CN104865292B - A kind of nitrogen dioxide gas sensor based on o-aminophenyl substitution porphyrin nano material - Google Patents
A kind of nitrogen dioxide gas sensor based on o-aminophenyl substitution porphyrin nano material Download PDFInfo
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- CN104865292B CN104865292B CN201510205948.5A CN201510205948A CN104865292B CN 104865292 B CN104865292 B CN 104865292B CN 201510205948 A CN201510205948 A CN 201510205948A CN 104865292 B CN104865292 B CN 104865292B
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Abstract
The invention belongs to material chemistry technical field, and in particular to the preparation and its application of gas sensor of the one kind based on the diphenyl porphyrin nano material of 5,10 2 p-aminophenyl 15,20.The gas sensor is using ITO electro-conductive glass piece as carrier, and interdigital electrode is etched on ITO electro-conductive glass pieces, and by the interdigital electrode of gas sensitive drop coating to ITO electro-conductive glass, NO is made2Gas sensor.Nitrogen dioxide gas sensor provided by the invention has the advantages of low response concentration, high sensitivity；And prepare simply, production cost is low, green, can be used for testing vehicle exhaust at room temperature, the NO in power plant exhaust2Concentration.
Description
Technical field
The invention belongs to material chemistry technical field, and in particular to one kind is based on the p-amino phenyl-s 15 of 5,10- bis-, 20- bis-
The nitrogen dioxide gas sensor of phenyl porphyrin nano material and its application.
Background technology
In the production and life of today's society, can touch various gases needs to be checked and controlled.Than
Benzaldehyde in such as room air pollution such as chemical fibre carpet, cosmetics, finishing material and new composite furniture, paint, apply
Benzene homologues in material, binder, wood-based plate, foam heat insulating material, plastic plate wallpaper etc.；In Chemical Manufacture and vehicle exhaust
The Detection ＆ Controling of nitrogen oxides (such as nitrogen dioxide)；The detection and alarm of coal mine gas concentration；The monitoring of environmental pollution states；
Gas leak etc..
Wherein, nitrogen dioxide (NO2) be have excitant, strong oxidizing property, can be combustion-supporting toxic gas, it is and a kind of important
Atmosphere pollution.It is mainly derived from Vehicular exhaust, heat power station and other industrial fuel combustions and nitric acid, nitrogenous fertilizer
In industrial processes, to the very harmful of human body, thus it is carried out detection there is very important value.
Studying more semiconductor gas sensor at present mainly includes metal-oxide semiconductor (MOS) gas sensor and has
Machine semiconductor gas sensor.Metal-oxide semiconductor (MOS) gas sensor is current most study, practical value highest one
Class gas sensor, but its preparation technology, production cost are more complicated compared to organic semiconductor sensor, metal oxide
Semiconductor gas sensor needs operating temperature at 200~400 DEG C, and organic semiconductor sensor can carry out work at normal temperatures
Make, the practicality of gas sensor can be greatly improved so that exploitation novel organic semi-conductor material prepares organic semiconductor biography
Sensor turns into emerging study hotspot；The invention reside in provide a kind of new nitrogen dioxide gas sensor.
The sensitivity (S) of gas sensor is index of the gas sensor to tested gas sensitization degree.S=Rg/Ra, wherein
Rg is resistance value of the sensitive layer under test gas, and Ra is the aerial resistance value of sensitive layer.
The content of the invention
The present invention provide it is a kind of based on the p-amino phenyl- 15,20- diphenyl porphyrin nano materials of 5,10- bis- two
Nitrogen oxide gas sensor, it can carry out detecting toxic gas nitrogen dioxide (NO at room temperature2) presence and its concentration, its property
Energy and preparation technology are substantially better than hot type, have good practical application meaning and commercial value.
First aspect present invention provides a kind of gas sensor element for being used to determine nitrogen dioxide gas, the sensor
Element includes ITO electro-conductive glass substrate (1), interdigital electrode (2) and porphyrin nano material coating (3)；The interdigital electrode (2) is carved
In ITO electro-conductive glass substrate (1), material coating (3) drop coating is obtained in interdigital electrode in ITO electro-conductive glass substrates for erosion, its
It is characterised by, the component of the material coating is the p-amino phenyl-s 15 of 5,10- bis-, and 20- diphenyl porphyrin nano materials are described
The p-amino phenyl- 15,20- diphenyl porphyrins of 5,10- bis- have the chemical constitution shown in Formulas I.
