CN102879430B - 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 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 meet commercial production and environment measuring in the urgent need to, metal-oxide semiconductor (MOS) nano particle, carbon nanomaterial and two-dimensional nano film etc. be all used as sensitive material form gas sensor.
Wherein, Graphene, due to its unique bi-dimensional cellular structure, has the irreplaceable advantage of many conventional sensors materials: the one, and in its planar structure, all carbon atoms are completely exposed, 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 make Graphene in the time that gas molecule is responded, have the signal to noise ratio (S/N ratio) more excellent than carbon nano-tube.Therefore, it has development and application prospect widely 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, electronation graphene oxide is because it adopts solwution method preparation, and method is simple, is convenient to extensive preparation, and therefore electronation graphene oxide has very wide application prospect at sensory field.We write articles and point out the 107th page of the 1st phase in 2012 in Sensors and Actuators B:Chemicals, adopt p-phenylenediamine (PPD) to reduce the redox graphene of preparing dimethyl methyl phosphonate (DMMP) gas molecule is had to good sensing sensitivity.
Although electronation graphene oxide makes great progress as sensing material, but 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 various gas molecules to selective response, to overcome above-mentioned defect.
Summary of the invention
Still there is the bottleneck of sensitvity constraint as sensing material in single Graphene, be necessary Graphene mutually compoundly with other sensing material, prepare hybrid material, give full play to the advantage of bi-material, realize material function integrated, will greatly improve the sensing capabilities of sensor.Polyaniline, as the molecule organic semiconductor of excellent performance, due to advantages such as its material are abundant, cost is low, filming technology is simple, be easy to work with other technical compatibility, at normal temperatures, is becoming focus aspect gas sensor research.Consider Graphene to combine with polyaniline, prepare graphene/polyaniline hybrid material gas sensor, give full play to the advantage of bi-material performance, have 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 graphene/polyaniline hybrid material and preparation method thereof.
For achieving the above object, the invention provides following technical scheme:
The method of the gas sensor of preparation of the present invention based on graphene/polyaniline hybrid material, comprises the steps:
1, the preparation of graphene oxide dispersion liquid
Graphite oxide is placed in to water, and the ultrasound wave of 40～100kHz is processed 1～3h, forms the suspending liquid that monolithic disperses.
Described graphite oxide is prepared from by Hummers method, Brodie method or Staudenmaier method.
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, after magnetic agitation 4～12h, in 10min～1h, splash into the liquor potassic permanganate of 0.1～1moL/L, magnetic agitation 12～24h, the solid obtaining separates, ethanol is washed, and 60 DEG C of dry 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
Graphene oxide/manganese dioxide hybrid material of step 2 gained is scattered in to 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), be placed in 60～90 DEG C of oil baths, magnetic agitation 12～24h, suction filtration, ethanol is washed, and 60 DEG C of vacuum drying 12～24h obtain pressed powder.
Described graphene oxide/manganese dioxide hybrid material and the mass ratio of p-phenylenediamine (PPD) are (1～3): (3～1).
4, the preparation of graphene/polyaniline hybrid material
Redox graphene/manganese dioxide hybrid material of step 3 gained is placed in to water, processing 1～3h with the ultrasound wave of 40～100kHz disperses, add the 1～2moL/L aniline aqueous sulfuric acid preparing, stirring at room temperature reaction 12～24h, filter, washing, 60 DEG C of dry 12～24h of last vacuum obtain pressed powder.
The compound method of described aniline aqueous sulfuric acid is in aniline, to add after a certain amount of concentrated sulphuric acid, and dilute with water forms clear solution for ultrasonic several minutes.
Described redox graphene/manganese dioxide hybrid material and the mass ratio of aniline are (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 organic solvent, form the dispersion liquid of 1～10mg/L, the dispersant liquid drop of getting 1～10mg/L of 0.1～0.5 μ L is added to electrode surface, and 60～150 DEG C 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, 1-METHYLPYRROLIDONE.
