CN1885025A - Organic nitrogen oxide sensitive composite material and nitrogen oxide gas sensor - Google Patents
Organic nitrogen oxide sensitive composite material and nitrogen oxide gas sensor Download PDFInfo
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- CN1885025A CN1885025A CN 200610021369 CN200610021369A CN1885025A CN 1885025 A CN1885025 A CN 1885025A CN 200610021369 CN200610021369 CN 200610021369 CN 200610021369 A CN200610021369 A CN 200610021369A CN 1885025 A CN1885025 A CN 1885025A
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- nitrogen oxide
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Abstract
The invention relates to an organic nitric oxide sensitive composite and nitric oxide gas sensor, belonging to the material technique, wherein said composite material is made by mixing organic small molecule nitric oxide sensitive material and organic macromolecule polymer nitric oxide sensitive material whose mass ratio is between 0.7:1-1:1; said small molecule material is phthalocyanines, TCNQ and relative derivant or porphyrin and relative derivant; the macromolecule polymer is thiofuran and relative derivant, pyrrole and relative derivant, polyaniline and derivant, or polymethyl methacryate. Said nitric oxide gas sensor comprises at least one nitric oxide gas sensor unit with interdigital electrode structure; the nitric oxide sensitive film is said composite material. The inventive composite material and nitric oxide gas sensor have high sensitivity, short response time, and better aging property, with simple method, low cost and wider application.
Description
Technical field
Organic nitrogen oxide sensitive composite material and nitrogen oxide gas sensor belong to the material technology field, particularly gas sensitive material and gas sensor.
Background technology
Nitrogen oxide (NO
X) gas is to environment and the very serious pollutant of human health risk.NO can autoxidation become NO in air
2, therefore, development nitrogen oxide (NO
2) gas sensor is so that know in the environment NO of relevant pollution source timely and accurately
XGas and concentration thereof are significant to environmental monitoring and environmental protection.SADAOKA YOSHIHIKO is at the patent " NO of application on April 30th, 1991
2SENSOR AND PRODUCTION THEREOF " be exactly a typical NO who adopts the polymeric material preparation
2The gas sensor patent, this sensor construction as shown in Figure 1.
Because its performance of solid state gas sensors is mainly by sensitive material and preparation technology decision, and present nitrogen oxide sensor is because the sensitive material difference that is adopted, and performance and practicality also have very big-difference.Existing nitrogen oxide sensor adopts metal oxide as sensitive material mostly, and its shortcoming needs well heater when mainly being work.In recent years, can obtain day by day paying attention to as gas sensitive material at the electronic material of working and room temperature especially conducting polymer materials.The conventional metals oxide gas sensor need use under the condition of high temperature, and the polymer gas sensor of rising in recent years then exists response and release time grows, is subject to shortcomings such as ambient moisture influence.
Summary of the invention
The object of the present invention is to provide a kind of organic nitrogen oxide sensitive composite material and nitrogen oxide gas sensor, have short, restorative characteristics such as good, with low cost of highly sensitive, response time.
Organic nitrogen oxide sensitive composite material is characterized in that, is evenly mixed by organic molecule nitrogen oxide sensitive material and organic high molecular polymer nitrogen oxide sensitive material and forms.
The mass ratio of described organic molecule nitrogen oxide sensitive material and organic high molecular polymer nitrogen oxide sensitive material is between 0.7: 1～1: 1.
Described organic molecule nitrogen oxide sensitive material is phthalocyanines, TCNQ and derivant class thereof or porphyrin and derivant class thereof, and described organic high molecular polymer nitrogen oxide sensitive material can be polythiophene and derivant, polypyrrole and derivant thereof, polyaniline and derivant, polymethyl methyl esters (PMMA) etc.
Described phthalocyanines organic molecule nitrogen oxide sensitive material can be metal phthalocyanine, two phthalocyanine, the two phthalocyanines of metal etc.
Organic nitrogen oxide sensitive composite material of the present invention, its preparation method mainly may further comprise the steps:
Step 1, configuration solution.The organic molecule nitrogen oxide sensitive material and the organic high molecular polymer nitrogen oxide sensitive material of certain mass ratio are dissolved in the organic solvent respectively.
