CN105784773A - Nitrogen dioxide gas sensitive sensor based on amino phenyl substituted porphyrin nanomaterial - Google Patents
Nitrogen dioxide gas sensitive sensor based on amino phenyl substituted porphyrin nanomaterial Download PDFInfo
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- CN105784773A CN105784773A CN201510759303.6A CN201510759303A CN105784773A CN 105784773 A CN105784773 A CN 105784773A CN 201510759303 A CN201510759303 A CN 201510759303A CN 105784773 A CN105784773 A CN 105784773A
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- amino phenyl
- triphenylporphyrin
- conductive glass
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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Abstract
The invention belongs to the technical field of material chemistry, and in particular, relates to preparation and an application of a gas sensitive element based on a 5-p-amino phenyl-10,15,20-triphenyl porphyrin nanomaterial. The gas sensitive element takes an ITO conductive glass sheet as a carrier, the ITO conductive glass sheet is etched with an interdigital electrode, and a gas sensitive material dropwise coats the interdigital electrode to prepare the NO2 gas sensitive sensor. The NO2 gas sensitive element provided by the invention has the advantages of low response concentration, high sensitivity, simple preparation, low production cost, and green environmental protection, and can be used for testing of the concentration of NO2 in automobile exhaust gas and power plant waste gas at ambient temperature.
Description
Technical field
The invention belongs to material chemistry technical field, be specifically related to a kind of based on 5-p-amino phenyl-10,15,20-tri-
The nitrogen dioxide gas sensor of phenyl porphyrin nano material and application thereof.
Background technology
In the production and life of society, can touch various gas needs check and control.Ratio
Such as the benzaldehyde in room air pollution such as chemical fibre carpet, cosmetics, finishing material and new composite furniture etc., paint, be coated with
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 of coal mine gas concentration and warning；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, be also a kind of important
Atmosphere pollution.It is mainly derived from the fuel combustion of Vehicular exhaust, heat power station and other industry and nitric acid, nitrogenous fertilizer
In industrial processes, very harmful to human body, thus it is carried out detection there is very important value.
Study more semiconductor gas sensor at present mainly include metal-oxide semiconductor (MOS) gas sensor and have
Machine semiconductor gas sensor.Metal-oxide semiconductor (MOS) gas sensor is that current most study, practical value are the highest
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, it is possible to be greatly improved the practicality of gas sensor so that exploitation novel organic semi-conductor material is prepared organic semiconductor and passed
Sensor becomes emerging study hotspot；A kind of new nitrogen dioxide gas sensor of offer is provided.
The sensitivity (S) of gas sensor is the gas sensor index to tested gas sensitization degree.S=Rg/Ra, wherein
Rg is sensitive layer resistance value in gas to be measured, and Ra is the aerial resistance value of sensitive layer.
Summary of the invention
The present invention provides a kind of nitrogen dioxide based on 5-p-amino phenyl-10,15,20-Triphenylporphyrin nano material
Gas sensor, can at room temperature carry out detecting toxic gas nitrogen dioxide (NO2) existence and concentration, its performance and system
Standby technique is substantially better than hot type, has good actual application value and commercial value.
First aspect present invention provides a kind of gas sensor element for measuring nitrogen dioxide gas, described sensor
Element comprises electro-conductive glass substrate (1), interdigital electrode (2) and material coating (3)；Described interdigital electrode (2) is etched in conduction glass
In glass (ITO) substrate (1), described porphyrin nano material coating (3) drop coating is in electro-conductive glass (ITO) substrate, it is characterised in that
The component of described material coating is 5-p-amino phenyl-10,15,20-Triphenylporphyrin nano material, described 5-p-aminophenyl
Base-10,15,20-Triphenylporphyrin has the chemical constitution shown in Formulas I.
Formulas I
Second aspect present invention provides the preparation method of gas sensor element described in first aspect present invention, the method include with
Lower step:
1) preparation of ITO electro-conductive glass interdigital electrode；
On transparent electro-conductive glass the most after cleaning, spin coating last layer bears photoresist, is then put into 70 C in drying box
Constant temperature 10 min；
2. paint sheet as mask plate with the light being designed with interdigital electrode pattern, develop after exposing 18 seconds under litho machine and rinse；
3. style clearly of developing is carried out 140 C and bakes 40 min, in the mixed liquor of hydrochloric acid and nitric acid etching after, spend from
Sub-water and negative glue cleaning fluid remove residual acid and photoresist, obtain the ITO electro-conductive glass interdigital electrode shown in Fig. 1.
2) above-mentioned ITO electro-conductive glass is cleaned up；
3) by 5-p-amino phenyl-10,15,20-Triphenylporphyrin nano material drop coating to step 2) fork of ITO substrate that obtains
Refer to, on electrode, dry, i.e. obtain the gas sensor of gas sensor；
Wherein, cleaning step described in step 1) is: by ITO electro-conductive glass substrate successively by toluene, acetone, ethanol, deionized water
Ultrasonic cleaning 5-10min, then dry for standby respectively.