Described electrode adopts photoetching and the lift-off technology in 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.
The graphene/polyaniline hybrid material gas sensor of preparing by said method has excellent sensing capabilities to ammonia molecule, and this preparation method's technique is simple, is suitable for a large amount of preparations of gas sensor.
Brief description of the drawings
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing of required use during embodiment is described is briefly described, apparently, accompanying drawing relevant of the present invention in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is the electrode scanning electron microscope (SEM) photograph of the gas sensor based on graphene/polyaniline hybrid material of the embodiment of the present invention 1;
Fig. 2 is the gas sensor based on graphene/polyaniline hybrid material of the embodiment of the present invention 1 response curve to variable concentrations ammonia molecule;
Fig. 3 is the graphene/polyaniline hybrid material of the embodiment of the present invention 1 and the response correlation curve figure of the pure redox graphene of routine to 50ppm ammonia molecule.
Embodiment
The method of the gas sensor of preparation of the present invention based on graphene/polyaniline hybrid material, comprises the steps:
1, the preparation of graphene oxide dispersion liquid
Graphite oxide is placed in to water, and the ultrasound wave of 40～100kHz is processed 1～3h, forms the suspending liquid that monolithic disperses.
Described graphite oxide is prepared from by Hummers method, Brodie method or Staudenmaier method.
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, after magnetic agitation 4～12h, in 10min～1h, splash into the liquor potassic permanganate of 0.1～1moL/L, magnetic agitation 12～24h, the solid obtaining separates, ethanol is washed, and 60 DEG C of dry 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
Graphene oxide/manganese dioxide hybrid material of step 2 gained is scattered in to 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), be placed in 60～90 DEG C of oil baths, magnetic agitation 12～24h, suction filtration, ethanol is washed, and 60 DEG C of vacuum drying 12～24h obtain pressed powder.
Described graphene oxide/manganese dioxide hybrid material and the mass ratio of p-phenylenediamine (PPD) are (1～3): (3～1).
4, the preparation of graphene/polyaniline hybrid material
Redox graphene/manganese dioxide hybrid material of step 3 gained is placed in to water, processing 1～3h with the ultrasound wave of 40～100kHz disperses, add the 1～2moL/L aniline aqueous sulfuric acid preparing, stirring at room temperature reaction 12～24h, filter, washing, 60 DEG C of dry 12～24h of last vacuum obtain pressed powder.
The compound method of described aniline aqueous sulfuric acid is in aniline, to add after a certain amount of concentrated sulphuric acid, and dilute with water forms clear solution for ultrasonic several minutes.
Described redox graphene/manganese dioxide hybrid material and the mass ratio of aniline are (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 organic solvent, form the dispersion liquid of 1～10mg/L, the dispersant liquid drop of getting 1～10mg/L of 0.1～0.5 μ L is added to electrode surface, and 60～150 DEG C 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, 1-METHYLPYRROLIDONE.
Described electrode adopts photoetching and the lift-off technology in 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 present invention, the technical scheme in the embodiment of the present invention is described in detail, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiment.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite of not making creative work, belongs to the scope of protection of the invention.
The present invention's each raw material used all can be buied by market.
Embodiment 1
1,, by ultrasonic in water the graphite oxide 0.4g obtaining by Hummers method (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in graphene oxide dispersion liquid, add 0.7859g tetra-hydration manganous chloride, stir after 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and potpourri continues after magnetic agitation reaction 12h, 0.22 μ m teflon membrane filter suction filtration for the reaction product obtaining, washing, ethanol is washed, and 60 DEG C of dry 12h of vacuum, obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed in to N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h, forms after the dispersion liquid of 1mg/mL, adds 0.6g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 DEG C of oil baths, 0.22 μ m teflon membrane filter suction filtration for the black suspension obtaining, washing, ethanol is washed, 60 DEG C of vacuum drying 12h, obtain redox graphene/manganese dioxide hybrid material.