Step 2 mixed solution.Two kinds of solution are mixed, stir 6-12 hour, and then ultrasonic mixing 40 minutes.
Step 3 processed.Adopt vacuum drying oven to preserve 6～12 hours, to remove organic solvent and moisture content with uniform temperature.
When configuration solution, the weight ratio of organic small molecule material and polymeric material is controlled at was advisable in 0.7: 1～1: 1, and the organic solvent that is adopted can be organic solvents such as acetone, ethanol, methylene chloride, methenyl choloride, propyl alcohol, monoethanolamine, diethanolamine, triethanolamine, ethylene glycol, glycol monoethyl ether, ethylene glycol monoethyl ether.
Because organic small molecule material of the present invention itself is to NO
2Gas has reasonable susceptibility, adds that organic high molecular polymer is also to NO
2Gas has reasonable susceptibility, and therefore organic nitrogen oxide sensitive composite material provided by the invention is better than the sensitive property of simple organic molecule nitrogen oxide sensitive material or organic high molecular polymer nitrogen oxide sensitive material; Simultaneously; organic molecule nitrogen oxide sensitive material is evenly distributed in the high molecular polymer; make high molecular polymer provide good " support " and " protection " for organic molecule nitrogen oxide sensitive material; the whole material sensitivity that can prevent micromolecular crystallization and cause can reduction, make whole organic nitrogen oxide sensitive composite material ageing properties to bigger raising.
Nitrogen oxide gas sensor according to above-mentioned organic nitrogen oxide sensitive composite material, the nitrogen oxide gas sensor unit that comprises at least more than one, described nitrogen oxide gas sensor unit has typical interdigital electrode structure, as shown in Figure 5, constitute by insulating substrate 7, interdigital electrode 8 and nitrogen oxide sensitive film 9, interdigital electrode 8 is positioned at the surface of insulating substrate 7, nitrogen oxide sensitive film 9 covers insulating substrate 7 and above the interdigital electrode 8, it is characterized in that described nitrogen oxide sensitive film 9 materials are organic nitrogen oxide sensitive composite material of the present invention.
Described insulating substrate 7 is a silicon chip, specifically can be n type silicon chip or High Resistivity Si substrate, but its shape rectangle, square or circular.
Utilize nitrogen oxide gas sensor that organic nitrogen oxide sensitive composite material of the present invention makes for low concentration of NO after tested
2Gas has the very fast response time and than higher sensitivity, test result such as Fig. 5, shown in Figure 6.
Provided by the invention with organic molecule nitrogen oxide sensitive material and the mixed uniformly organic nitrogen oxide sensitive composite material of organic high molecular polymer nitrogen oxide sensitive material; and as the nitrogen oxide gas sensor of nitrogen oxide sensitive membraneous material; has the susceptibility height; response time is short; help the long-term maintenance of susceptibility; and method for making is easy, cost is low, has the practical application foreground of large-scale production.
Description of drawings
Fig. 1 is typical NO
2The gas sensor configuration synoptic diagram, wherein, the 1st, substrate, the 2nd, the plumbous nitrogen oxide sensitive film of phthalocyanine, the 3, the 4th, Pt electrode, the 5, the 6th, Pt contact conductor.
Fig. 2 is the schematic arrangement of metal phthalocyanine organic molecule nitrogen oxide sensitive material.
Fig. 3 is the schematic arrangement of TCNQ organic molecule nitrogen oxide sensitive material.
Fig. 4 is the schematic arrangement of polymethyl methyl esters (PMMA) organic high molecular polymer nitrogen oxide sensitive material.
Fig. 5 is the structural representation of nitrogen oxide gas sensor unit in the nitrogen oxide gas sensor of the present invention, wherein, the 7th, insulating substrate, the 8th, interdigital electrode, the 9th, nitrogen oxide sensitive film.
Fig. 6 is that nitrogen oxide gas sensor of the present invention is to 3ppmNO
2Resonse characteristic.
Fig. 7 is that nitrogen oxide gas sensor of the present invention is to NO
2Sensitivity curve.
Claims (9)
1, organic nitrogen oxide sensitive composite material is characterized in that, is evenly mixed by organic molecule nitrogen oxide sensitive material and organic high molecular polymer nitrogen oxide sensitive material and forms.