Second aspect of the present invention provides the preparation method of gas sensor element described in first aspect present invention, this method bag
Include following steps：
1) preparation of ITO electro-conductive glass interdigital electrode
1. spin coating last layer bears photoresist on transparent electro-conductive glass after cleaning, then it is put into drying box
70 DEG C of constant temperature 10min；
2. the light to be designed with interdigital electrode pattern paints piece as mask plate, develop after being exposed 18 seconds under litho machine and float
Wash；
3. by development, clearly 140 DEG C of style progress bakes 40min, after being etched in the mixed liquor of hydrochloric acid and nitric acid, uses
Deionized water and negtive photoresist cleaning fluid remove residual acid and photoresist, obtain the ITO electro-conductive glass interdigital electrodes shown in Fig. 1.
2) above-mentioned ITO electro-conductive glass is cleaned up；
3) the p-amino phenyl- 15,20- diphenyl porphyrin nano droplets of material of 5,10- bis- is coated onto the ITO bases that step 2) obtains
In the interdigital electrode of piece, dry, that is, obtain the gas sensor of gas sensor；
Wherein, the step 1) cleaning step is：ITO electro-conductive glass substrate is used into toluene successively, acetone, ethanol, go from
Sub- water is cleaned by ultrasonic 5-10min respectively, is then dried for standby；
Third aspect present invention provides one kind and prepares the p-amino phenyl- 15,20- diphenyl porphyrin nano materials of 5,10- bis-
Method, this method comprises the following steps：
1) p-amino phenyl-s 15 of 5,10- bis-, 20- diphenyl porphyrins are added in good solvent, filtered；
2) injection or dropwise addition poor solvent into filtrate obtained by step 1), sealing, stand 3~4 days, it is right to obtain 5,10- bis-
Aminophenyl -15,20- diphenyl porphyrin aggregations；
Wherein, 5,10 ,-two p-amino phenyl-s 15,20- diphenyl porphyrin (mol) is with good solvent (ml) molal volume ratio
1：5~100, preferably 1:4~80；
The volume ratio of poor solvent and good solvent is 1:3~10；The good solvent is in chloroform, dichloromethane
It is one or two kinds of；The poor solvent is selected from one or both of methanol, n-hexane.
In one embodiment of the invention, the preparation method of above-mentioned aggregation comprises the following steps：
(1) raw material 5, the p-amino phenyl-s 15 of 10- bis-, 20- diphenyl porphyrins are added in chloroform, then filtered,
5,10 are obtained, the chloroform soln of-two p-amino phenyl- 15,20- diphenyl porphyrins.
(2) poor solvent is carefully slowly injected into the three of the p-amino phenyl- 15,20- diphenyl porphyrins of 5,10- bis-
In chloromethanes solution, the volume ratio of poor solvent and chloroform is 1:3~10, sealing, about 3-4 days are stood at room temperature, is obtained
Aggregation.
Fourth aspect present invention protection 5,10- bis- p-amino phenyl- 15,20- diphenyl porphyrins are used to prepare nitrogen dioxide
The purposes of gas sensor.
Gas sensor provided by the invention is characterised by that low concentration (1- can be carried out to nitrogen dioxide at normal temperatures
40ppm) range detection；
The p-amino phenyl- 15,20- diphenyl porphyrin nano materials of 5,10- bis- that the present invention is prepared in methyl alcohol are to NO2's
Minimum response concentration 2ppm, sensitivity at this concentration is 1.24；The p-amino phenyl-s 15 of 5,10- bis- prepared in n-hexane,
20- diphenyl porphyrin nano materials are to NO2Minimum response concentration 4ppm, at this concentration sensitivity be 1.02.
The advantages of gas sensor of the present invention：
(1) gas sensor that the present invention uses is to toxic gas NO2Response concentration it is low, improve anti-to gas absorption
The sensitivity answered, and in low concentration of NO2In the range of there is good linear rule to response sensitivity.
(2) gas sensor that the present invention uses can be carried out at room temperature, no potential safety hazard.
(3) gas-sensitive sensor structure and preparation technology that the present invention uses are simple, and cost is cheap, is easy to produce in batches.