4,, by ultrasonic in water redox graphene/manganese dioxide hybrid material (45KHz) 1h, form the dispersion liquid of 1mg/mL.(mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:1 to another preparation aniline aqueous sulfuric acid, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in 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 DEG C of dry 12h of vacuum, obtain graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in micro-processing technology to prepare gold electrode, the spacing of controlling 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 DEG C 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 between interdigital electrode, forms galvanic circle.
From the response curve of the variable concentrations ammonia molecule of Fig. 2, can find out the increase along with ammonia molecular conecentration, the response of graphene/polyaniline hybrid material gas sensor strengthens gradually.
The response comparison diagram to 50ppm ammonia molecule from the graphene/polyaniline hybrid material of Fig. 3 and conventional pure redox graphene, can find out Polyaniline-modified after hybrid material sensor the response of ammonia molecule is obviously strengthened.
Embodiment 2
1,, by ultrasonic in water the graphite oxide 0.2g obtaining by Hummers method (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in graphene oxide dispersion liquid, add 0.7859g tetra-hydration manganous chloride, stir after 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and potpourri continues after magnetic agitation reaction 12h, 0.22 μ m teflon membrane filter suction filtration for the reaction product obtaining, washing, ethanol is washed, and 60 DEG C of dry 12h of vacuum, obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed in to N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h, forms after the dispersion liquid of 1mg/mL, adds 0.6g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 DEG C of oil baths, 0.22 μ m teflon membrane filter suction filtration for the black suspension obtaining, washing, ethanol is washed, 60 DEG C of vacuum drying 12h, obtain redox graphene/manganese dioxide hybrid material.
4,, by ultrasonic in water redox graphene/manganese dioxide hybrid material (45KHz) 1h, form the dispersion liquid of 1mg/mL.(mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:1 to another preparation aniline aqueous sulfuric acid, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in 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 DEG C of dry 12h of vacuum, obtain graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in micro-processing technology to prepare gold electrode, the spacing of controlling 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 DEG C of vacuum drying 1h, thus obtaining graphene/polyaniline hybrid material gas sensor, the resistance for preparing device is 1.4M Ω.
Embodiment 3
1,, by ultrasonic in water the graphite oxide 0.4g obtaining by Hummers method (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in graphene oxide dispersion liquid, add 0.7859g tetra-hydration manganous chloride, stir after 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and potpourri continues after magnetic agitation reaction 12h, 0.22 μ m teflon membrane filter suction filtration for the reaction product obtaining, washing, ethanol is washed, and 60 DEG C of dry 12h of vacuum, obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed in to N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h, forms after the dispersion liquid of 1mg/mL, adds 0.6g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 DEG C of oil baths, 0.22 μ m teflon membrane filter suction filtration for the black suspension obtaining, washing, ethanol is washed, 60 DEG C of vacuum drying 12h, obtain redox graphene/manganese dioxide hybrid material.
4,, by ultrasonic in water redox graphene/manganese dioxide hybrid material (45KHz) 1h, form the dispersion liquid of 1mg/mL.(mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:1 to another preparation aniline aqueous sulfuric acid, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in 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 DEG C of dry 12h of vacuum, obtain graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in micro-processing technology to prepare gold electrode, the spacing of controlling 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 DEG C of vacuum drying 1h, thus obtaining graphene/polyaniline hybrid material gas sensor, the resistance for preparing device is 0.5M Ω.