2, organic nitrogen oxide sensitive composite material according to claim 1 is characterized in that, the mass ratio of described organic molecule nitrogen oxide sensitive material and organic high molecular polymer nitrogen oxide sensitive material is between 0.7: 1～1: 1.
3, organic nitrogen oxide sensitive composite material according to claim 1, it is characterized in that, described organic molecule nitrogen oxide sensitive material is phthalocyanines, TCNQ and derivant class thereof or porphyrin and derivant class thereof, and described organic high molecular polymer nitrogen oxide sensitive material is polythiophene and derivant, polypyrrole and derivant thereof, polyaniline and derivant or polymethyl methyl esters.
4, organic nitrogen oxide sensitive composite material according to claim 2, described phthalocyanines organic molecule nitrogen oxide sensitive material can be the two phthalocyanines of metal phthalocyanine, two phthalocyanine or metal.
5, the preparation method of organic nitrogen oxide sensitive composite material is characterized in that, it may further comprise the steps:
Step 1, configuration solution
Be dissolved in the organic molecule nitrogen oxide sensitive material and the organic high molecular polymer nitrogen oxide sensitive material of certain mass ratio in the organic solvent respectively;
Step 2, mixed solution
Two kinds of solution are mixed, stir 6-12 hour, and then ultrasonic mixing is about 40 minutes;
Step 3, processed
Adopt vacuum drying oven to preserve 6～12 hours, remove organic solvent and moisture content with uniform temperature.
6, the preparation method of organic nitrogen oxide sensitive composite material according to claim 5, it is characterized in that organic solvent described in the step 1 can be acetone, ethanol, methylene chloride, methenyl choloride, propyl alcohol, monoethanolamine, diethanolamine, triethanolamine, ethylene glycol, glycol monoethyl ether, ethylene glycol monoethyl ether etc.
7, the preparation method of organic nitrogen oxide sensitive composite material according to claim 5 is characterized in that, the mass ratio of organic molecule nitrogen oxide sensitive material and organic high molecular polymer nitrogen oxide sensitive material is between 0.7: 1～1: 1 in the step 1.
8, nitrogen oxide gas sensor, the nitrogen oxide gas sensor unit that comprises at least more than one, described nitrogen oxide gas sensor unit has typical interdigital electrode structure, constitute by insulating substrate (7), interdigital electrode (8) and nitrogen oxide sensitive film (9), interdigital electrode (8) is positioned at the surface of insulating substrate (7), nitrogen oxide sensitive film (9) covers insulating substrate (7) and above the interdigital electrode (8), it is characterized in that described nitrogen oxide sensitive film (9) material is an organic nitrogen oxide sensitive composite material according to claim 1.
9, nitrogen oxide gas sensor according to claim 8 is characterized in that, described insulating substrate (7) is a silicon chip, specifically can be n type silicon chip or High Resistivity Si substrate, but its shape rectangle, square or circular.
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| CN101776632A (en) * | 2010-03-09 | 2010-07-14 | 浙江大学 | Water dispersible polyaniline nano-particle gas-sensitive element and method for preparing same |
| CN102221569A (en) * | 2011-03-25 | 2011-10-19 | 中国科学院长春应用化学研究所 | Gas sensor with gas-sensitive layer adopting weak epitaxial organic semiconductor film |
| CN101368925B (en) * | 2008-09-19 | 2011-10-26 | 浙江大学 | Poly-pyrrole and metal nanometer particle composite gas sensor and preparation thereof |
| CN102768230A (en) * | 2012-08-09 | 2012-11-07 | 电子科技大学 | Vertical flat plate capacitive gas sensor and preparation method thereof |
| CN103852495A (en) * | 2014-03-21 | 2014-06-11 | 福建师范大学 | Two-electrode sensor for measuring liquid conductivity |
| CN105651814A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Nanometer tin-sulfide-based gas sensor and preparation method thereof |
