CN101354368A - Polypyrrole and carbon nano-tube composite gas sensor and manufacturing method thereof - Google Patents
Polypyrrole and carbon nano-tube composite gas sensor and manufacturing method thereof Download PDFInfo
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- CN101354368A CN101354368A CNA2008101205520A CN200810120552A CN101354368A CN 101354368 A CN101354368 A CN 101354368A CN A2008101205520 A CNA2008101205520 A CN A2008101205520A CN 200810120552 A CN200810120552 A CN 200810120552A CN 101354368 A CN101354368 A CN 101354368A
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Abstract
The invention discloses a composite gas sensor of polypyrrole and carbon nanotube and a manufacturing method of the gas sensor. A ceramic glass is used as a substrate, multiple pairs of interdigital gold electrodes are arranged on the substrate, and a composite gas sensing film of the polypyrrole and the carbon nanotube is coated on the surfaces of the ceramic substrate and the interdigital gold electrodes. The manufacturing method of the gas sensor has simple preparation techniques, mild condition and low cost, and is especially applicable to batch production. The prepared gas sensor can measure ammonia concentration at room temperature, is characterized by high responsive sensitivity, good recoverability and quick response in responding to ammonia gas of 50 to 12500 ppm, and can be used for the ammonia concentration detection in industrial and agricultural production as well as environment monitoring.
Description
Technical field
The present invention relates to a kind of polypyrrole and carbon nano-tube composite gas sensor and preparation method thereof.
Background technology
Along with the mankind deepen day by day to the attention of self health with to the concern of ecologic environment, the demand of national economy sustainable development strategy is had higher requirement to the Monitoring and Controlling of environmental gas.This research for gas sensor, exploitation and production provide opportunities and challenges.The macromolecule gas sensor has high sensitivity, high selectivity, advantage such as can at room temperature use.And, can need carry out MOLECULE DESIGN and synthetic according to response because the macromolecule gas sensitive is convenient to modify, of a great variety, applicability is wide, has become one of emphasis of gas sensor research.And composite high-molecular type gas sensor comprehensively macromolecule with the excellent air-sensitive response characteristic of its gas sensitive, overcome its limitation, improve response sensitivity, the selectivity of gas sensor effectively, improve the stability and the reliability of its response, be expected to become the gas sensor that a class has the applications well prospect.
Summary of the invention
A kind ofly can have reverse response at the ammonia of 50～12500ppm but the purpose of this invention is to provide to concentration, and highly sensitive, response is very fast, but the polypyrrole that room temperature detects and carbon nano-tube composite gas sensor and preparation method thereof.
Polypyrrole of the present invention and carbon mano-tube composite gas sensor have ceramic substrate, have many at ceramic substrate photomask surface and evaporation to interdigital gold electrode, on interdigital gold electrode, be connected with lead-in wire, surface-coated at ceramic substrate and interdigital gold electrode has air-sensitive film, and air-sensitive film is polypyrrole and carbon mano-tube composite.
The method for making of polypyrrole and carbon mano-tube composite gas sensor may further comprise the steps:
1) clean surface photoetching and evaporation have the ceramic substrate of interdigital gold electrode, dry for standby;
2) concentrated sulphuric acid and red fuming nitric acid (RFNA) being mixed into mixed acid solution in 3: 7 by volume～3: 12 joins in the carbon nano-tube, consumption is that every g carbon nano-tube adds 100～220ml mixed acid solution, the potpourri that obtains was through sonicated 10～30 minutes, at 40～60 ℃ of 1～12h that reflux down, cooling is filtered, be neutral with washed with de-ionized water to filtrate, obtain acid-treated carbon nano-tube, vacuum drying is ground stand-by;
3) adopt the method for sonicated, oxygenant, adulterant, acid treatment carbon nano-tube are scattered in prepare precursor solution in the water, the total concentration of oxygenant and adulterant is 10～50mg/ml, and the consumption of acid treatment carbon nano-tube is 0.1～2mg/ml;
4) will impregnated in 0.5～2min in the precursor solution through the interdigital gold electrode of the ceramic substrate that step 1) is cleaned, lift taking-up after, leave standstill and dry, place pyrroles's saturated vapour vapour phase polymerization 1～24h, behind absolute ethyl alcohol, deionized water cyclic washing, vacuum drying gets final product.
The interdigital gold electrode on ceramic substrate of the present invention surface has 8～16 pairs, and the interdigital width of interdigital gold electrode is 20～200 μ m, and interdigital gap is 20～200 μ m.
Among the present invention, oxygenant can be ammonium persulfate or ferric trichloride.Said adulterant can be ferric trichloride, neopelex or paratoluenesulfonic acid sodium salt.When adopting ferric trichloride, it plays the effect of oxygenant and adulterant simultaneously.