Embodiment 4
1,, by ultrasonic in water the graphite oxide 0.4g obtaining by Hummers method (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in graphene oxide dispersion liquid, add 0.7859g tetra-hydration manganous chloride, stir after 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and potpourri continues after magnetic agitation reaction 12h, 0.22 μ m teflon membrane filter suction filtration for the reaction product obtaining, washing, ethanol is washed, and 60 DEG C of dry 12h of vacuum, obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed in to N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h, forms after the dispersion liquid of 1mg/mL, adds 0.6g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 DEG C of oil baths, 0.22 μ m teflon membrane filter suction filtration for the black suspension obtaining, washing, ethanol is washed, 60 DEG C of vacuum drying 12h, obtain redox graphene/manganese dioxide hybrid material.
4,, by ultrasonic in water redox graphene/manganese dioxide hybrid material (45KHz) 1h, form the dispersion liquid of 1mg/mL.(mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:0.5 to another preparation aniline aqueous sulfuric acid, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in 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 DEG C of dry 12h of vacuum, obtain graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in micro-processing technology to prepare gold electrode, the spacing of controlling 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 DEG C of vacuum drying 1h, thus obtaining graphene/polyaniline hybrid material gas sensor, the resistance for preparing device is 0.7M Ω.
Embodiment 5
1,, by ultrasonic in water the graphite oxide 0.4g obtaining by Hummers method (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in graphene oxide dispersion liquid, add 0.7859g tetra-hydration manganous chloride, stir after 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and potpourri continues after magnetic agitation reaction 12h, 0.22 μ m teflon membrane filter suction filtration for the reaction product obtaining, washing, ethanol is washed, and 60 DEG C of dry 12h of vacuum, obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed in to N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h, forms after the dispersion liquid of 1mg/mL, adds 1.2g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 DEG C of oil baths, 0.22 μ m teflon membrane filter suction filtration for the black suspension obtaining, washing, ethanol is washed, 60 DEG C of vacuum drying 12h, obtain redox graphene/manganese dioxide hybrid material.
4,, by ultrasonic in water redox graphene/manganese dioxide hybrid material (45KHz) 1h, form the dispersion liquid of 1mg/mL.(mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:1 to another preparation aniline aqueous sulfuric acid, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in 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 DEG C of dry 12h of vacuum, obtain graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in micro-processing technology to prepare gold electrode, the spacing of controlling 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 DEG C of vacuum drying 1h, thus obtaining graphene/polyaniline hybrid material gas sensor, the resistance for preparing device is 0.6M Ω.
Embodiment 6
1,, by ultrasonic in water the graphite oxide 0.4g obtaining by Hummers method (45KHz) 1h, form the graphene oxide dispersion liquid of 1mg/mL.
2, in graphene oxide dispersion liquid, add 0.7859g tetra-hydration manganous chloride, stir after 5h, splash into potassium permanganate solution (0.6285g potassium permanganate is dissolved in 10mL water), 15min drips off, and potpourri continues after magnetic agitation reaction 12h, 0.22 μ m teflon membrane filter suction filtration for the reaction product obtaining, washing, ethanol is washed, and 60 DEG C of dry 12h of vacuum, obtain graphene oxide/manganese dioxide hybrid material.
3, graphene oxide/manganese dioxide hybrid material is placed in to N, in dinethylformamide/water mixed solvent (volume ratio 1:1), ultrasonic (45KHz) 1h, forms after the dispersion liquid of 1mg/mL, adds 0.6g p-phenylenediamine (PPD), magnetic agitation reaction 24h in 80 DEG C of oil baths, 0.22 μ m teflon membrane filter suction filtration for the black suspension obtaining, washing, ethanol is washed, 60 DEG C of vacuum drying 12h, obtain redox graphene/manganese dioxide hybrid material.
4,, by ultrasonic in water redox graphene/manganese dioxide hybrid material (45KHz) 1h, form the dispersion liquid of 1mg/mL.(mass ratio of redox graphene/manganese dioxide hybrid material and aniline is 1:1 to another preparation aniline aqueous sulfuric acid, the volumetric molar concentration of sulfuric acid is 1moL/L), and add in 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 DEG C of dry 12h of vacuum, obtain graphene/polyaniline hybrid material.