Third aspect present invention provides a kind of 5-p-amino phenyl-10,15,20-Triphenylporphyrin nano material prepared
Method, the method comprises the following steps:
1) 5-p-amino phenyl-10,15,20-Triphenylporphyrin is joined in good solvent and dissolve, filter；
2) in step 1) gained filtrate, inject or drip poor solvent, seal, stand 3～4 days, obtain 5-p-amino phenyl-
10,15,20-Triphenylporphyrin aggregation；
Wherein, 5-p-amino phenyl-10,15,20-Triphenylporphyrin (mol) and good solvent (ml) molal volume than for 1:5～
100, preferably 1:4～80；
Poor solvent is 1: 3～10 with the volume ratio of good solvent；Described good solvent is selected from chloroform, dichloromethane
Plant or two kinds；Described poor solvent is selected from one or both in methyl alcohol, n-hexane.
In one embodiment of the invention, the preparation method of above-mentioned aggregation comprises the following steps:
(1) raw material 5-p-amino phenyl-10,15,20-Triphenylporphyrin is joined in chloroform, then filter, obtain 5-
The chloroform soln of p-amino phenyl-10,15,20-Triphenylporphyrin.
(2) poor solvent carefully and is lentamente injected into the trichlorine of 5-p-amino phenyl-10,15,20-Triphenylporphyrin
In dichloromethane, poor solvent is 1: 3～10 with the volume ratio of chloroform, seals, left at room temperature about 3-4 days, obtains
Aggregation.
Fourth aspect present invention protection 5-p-amino phenyl-10,15,20-Triphenylporphyrin is used for preparing titanium dioxide nitrogen
The purposes of dependent sensor.
The gas sensor that the present invention provides is characterised by nitrogen dioxide to be carried out low concentration (1-at normal temperatures
40ppm) range detection；
The 5-p-amino phenyl-10,15,20-Triphenylporphyrin nano material that the present invention is prepared in methyl alcohol is to NO2Minimum sound
Answering concentration 2ppm, sensitivity is 1.22 at this concentration；The 5-p-amino phenyl-10,15,20-triphen of preparation in n-hexane
Base porphyrin nano material is to NO2Minimum response concentration 4ppm, sensitivity is 1.06 at this concentration.
The advantage of gas sensor of the present invention:
(1) gas sensor that the present invention uses is to toxic gas NO2Response concentration low, improve to gas absorption reaction
Sensitivity, and in low concentration of NO2In the range of response sensitivity had good linear rule.
(2) gas sensor that the present invention uses can at room temperature be carried out, without potential safety hazard.
(3) present invention uses gas-sensitive sensor structure and preparation technology are simple, with low cost, it is simple to batch production.
Accompanying drawing explanation
The structural representation of Fig. 1 gas sensor element；
The cross sectional representation of Fig. 2 gas sensor；
The gas sensor (in methyl alcohol) that Fig. 3 embodiment 3 obtains is to NO2Concentration time curve (room temperature condition)；
The gas sensor (in n-hexane) that Fig. 4 embodiment 3 obtains is to NO2Concentration time curve (room temperature condition)；
The gas sensor (in methyl alcohol) that Fig. 5 embodiment 3 obtains is to NO2Sensitivity-concentration curve (room temperature condition)；
The gas sensor (in n-hexane) that Fig. 6 embodiment 3 obtains is to NO2Sensitivity-concentration curve (room temperature condition)；
In figure, 1 is transparent conducting glass (ITO) substrate, and 2 is interdigital electrode, and 3 is material coating.
Detailed description of the invention
Below the specific embodiment of the invention is further described
Embodiment 1 5-p-amino phenyl-10,15,20-Triphenylporphyrin preparation method of nano material
Pipette 1 mL chloroform, add 3 mg 5-p-amino phenyl-10,15,20-Triphenylporphyrins, ultrasonic make it dissolve,
Then filter, in assembling the chloroform soln obtaining 5-p-amino phenyl-10,15,20-Triphenylporphyrin in bottle.By bad
Solvent hexane carefully and is lentamente injected in the chloroform soln of 5-p-amino phenyl-10,15,20-Triphenylporphyrin,
The volume ratio of methyl alcohol and chloroform is 1: 3, seals, left at room temperature about 3-4 days, assembles in bottle i.e. it can be seen that aggregation material
Material occurs, i.e. 5-p-amino phenyl-10,15,20-Triphenylporphyrin nano material.
Embodiment 2 5-p-amino phenyl-10,15,20-Triphenylporphyrin preparation method of nano material
Pipette 1 mL chloroform, add 3 mg 5-p-amino phenyl-10,15,20-Triphenylporphyrins, ultrasonic make it dissolve,
Then filter, in assembling the chloroform soln obtaining 5-p-amino phenyl-10,15,20-Triphenylporphyrin in bottle.By bad
Solvent methanol carefully and is lentamente injected in the chloroform soln of 5-p-amino phenyl-10,15,20-Triphenylporphyrin, first
The volume ratio of alcohol and chloroform is 1: 3, seals, left at room temperature about 3-4 days, assembles in bottle i.e. it can be seen that aggregate material
Occur, i.e. 5-p-amino phenyl-10,15,20-Triphenylporphyrin nano material.