The concentration of the above-mentioned concentrated sulphuric acid is mass concentration 96-98%, and the concentration of red fuming nitric acid (RFNA) is mass concentration 65-68%.
Advantage of the present invention is:
1) prepared polypyrrole and carbon nano-tube composite gas sensor are the methods by vapour phase polymerization, at ceramic substrate that is coated with carbon nano-tube and interdigital gold electrode surfaces deposition polypyrrole, preparation polypyrrole and carbon nano-tube composite air-sensitive film, solved the problem that polypyrrole is difficult to process film forming, and film forming is not subjected to the restriction of substrate size and shape.By polypyrrole and carbon mano-tube composite air-sensitive film that gas phase polymerization process makes, not only film forming is even, and can contact well with interdigital gold electrode surfaces with ceramic substrate;
When 2) adopting vapour phase polymerization to prepare polypyrrole and carbon mano-tube composite film, the introducing of adulterant has improved the stability of air-sensitive film, and changes oxygenant and the kind scalable polypyrrole of adulterant and the response sensitivity and the recovery of carbon mano-tube composite gas sensor;
3) polypyrrole and the carbon nano-tube composite gas sensor that adopts gaseous polymerization to prepare, polypyrrole deposits equably in carbon nano tube surface, helps to improve the consistance of element responds;
4) prepared polypyrrole and carbon mano-tube composite gas sensor, combine the advantage of polypyrrole and carbon nano-tube, the good conductive properties of carbon nano-tube and big specific surface area have been given full play to, and the good response sensitivity of doping polypyrrole and the characteristics of recovery, polypyrrole that makes and carbon nano-tube composite gas sensor have higher response sensitivity to ammonia, and the response recovery is fine;
5) adopt gas phase polymerization process to prepare polypyrrole, can realize regulation and control easily by changing the parameters such as composition of polymerization time and precursor solution for the composite gas sensor response characteristic;
6) at ambient temperature, polypyrrole that makes and carbon mano-tube composite gas sensor all have good response sensitivity to the ammonia in the broad concentration range of 50～12500ppm, and in survey ammonia concentration scope, the response recovery is all fine;
7) much smaller than the ammonia with concentration, its response to ammonia has certain selectivity to the response of various organic steams for prepared polypyrrole and carbon mano-tube composite gas sensor;
8) adopt the method for dip-coating and vapour phase polymerization growth to prepare gas sensor, simple and easy to do, the yield rate height, high conformity is suitable for producing in batches;
9) to have a volume little for gas sensor of the present invention, and advantage such as cost is low, and is easy to use can be widely used in commercial production, the environmental monitoring of measurement and control to(for) ammonia.
Description of drawings
Fig. 1 is the structural representation of gas sensor of the present invention;
Fig. 2 is the polypyrrole of gas sensor of the present invention and the stereoscan photograph of composite air-sensitive membrane of carbon nano tube;
Fig. 3 is a gas sensor of the present invention to the response of ammonia change curve in time;
Fig. 4 is based on the response sensitivity curve of the gas sensor of polypyrrole, carbon nano-tube and polypyrrole and carbon mano-tube composite to ammonia;
Fig. 5 adopts polypyrrole that different oxygenants and adulterant make and the carbon nano-tube composite gas sensor response sensitivity curve to ammonia.
Embodiment
Further specify the present invention below in conjunction with drawings and Examples.
With reference to Fig. 1, polypyrrole of the present invention and carbon mano-tube composite gas sensor have ceramic substrate 1, have many to interdigital gold electrode 2 on the ceramic substrate surface, on interdigital gold electrode, be connected with lead-in wire 4, be coated with air-sensitive film 3 at ceramic substrate and interdigital gold electrode surfaces, air-sensitive film 3 is polypyrrole and carbon mano-tube composite.
The interdigital gold electrode on said ceramic substrate surface has 8～16 pairs, and the width of interdigital gold electrode is 20～200 μ m, and interdigital gap is 20～200 μ m.
Embodiment 1
1) ceramic substrate of interdigital gold electrode is arranged with absolute ethyl alcohol and acetone soaking and washing photomask surface and evaporation, dry for standby;
2) acid treatment carbon nano-tube, be about to 30ml red fuming nitric acid (RFNA) and 80ml concentrated sulphuric acid mixed preparing mixed acid solution, it is added in the carbon nano-tube of 0.5g, behind the potpourri process sonicated 60min that obtains, at 50 ℃ of following backflow 8h, after the cooling, through filtering with microporous membrane, and being neutral with washed with de-ionized water to filtrate, the acid treatment carbon nano-tube vacuum drying that obtains is ground stand-by;
3) method of employing sonicated, ammonium persulfate, neopelex and acid treatment carbon nano-tube be scattered in prepare precursor solution in the water, wherein the concentration of ammonium persulfate is 5mg/ml, and the concentration of neopelex is 20mg/ml, and the concentration of acid treatment carbon nano-tube is 2mg/ml;
4) adopt dip coater impregnated in 1min in the precursor solution through the ceramic interdigital gold electrode that step 1) is cleaned, after lifting taking-up, leave standstill and dry, vapour phase polymerization 18h in pyrroles's saturated vapour, behind absolute ethyl alcohol, deionization cyclic washing, dry 12h under the vacuum obtains polypyrrole and carbon nano-tube composite gas sensor.