Brief description of the drawings
The structural representation of Fig. 1 gas sensor elements；
The cross-sectional view of Fig. 2 gas sensors；
Gas sensor prepared by the aggregation that Fig. 3 embodiments 1 obtain is to NO2Concentration time curve (room temperature condition)；
Gas sensor prepared by the aggregation that Fig. 4 embodiments 2 obtain is to NO2Concentration time curve (room temperature condition)；
Gas sensor prepared by the aggregation that Fig. 5 embodiments 1 obtain is to NO2Sensitivity-concentration curve (room temperature bar
Part)；
Gas sensor prepared by the aggregation that Fig. 6 embodiments 2 obtain is to NO2Sensitivity-concentration curve (room temperature bar
Part)；
In figure, 1 is transparent conducting glass (ITO) substrate, and 2 be interdigital electrode, and 3 be material coating.
Embodiment
The specific embodiment of the invention is further described below
The p-amino phenyl- 15,20- diphenyl porphyrin nano material preparation methods of 1 5,10- of embodiment bis-
Pipette 1mL chloroforms, add 3mg 5, the p-amino phenyl-s 15 of 10- bis-, 20- diphenyl porphyrins, ultrasound makes its molten
Solution, then filters, the p-amino phenyl-s 15 of 5,10- bis-, the chloroform soln of 20- diphenyl porphyrins is obtained in bottle in assembling.Will
Poor solvent n-hexane is careful and is slowly injected into the chloroform of the p-amino phenyl- 15,20- diphenyl porphyrins of 5,10- bis-
In solution, the volume ratio of methanol and chloroform is 1:3, sealing, about 3-4 days are stood at room temperature, i.e. it can be seen that poly- in assembling bottle
Aggregate material occurs, i.e. the p-amino phenyl-s 15 of 5,10- bis-, 20- diphenyl porphyrin nano materials.
The p-amino phenyl- 15,20- diphenyl porphyrin nano material preparation methods of 2 5,10- of embodiment bis-
Pipette 1mL chloroforms, add 3mg 5, the p-amino phenyl-s 15 of 10- bis-, 20- diphenyl porphyrins, ultrasound makes its molten
Solution, then filters, the p-amino phenyl-s 15 of 5,10- bis-, the chloroform soln of 20- diphenyl porphyrins is obtained in bottle in assembling.Will
The chloroform that poor solvent methanol is careful and is slowly injected into the p-amino phenyl- 15,20- diphenyl porphyrins of 5,10- bis- is molten
In liquid, the volume ratio of methanol and chloroform is 1:3, sealing, about 3-4 days are stood at room temperature, i.e. it can be seen that aggregation in assembling bottle
Body material occurs, i.e. the p-amino phenyl-s 15 of 5,10- bis-, 20- diphenyl porphyrin nano materials.
The p-amino phenyl- 15,20- diphenyl porphyrin nano material silica nitrogen dependent sensors of 3 5,10- of embodiment bis-
Preparation
(1) preparation of ITO electro-conductive glass interdigital electrode
1. spin coating last layer bears photoresist on transparent electro-conductive glass after cleaning, then it is put into drying box
70 DEG C of constant temperature 10min；2. painting piece as mask plate to design figuratum light, develop after being exposed 18 seconds under litho machine and rinse；
3. by development, clearly 140 DEG C of style progress bakes 40min, after being etched in the mixed liquor of hydrochloric acid and nitric acid, uses deionized water
Residual acid and photoresist are removed with negtive photoresist cleaning fluid, obtains the ITO electro-conductive glass interdigital electrodes shown in Fig. 1.
(2) ITO substrate is used into toluene successively, acetone, ethanol, deionized water is cleaned by ultrasonic 5-10min, then dries respectively
It is standby；
(3) the p-amino phenyl- 15,20- diphenyl porphyrins of 5,10- bis- that embodiment 1 and embodiment 2 are prepared respectively
In the interdigital electrode for the ITO substrates that nano material drop coating obtains to step (2), dry, that is, obtain the gas sensitive element of gas sensor
Part；
The performance measurement of the nitrogen dioxide gas sensor of embodiment 4
Air-sensitive test device is built by laboratory, air-sensitive test process be a comparatively gentle environment (room temperature,
Under external atmosphere pressure and dry air) carried out between two electrodes under fixed-bias transistor circuit 5V.Use tester：Agilent
B290a precisions source/measuring unit.
Two kinds of gas sensors are in NO2Response sensitivity has good linear rule in low strength range.Two kinds of air-sensitives
Sensor contrast understand, 5,10- bis- p-amino phenyl-s 15,20- diphenyl porphyrin in methyl alcohol aggregation gas sensor than 5,
The p-amino phenyl- 15,20- diphenyl porphyrins aggregation gas sensors in n-hexane of 10- bis- are slightly good.