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| CN105651815A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Nitrogen dioxide sensor and preparation method thereof |
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| CN105699441A (en) * | 2016-03-24 | 2016-06-22 | 电子科技大学 | Resistance-type gas sensor and manufacturing method thereof |
| CN105891267A (en) * | 2015-04-27 | 2016-08-24 | 济南大学 | Nitrogen dioxide gas sensitive sensor based on aminophenyl substituted porphyrin nanometer material |
| CN106415255A (en) * | 2014-03-02 | 2017-02-15 | 麻省理工学院 | Gas sensors based upon metal carbon complexes |
| CN109440159A (en) * | 2018-10-29 | 2019-03-08 | 武汉大学 | One kind is based on polypyrrole/metalloporphyrin electro-deposition sensor and the preparation method and application thereof |
| CN112763551A (en) * | 2020-12-29 | 2021-05-07 | 电子科技大学 | Nitrogen dioxide sensor based on composite material blocking effect and preparation method thereof |
| TWI772711B (en) * | 2019-11-18 | 2022-08-01 | 新唐科技股份有限公司 | Gas sensors |
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| CN101368925B (en) * | 2008-09-19 | 2011-10-26 | 浙江大学 | Poly-pyrrole and metal nanometer particle composite gas sensor and preparation thereof |
| CN101776632A (en) * | 2010-03-09 | 2010-07-14 | 浙江大学 | Water dispersible polyaniline nano-particle gas-sensitive element and method for preparing same |
| CN102221569A (en) * | 2011-03-25 | 2011-10-19 | 中国科学院长春应用化学研究所 | Gas sensor with gas-sensitive layer adopting weak epitaxial organic semiconductor film |
| CN102221569B (en) * | 2011-03-25 | 2013-06-05 | 中国科学院长春应用化学研究所 | Gas sensor with gas-sensitive layer adopting weak epitaxial organic semiconductor film |
| CN102768230A (en) * | 2012-08-09 | 2012-11-07 | 电子科技大学 | Vertical flat plate capacitive gas sensor and preparation method thereof |
| CN102768230B (en) * | 2012-08-09 | 2014-03-19 | 电子科技大学 | Vertical flat plate capacitive gas sensor and preparation method thereof |
| CN106415255A (en) * | 2014-03-02 | 2017-02-15 | 麻省理工学院 | Gas sensors based upon metal carbon complexes |
| CN103852495A (en) * | 2014-03-21 | 2014-06-11 | 福建师范大学 | Two-electrode sensor for measuring liquid conductivity |
| CN105651813A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Novel aniline gas sensor and preparation method thereof |
| CN105651816B (en) * | 2014-11-12 | 2019-01-25 | 长沙理工大学 | A kind of novel ammonia gas sensor and preparation method thereof |
| CN105651816A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Novel ammonia gas sensor and preparation method thereof |
| CN105651815A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Nitrogen dioxide sensor and preparation method thereof |
| CN105651813B (en) * | 2014-11-12 | 2019-01-11 | 长沙理工大学 | A kind of novel aniline gas sensor and preparation method thereof |
| CN105651814A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Nanometer tin-sulfide-based gas sensor and preparation method thereof |
| CN105651815B (en) * | 2014-11-12 | 2018-07-31 | 长沙理工大学 | A kind of nitrogen dioxide sensor and preparation method thereof |
| CN105891267B (en) * | 2015-04-27 | 2018-08-28 | 济南大学 | A kind of nitrogen dioxide gas sensor replacing porphyrin nano material based on an aminophenyl |
| CN105891267A (en) * | 2015-04-27 | 2016-08-24 | 济南大学 | Nitrogen dioxide gas sensitive sensor based on aminophenyl substituted porphyrin nanometer material |
| CN105699441B (en) * | 2016-03-24 | 2018-04-13 | 电子科技大学 | A kind of resistance-type gas sensor and preparation method thereof |
| CN105699441A (en) * | 2016-03-24 | 2016-06-22 | 电子科技大学 | Resistance-type gas sensor and manufacturing method thereof |
| CN109440159A (en) * | 2018-10-29 | 2019-03-08 | 武汉大学 | One kind is based on polypyrrole/metalloporphyrin electro-deposition sensor and the preparation method and application thereof |
| TWI772711B (en) * | 2019-11-18 | 2022-08-01 | 新唐科技股份有限公司 | Gas sensors |
| CN112763551A (en) * | 2020-12-29 | 2021-05-07 | 电子科技大学 | Nitrogen dioxide sensor based on composite material blocking effect and preparation method thereof |
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