Embodiment 2
1) ceramic substrate of interdigital gold electrode is arranged with absolute ethyl alcohol and acetone soaking and washing photomask surface and evaporation, dry for standby;
2) acid treatment carbon nano-tube, be about to 20ml red fuming nitric acid (RFNA) and 80ml concentrated sulphuric acid mixed preparing mixed acid solution, it is added in the carbon nano-tube of 0.5g, behind the potpourri process sonicated 20min that obtains, at 60 ℃ of following backflow 6h, after the cooling, through filtering with microporous membrane, and being neutral with washed with de-ionized water to filtrate, the acid treatment carbon nano-tube vacuum drying that obtains is ground stand-by;
3) method of employing sonicated, ammonium persulfate, paratoluenesulfonic acid sodium salt and acid treatment carbon nano-tube be scattered in prepare precursor solution in the aqueous solution, wherein the concentration of ammonium persulfate is 5mg/ml, and the concentration of paratoluenesulfonic acid sodium salt is 5mg/ml, and the concentration of acid treatment carbon nano-tube is 0.1mg/ml;
4) adopt dip coater impregnated in 2min in the precursor solution through the ceramic interdigital gold electrode that step 1) is cleaned, after lifting taking-up, leave standstill and dry, vapour phase polymerization 3h in pyrroles's saturated vapour, behind absolute ethyl alcohol, deionization cyclic washing, dry 4h under the vacuum obtains polypyrrole and carbon nano-tube composite gas sensor.
Embodiment 3
1) ceramic substrate of interdigital gold electrode is arranged with absolute ethyl alcohol and acetone soaking and washing photomask surface and evaporation, dry for standby;
2) acid treatment carbon nano-tube, be about to 30ml red fuming nitric acid (RFNA) and 70ml concentrated sulphuric acid mixed preparing mixed acid solution, it is added in the carbon nano-tube of 1g, behind the potpourri process sonicated 30min that obtains, at 40 ℃ of following backflow 12h, after the cooling, through filtering with microporous membrane, and being neutral with washed with de-ionized water to filtrate, the acid treatment carbon nano-tube vacuum drying that obtains is ground stand-by;
3) adopt the method for sonicated, ferric trichloride and acid treatment carbon nano-tube are scattered in prepare precursor solution in the aqueous solution, wherein the concentration of ferric trichloride is 50mg/ml, and the concentration of acid treatment carbon nano-tube is 1mg/ml;
4) adopt dip coater impregnated in 1min in the precursor solution through the ceramic interdigital gold electrode that step 1) is cleaned, after lifting taking-up, leave standstill and dry, vapour phase polymerization 22h in pyrroles's saturated vapour, behind absolute ethyl alcohol, deionization cyclic washing, dry 24h under the vacuum obtains polypyrrole and carbon nano-tube composite gas sensor.
The polypyrrole of gas sensor and the stereoscan photograph of composite air-sensitive membrane of carbon nano tube, as shown in Figure 2.
Fig. 3 is the polypyrrole that makes and the carbon nano-tube composite gas sensor response characteristic to ammonia.As seen from the figure, response has reversibility to gas sensor to ammonia.
Figure 4 shows that the carbon nano-tube, polypyrrole and the polypyrrole that make and carbon nano-tube composite gas sensor response sensitivity curve to ammonia, as seen from the figure, in whole measurement ammonia concentration scope, polypyrrole and carbon nano-tube composite gas sensor to the ammonia response sensitivity all apparently higher than the homogenous material gas sensor.
Figure 5 shows that the polypyrrole that makes by different oxygenants, adulterant and carbon nano-tube composite gas sensor response sensitivity curve to ammonia, as seen from the figure, can regulate and control polypyrrole and carbon nano-tube composite gas sensor response sensitivity to a great extent by the kind that changes oxygenant or adulterant to ammonia.
Claims (6)
1. polypyrrole and carbon nano-tube composite gas sensor, it is characterized in that it has ceramic substrate (1), have many at ceramic substrate photomask surface and evaporation to interdigital gold electrode (2), on interdigital gold electrode, be connected with lead-in wire (4), be coated with air-sensitive film (3) at ceramic substrate and interdigital gold electrode surfaces, air-sensitive film is polypyrrole and carbon mano-tube composite.