5, adopt photoetching and lift-off technology in micro-processing technology to prepare gold electrode, the spacing of controlling 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 DEG C 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 of preparing by said method has excellent sensing capabilities to 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 not deviating 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 instead of above-mentioned explanation, is therefore intended to all changes that drop in the implication and the scope that are equal to important document of claim to include in the present invention.Any Reference numeral in claim should be considered as limiting 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 is only for clarity sake, those skilled in the art should make instructions as a whole, and the technical scheme in each embodiment also can, through appropriately combined, form other embodiments that it will be appreciated by those skilled in the art that.
Claims (11)
1. a preparation method for the gas sensor based on graphene/polyaniline hybrid material, is characterized in that, comprises the steps:
The preparation of a, graphene oxide dispersion liquid
Graphite oxide is placed in to 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, after magnetic agitation 4～12h, in 10min～1h, splash into the liquor potassic permanganate of 0.1～1moL/L, magnetic agitation 12～24h, the solid obtaining separates, ethanol is washed, and 60 DEG C of dry 12～24h of vacuum obtain pressed powder;
The preparation of c, redox graphene/manganese dioxide hybrid material
Graphene oxide/manganese dioxide hybrid material of step b gained is scattered in to 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), be placed in 60～90 DEG C of oil baths, magnetic agitation 12～24h, suction filtration, ethanol is washed, and 60 DEG C of vacuum drying 12～24h obtain pressed powder;
The preparation of d, graphene/polyaniline hybrid material
Redox graphene/manganese dioxide hybrid material of step c gained is placed in to water, processing 1～3h with the ultrasound wave of 40～100kHz disperses, add the 1～2moL/L aniline aqueous sulfuric acid preparing, stirring at room temperature reaction 12～24h, filter, washing, 60 DEG C of dry 12～24h of last 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 organic solvent, form the dispersion liquid of 1～10mg/L, the dispersant liquid drop of getting 1～10mg/L of 0.1～0.5 μ L is added to electrode surface, and 60～150 DEG C of vacuum drying obtain graphene/polyaniline hybrid material gas sensor.
2. preparation method according to claim 1, 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, is characterized in that: the mol ratio of the graphene oxide described in step b, four hydration manganous chloride and potassium permanganate is 1:1:1.
4. preparation method according to claim 1, is characterized in that: the separation described in 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/manganese dioxide hybrid material described in step c 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 steps d is in aniline, to add after a certain amount of concentrated sulphuric acid, and dilute with water forms clear solution for ultrasonic several minutes.
7. preparation method according to claim 1, is characterized in that: the mass ratio of the redox graphene/manganese dioxide hybrid material described in steps d and aniline is (1～4): (4～1).
8. preparation method according to claim 1, is characterized in that: the organic solvent described in step e is selected from one or more in ethanol, acetone, tetrahydrofuran, DMF, DMA, 1-METHYLPYRROLIDONE.
9. preparation method according to claim 1, is characterized in that: the electrode described in step e adopts photoetching and the lift-off technology in 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. the gas sensor based on graphene/polyaniline hybrid material, is prepared by the preparation method described in claim 1～9 any one.
The application of 11. gas sensors according to claim 10 in ammonia detects.
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| CN103575771B (en) * | 2013-11-20 | 2015-07-29 | 江苏大学 | A kind of gas sensor and preparation method thereof |
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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 |
| CN107086130B (en) * | 2017-04-21 | 2019-07-02 | 南京信息工程大学 | A kind of graphene/DyCoO3Composite material and preparation method and application |
| CN107782773B (en) * | 2017-08-31 | 2020-02-21 | 南京航空航天大学 | Nano gas sensor processing technology based on ultrasonic aggregation method |
| CN107490611B (en) * | 2017-09-05 | 2019-09-27 | 济南大学 | Polyaniline hybridized material of a kind of chirality MOF- and its preparation method and application |
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