sensor, the resistance for preparing device is 0.6M Ω.
Embodiment 6
1, will with the graphite oxide 0.4g that the Hummers method obtains ultrasonic in water (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in the graphene oxide dispersion liquid, add 0.7859g four hydration manganous chloride, after stirring 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and after potpourri continued magnetic agitation reaction 12h, the reaction product that obtains was with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, and 60 ℃ of dry 12h of vacuum obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h behind the dispersion liquid of formation 1mg/mL, adds the 0.6g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 ℃ of oil baths, the black suspension that obtains is washed with 0.22 μ m teflon membrane filter suction filtration, and ethanol is washed, 60 ℃ of vacuum drying 12h obtain redox graphene/manganese dioxide hybrid material.
4, with redox graphene/manganese dioxide hybrid material ultrasonic in water (45KHz) 1h, form the dispersion liquid of 1mg/mL.Other prepares the aniline aqueous sulfuric acid, and (mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:1, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in the above-mentioned hybrid material aqueous dispersions, room temperature magnetic agitation 12h, with 0.22 μ m teflon membrane filter suction filtration, washing, ethanol is washed, 60 ℃ of dry 12h of vacuum obtain the graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in the micro-processing technology to prepare gold electrode, the spacing of control positive and negative electrode is 800 μ m, and the spacing of adjacent electrode is 30 μ m.Get 0.2 μ L graphene/polyaniline hybrid material alcohol dispersion liquid (1mg/L) and be added drop-wise to electrode surface, 80 ℃ of vacuum drying 1h, thus obtaining graphene/polyaniline hybrid material gas sensor, the resistance for preparing device is 0.6M Ω.
In sum, the graphene/polyaniline hybrid material gas sensor for preparing by said method has excellent sensing capabilities to the ammonia molecule, and this preparation method's technique is simple, is suitable for a large amount of preparations of gas sensor.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned example embodiment, and in the situation that does not deviate from spirit of the present invention or essential characteristic, can realize the present invention with other concrete form.Therefore, no matter from which point, all should regard embodiment as exemplary, and be nonrestrictive, scope of the present invention is limited by claims rather than above-mentioned explanation, therefore is intended to include in the present invention dropping on the implication that is equal to important document of claim and all changes in the scope.Any Reference numeral in the claim should be considered as limit related claim.
In addition, be to be understood that, although this instructions is described according to embodiment, but be not that each embodiment only comprises an independently technical scheme, this narrating mode of instructions only is for clarity sake, those skilled in the art should make instructions as a whole, and the technical scheme among each embodiment also can through appropriate combination, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (11)
1. the preparation method based on the gas sensor of graphene/polyaniline hybrid material is characterized in that, comprises the steps:
The preparation of a, graphene oxide dispersion liquid
Graphite oxide is placed water, and the ultrasound wave of 40～100kHz is processed 1～3h, forms the suspending liquid that monolithic disperses;
The preparation of b, graphene oxide/manganese dioxide hybrid material
In the graphene oxide dispersion liquid of step a gained, add four hydration manganous chloride, behind magnetic agitation 4～12h, in 10min～1h, splash into the liquor potassic permanganate of 0.1～1moL/L, magnetic agitation 12～24h, the solid that obtains separates, ethanol is washed, and 60 ℃ of drying 12～24h of vacuum obtain pressed powder;
The preparation of c, redox graphene/manganese dioxide hybrid material
The graphene oxide of step b gained/manganese dioxide hybrid material is scattered in the N that volume ratio is 1:1, in the mixed solvent of dinethylformamide and water, the ultrasound wave of 40～100kHz is processed 1～3h, add p-phenylenediamine (PPD), place 60～90 ℃ of oil baths, magnetic agitation 12～24h, suction filtration, ethanol is washed, and 60 ℃ of vacuum drying 12～24h obtain pressed powder;
The preparation of d, graphene/polyaniline hybrid material
The redox graphene of step c gained/manganese dioxide hybrid material is placed water, processing 1～3h with the ultrasound wave of 40～100kHz disperses, add the 1～2moL/L aniline aqueous sulfuric acid for preparing, stirring at room reaction 12～24h, filter, washing, last 60 ℃ of drying 12～24h of vacuum obtain pressed powder;
The preparation of e, graphene/polyaniline hybrid material gas sensor
The graphene/polyaniline hybrid material of steps d gained is dispersed in the organic solvent, form the dispersion liquid of 1～10mg/L, get 0.1～0.5 μ L dispersant liquid drop and be added to electrode surface, 60～150 ℃ of vacuum drying obtain graphene/polyaniline hybrid material gas sensor.
2. preparation method according to claim 1, it is characterized in that: the graphene oxide dispersion liquid concentration of step a gained is 0.5～3mg/mL.
3. preparation method according to claim 1, it is characterized in that: the mol ratio of the graphene oxide described in the step b, four hydration manganous chloride and potassium permanganate is 1:1:1.
4. preparation method according to claim 1, it is characterized in that: the separation described in the step b is centrifugal or suction filtration, and centrifugation rate is 4500rad/min, and suction filtration filter membrane aperture is 0.22 μ m.
5. preparation method according to claim 1 is characterized in that: the mass ratio of the graphene oxide described in the step c/manganese dioxide hybrid material and p-phenylenediamine (PPD) is (1～3): (3～1).
6. preparation method according to claim 1 is characterized in that: the compound method of the aniline aqueous sulfuric acid described in the steps d is add a certain amount of concentrated sulphuric acid in aniline after, and dilute with water formed clear solution in ultrasonic several minutes.
7. preparation method according to claim 1 is characterized in that: the mass ratio of the redox graphene described in the steps d/manganese dioxide hybrid material and aniline is (1～4): (4～1).
8. preparation method according to claim 1, it is characterized in that: the organic solvent described in the step e is selected from one or more in ethanol, acetone, tetrahydrofuran, DMF, DMA, the 1-METHYLPYRROLIDONE.
9. preparation method according to claim 1 is characterized in that: the electrode described in the step e adopts photoetching and the lift-off technology in the micro-processing technology to prepare, and the spacing of positive and negative electrode is 300～800 μ m, and the spacing of adjacent electrode is 10～100 μ m.
10. gas sensor based on redox graphene is by each described preparation method's preparation of claim 1～9.
11. the application of gas sensor according to claim 10 in ammonia detects.
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| CN107064218A (en) * | 2016-10-31 | 2017-08-18 | 扬州大学 | Based on reduced graphene semiconductor room temperature nitrogen dioxide sensor preparation method |
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