Claims (7)
1. a kind of gas sensor element for being used to determine nitrogen dioxide gas, the sensor element include ITO electro-conductive glass
Substrate (1), interdigital electrode (2) and material coating (3)；Interdigital electrode (2) etching is in ITO electro-conductive glass substrate (1), institute
Material coating (3) drop coating is stated in the interdigital electrode in ITO electro-conductive glass substrates, it is characterised in that the group of the material coating
It is divided into the p-amino phenyl- 15,20- diphenyl porphyrin nano materials of 5,10- bis-.
2. a kind of method for preparing gas sensor element described in claim 1, this method comprise the following steps：
1) preparation of ITO electro-conductive glass interdigital electrode；
2) above-mentioned ITO electro-conductive glass is cleaned up；
3) the p-amino phenyl- 15,20- diphenyl porphyrin nano droplets of material of 5,10- bis- is coated onto the ITO substrates that step 2) obtains
In interdigital electrode, dry, that is, obtain the gas sensor of gas sensor.
3. according to the method for claim 2, it is characterised in that the preparation of step 1) the ITO electro-conductive glass interdigital electrode
Method is：
1. spin coating last layer bears photoresist on transparent electro-conductive glass after cleaning, 70 DEG C are then put into drying box
Constant temperature 10min；
2. the light to be designed with interdigital electrode pattern paints piece as mask plate, develop after being exposed 18 seconds under litho machine and rinse；
3. will development clearly style carry out 140 DEG C bake 40min, in the mixed liquor of hydrochloric acid and nitric acid etch after, spend from
Sub- water and negtive photoresist cleaning fluid remove residual acid and photoresist, obtain ITO electro-conductive glass interdigital electrodes.
4. the p-amino phenyl-s 15 of 5,10- bis- described in a kind of claim 2, the preparation method of 20- diphenyl porphyrin nano materials,
This method comprises the following steps：
1) p-amino phenyl-s 15 of 5,10- bis-, 20- diphenyl porphyrins are added in good solvent, filtered；
2) injection or dropwise addition poor solvent into filtrate obtained by step 1), sealing and standing 3~4 days, filtering, it is right to obtain 5,10- bis-
Aminophenyl -15,20- diphenyl porphyrin aggregations.
5. according to the method for claim 4, it is characterised in that 5,10- bis- p-amino phenyl-s 15,20- diphenyl porphyrin with
Good solvent molal volume ratio is 1：5~100, unit：mol/ml；
The volume ratio of poor solvent and good solvent is 1:3~10；
The good solvent is selected from one or both of chloroform, dichloromethane；
The poor solvent is selected from one or both of methanol, n-hexane.
6. according to the method for claim 5, it is characterised in that 5,10- bis- p-amino phenyl-s 15,20- diphenyl porphyrin with
Good solvent molal volume ratio is 1:4~80, unit：mol/ml.
The p-amino phenyl- 15,20- diphenyl porphyrins of 7.5,10- bis- are used to prepare gas sensor element described in claim 1
Purposes.
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| CN105223237B (en) * | 2015-09-10 | 2017-12-26 | 济南大学 | A kind of organic semiconductor nano-tube material and preparation method thereof and purposes and a kind of NO2Gas sensor |
| CN106349248B (en) * | 2016-08-09 | 2018-10-23 | 济南大学 | A kind of Metalloporphyrins and its preparation method and application |
| CN106349247B (en) * | 2016-08-09 | 2018-10-19 | 济南大学 | A kind of 5- p-hydroxybenzenes -10,15,20- trichlorophenyl porphyrin nano pipes and its preparation method and application |
| CN107219280B (en) * | 2017-07-21 | 2019-07-05 | 济南大学 | A kind of Metalloporphyrins gas sensor element and its preparation method and application |
| CN107356648B (en) * | 2017-07-21 | 2020-10-16 | 济南大学 | Gas sensor element for determining ethanol and preparation method and application thereof |
| CN109030577B (en) * | 2018-07-04 | 2020-05-05 | 吉林大学 | Room temperature NH3Sensor and preparation method thereof |
| CN110068588A (en) * | 2019-04-28 | 2019-07-30 | 济南大学 | For detecting NO2Organo-mineral complexing nano material and gas sensor |
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