2. polypyrrole according to claim 1 and carbon mano-tube composite gas sensor is characterized in that the interdigital gold electrode on ceramic substrate surface has 8～16 pairs, and the interdigital width of interdigital gold electrode is 20～200 μ m, and interdigital gap is 20～200 μ m.
3. the method for making of polypyrrole according to claim 1 and carbon nano-tube composite gas sensor is characterized in that:
1) clean surface photoetching and evaporation have the ceramic substrate of interdigital gold electrode, dry for standby;
2) concentrated sulphuric acid and red fuming nitric acid (RFNA) being mixed into mixed acid solution in 3: 7 by volume～3: 12 joins in the carbon nano-tube, consumption is that every g carbon nano-tube adds 100～220ml mixed acid solution, the potpourri that obtains was through sonicated 10～30 minutes, at 40～60 ℃ of 1～12h that reflux down, cooling is filtered, be neutral with washed with de-ionized water to filtrate, obtain acid-treated carbon nano-tube, vacuum drying is ground stand-by;
3) adopt the method for sonicated, oxygenant, adulterant, acid treatment carbon nano-tube are scattered in prepare precursor solution in the water, the total concentration of oxygenant and adulterant is 10～50mg/ml, and the consumption of acid treatment carbon nano-tube is 0.1～2mg/ml;
4) will impregnated in 0.5～2min in the precursor solution through the interdigital gold electrode of the ceramic substrate that step 1) is cleaned, lift taking-up after, leave standstill and dry, place pyrroles's saturated vapour vapour phase polymerization 1～24h, behind absolute ethyl alcohol, deionized water cyclic washing, vacuum drying gets final product.
4. according to the method for making of described polypyrrole of claim 3 and carbon nano-tube composite gas sensor, the interdigital width that it is characterized in that said interdigital gold electrode is 20～200 μ m, and interdigital gap is 20～200 μ m.
5. according to the method for making of described polypyrrole of claim 3 and carbon nano-tube composite gas sensor, it is characterized in that said oxygenant is ammonium persulfate or ferric trichloride.
6. according to the method for making of described polypyrrole of claim 3 and carbon nano-tube composite gas sensor, it is characterized in that said adulterant is ferric trichloride, neopelex or paratoluenesulfonic acid sodium salt.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358610A (en) * | 2011-07-09 | 2012-02-22 | 电子科技大学 | Preparation method of conductive polymer one-dimensional nanostructured array |
| CN102944578A (en) * | 2012-11-09 | 2013-02-27 | 江苏康宝电器有限公司 | Preparation method of MoO3@Ag nanowire gas sensor quickly responsive to hydrogen and oxygen at room temperature |
| CN103308563A (en) * | 2013-05-16 | 2013-09-18 | 黑龙江大学 | Gas sensitive element by taking single-walled carbon nanotube/phthalocyanine composite material as ammonia-sensitive material and preparation method thereof |
| CN103336032A (en) * | 2013-06-28 | 2013-10-02 | 苏州大学 | Preparation method of gas sensitive sensor based on carbon nano tube-polypyrrole complex network structure |
| CN117467226A (en) * | 2023-12-28 | 2024-01-30 | 上海拜安传感技术有限公司 | Composition, sensing film, sensor, preparation method and application |
-
2008
- 2008-08-19 CN CNA2008101205520A patent/CN101354368A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102358610A (en) * | 2011-07-09 | 2012-02-22 | 电子科技大学 | Preparation method of conductive polymer one-dimensional nanostructured array |
| CN102944578A (en) * | 2012-11-09 | 2013-02-27 | 江苏康宝电器有限公司 | Preparation method of MoO3@Ag nanowire gas sensor quickly responsive to hydrogen and oxygen at room temperature |
| CN103308563A (en) * | 2013-05-16 | 2013-09-18 | 黑龙江大学 | Gas sensitive element by taking single-walled carbon nanotube/phthalocyanine composite material as ammonia-sensitive material and preparation method thereof |
| CN103336032A (en) * | 2013-06-28 | 2013-10-02 | 苏州大学 | Preparation method of gas sensitive sensor based on carbon nano tube-polypyrrole complex network structure |
| CN117467226A (en) * | 2023-12-28 | 2024-01-30 | 上海拜安传感技术有限公司 | Composition, sensing film, sensor, preparation method and application |
| CN117467226B (en) * | 2023-12-28 | 2024-03-19 | 上海拜安传感技术有限公司 | Composition, sensing film, sensor, preparation method and application |
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Open date: 20090128 |