The system of embodiment 3 5-p-amino phenyl-10,15,20-Triphenylporphyrin aggregation nitrogen dioxide gas sensor
Standby
(1) preparation of ITO electro-conductive glass interdigital electrode；
On transparent electro-conductive glass the most after cleaning, spin coating last layer bears photoresist, is then put into 70 C in drying box
Constant temperature 10 min；2. paint sheet as mask plate designing figuratum light, develop after exposing 18 seconds under litho machine and rinse；3. will
Style clearly of developing carries out 140 C and bakes 40 min, in the mixed liquor of hydrochloric acid and nitric acid after etching, by deionized water with negative
Glue cleaning fluid removes residual acid and photoresist, obtains the ITO electro-conductive glass interdigital electrode shown in Fig. 1.
(2) by ITO substrate successively with toluene, acetone, ethanol, deionized water ultrasonic cleaning 5-10min respectively, then dry
Standby；
(3) the 5-p-amino phenyl-10,15,20-Triphenylporphyrin nanometer material respectively embodiment 1 and embodiment 2 prepared
Gob is coated onto step 2) in the interdigital electrode of ITO substrate that obtains, dry, i.e. obtain the gas sensor of gas sensor；
The performance measurement of embodiment 4 nitrogen dioxide gas sensor
Air-sensitive test device is built by laboratory, and air-sensitive test process is in comparatively gentle environment (room temperature, an external world
Under atmospheric pressure and dry air) and two electrodes between carry out under fixed-bias transistor circuit 5V.Use tester: Agilent B290a is smart
Mi Yuan/measuring unit.
Claims (5)
1., for measuring a gas sensor element for nitrogen dioxide gas, described sensor element comprises ITO electro-conductive glass
Substrate (1) interdigital electrode (2) and porphyrin nano material coating (3)；Described interdigital electrode (2) is etched in ITO electro-conductive glass substrate
(1) on, described material coating (3) drop coating is in interdigital electrode, it is characterised in that the component of described material coating is that 5-is to amino
Phenyl-10,15,20-Triphenylporphyrin nano material.
2. preparing a method for gas sensor element described in claim 1, the method comprises the following steps:
1) preparation of ITO electro-conductive glass interdigital electrode；
2) above-mentioned ITO electro-conductive glass is cleaned up；
3) by 5-p-amino phenyl-10,15,20-Triphenylporphyrin aggregation drop coating to step 2) the ITO electro-conductive glass base that obtains
In the interdigital electrode of sheet, dry, i.e. obtain the gas sensor of gas sensor.
Preparation method the most according to claim 2, it is characterised in that ITO electro-conductive glass interdigital electrode described in step 1)
Preparation method is:
On transparent electro-conductive glass the most after cleaning, spin coating last layer bears photoresist, is then put into 70 C in drying box
Constant temperature 10 min；
2. paint sheet as mask plate designing figuratum light, develop after exposing 18 seconds under litho machine and rinse；
3. style clearly of developing is carried out 140 C and bakes 40 min, in the mixed liquor of hydrochloric acid and nitric acid etching after, spend from
Sub-water and negative glue cleaning fluid remove residual acid and photoresist, obtain the ITO electro-conductive glass interdigital electrode shown in Fig. 1.
4. the preparation of 5-p-amino phenyl-10,15,20-Triphenylporphyrin nano material described in claim 2 step 3
Method, the method comprises the following steps:
1) 5-p-amino phenyl-10,15,20-Triphenylporphyrin is joined in good solvent and dissolve, filter；
2) in step 1) gained filtrate, inject or drip poor solvent, seal, stand 3～4 days, obtain 5-p-amino phenyl-
10,15,20-Triphenylporphyrin nano material；
Preparation method according to claim 3, it is characterised in that 5-p-amino phenyl-10,15,20-Triphenylporphyrin
(mol) with good solvent (ml) molal volume ratio for 1:5～100, preferably 1:4～80；
Poor solvent is 1: 3～10 with the volume ratio of good solvent；
Described good solvent is selected from one or both in chloroform, dichloromethane；
Described poor solvent is selected from one or both in methyl alcohol, n-hexane.
5.5-p-amino phenyl-10,15,20-Triphenylporphyrin is for preparing the purposes of nitrogen dioxide gas sensor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188111A (en) * | 2016-08-02 | 2016-12-07 | 济南大学 | A kind of porphyrin phthalocyanine double-level-metal coordination compound and its preparation method and application |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188111A (en) * | 2016-08-02 | 2016-12-07 | 济南大学 | A kind of porphyrin phthalocyanine double-level-metal coordination compound and its preparation method and application |
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