CN108663412A - A kind of sensor of chemical gas and preparation method thereof - Google Patents
A kind of sensor of chemical gas and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of sensor of chemical gas and preparation method thereof, which contains conducting polymer sensitive thin film, interdigital electrode substrate.Contain any one in hexafluoroisopropanol group, hexafluoroisopropanol aniline group, 3,5 dual-trifluoromethyl phenol groups in the conducting polymer.Compared with existing sensor of chemical gas, which has the characteristics that organic phosphorus compound high sensitivity, gas-selectively is good, room temperature detects in real time, senses that power consumption is extremely low, portability is excellent, preparation process is simple, easy to process, of low cost.
Description
Technical field
The invention belongs to gas sensor domains, are related to a kind of gas sensor detected in real time based on impedance, specifically relate to
And a kind of interdigital electrode senser element detected in real time based on functionalization conductive polymer resistive and pass through coat conducting polymer
Object solution is in the preparation method for preparing gas sensor in interdigital electrode substrate.
Background technology
Can the research and development of organic phosphorus compound detection sensor that can detect in real time of portable, room temperature be that research both domestic and external is hot at present
Point.Based on the chemical sensor of conducting polymer due to its high sensitivity, reproducible, compact, it is low in energy consumption the advantages that at
For the development trend of organic phosphorus compound real-time on-site detection.Nano particle that Sunghun Cho et al. are prepared based on polyaniline is received
Gas sensor prepared by rice stick, nanofiber shows organic phosphorus compound methyl-phosphoric acid dimethyl ester (DMMP) excellent sensitive
Degree, nanofiber to DMMP minimal detectable concentrations be 5ppb (Journal of Materials Chemistry A, 2013,1
(18):5679-5688.).The surface hydroxyl functionalization sea that Jun Seop Lee et al. are prepared using electrojet and thermal agitation technology
Courage shape polypyrrole nano particle has higher specific surface area, up to SBET=227m2/g, the gas sensing based on this preparation
Device, is compared to polyaniline, specific surface area and is effectively conducted area and is significantly promoted, therefore is obtained very to DMMP detection minimum concentrations
It is big to be promoted, it is 0.1ppb (Acs Nano, 2013,7 (11):10139-47.).Oh Seok Kwon et al. use PMMA Nanowires
Dimension is template, and hydroxy functionalized poly- (3,4-rthylene dioxythiophene) nanotube is prepared for using chemical vapour deposition technique, is based on this
The gas sensor of preparation organic phosphorus compound are realized 10ppt ranks response (Nano Letters, 2012,12, (6):
2797.).Although these gas sensors based on nanometer conductive polymer can realize DMMP the real-time sound of trace concentration
It answers, but still faces highly sensitive with highly selective the problem of being difficult to take into account, polyaniline, monohydroxy functionalization such as non-functionalization
Poly- (3,4-rthylene dioxythiophene) although to DMMP have quite high sensitivity, often selectivity it is bad, especially
It is very sensitive to vapor, the alcohol vapor in air, it can not be applied in outdoor complicated atmosphere, and its be susceptible to
The side effect of false alarm, it is difficult to be used widely, therefore develop while having hypersensitivity, highly selective chemical gas to pass
Sensor receives significant attention.
Invention content
To solve the above-mentioned problems, prepared the invention discloses a kind of sensor of chemical gas and preparation method thereof
Gas sensor has excellent comprehensive detection performance, including highly sensitive and high gas-selectively to organic phosphorus compound.
In order to achieve the above objectives, the present invention provides a kind of sensor of chemical gas, it is characterised in that：The gas sensor
Contain conducting polymer sensitive thin film, interdigital electrode substrate.
Preferably, the sensing principle of the gas sensor be the real-time detection technique of impedance, applied voltage 1mV-10V,
Applied voltage frequency is 0.1Hz~1000000Hz, and temperature in use is -30 DEG C~60 DEG C.
Preferably, the conducting polymer has the following structure general formula (I)：
Wherein：
M1A kind of monomeric unit is represented, conducting polymer monomer N is come from1.Conducting polymer monomer N1With following knot
Structure general formula (II)：
Wherein P1The main part in a monomer is represented, is functionalization 3,4-ethylene dioxythiophene main bodyWork(
Trimethylene dioxy thiophene main body can be changedFunctionalization pyrroles's main bodyIn any one.
R1A group is represented, including the alkylidene of C1-C12 or wherein 1 to 3 alkyl groups are by-O- ,-NH- ,-C
(O)-group ,-C (O) NH- groups ,-C (O) O- groups, the substitution of benzene radicals one or more.
R2One is represented to Protic functional groups, including hexafluoroisopropanol groupHexafluoroisopropanol aniline group3,5- dual-trifluoromethyl phenol groupsIn any one.
M2A kind of monomeric unit of copolymerization is represented, conducting polymer monomer N is come from2.Conducting polymer monomer N2It is 3,
4- ethylenedioxy thiophenesTrimethylene dioxy thiophenePyrrolesIn any one.
M is positive integer, and n is 0 or positive integer.
Preferably, the interdigital electrode material of the interdigital electrode substrate includes gold, platinum, aluminium, copper, iron, silver, and interdigital spacing is
0.5 micron~50 microns.
Preferably, m in the general structure (I):N is 100:0~1:99；In view of control polymer molecular weight and molten
Solve sex chromosome mosaicism, m:N is more preferably 99:1~1:3；Simultaneously it is also contemplated that reducing the interaction of adjacent functional monomer, m:n
Most preferably 2:1~1:3.
Preferably, the conducting polymer monomer N1P in general structure (II)1For functionalization 3,4- ethylenedioxy thiophene masters
BodyFunctionalization trimethylene dioxy thiophene main bodyFunctionalization pyrroles's main bodyIn any one；
The conducting polymer monomer N1P in general structure (II)1More preferably functionalization 3,4- ethylenedioxy thiophenes main body
Preferably, the conducting polymer monomer N1R in general structure (II)1For the alkylidene of C1~C12；In view of side
Chain chain length influences main polymer chain electron delocalization, the conducting polymer monomer N1R in general structure (II)1For-CH2-。
Preferably, the conducting polymer monomer N1R in general structure (II)2For hexafluoroisopropanol groupSix
Fluorine isopropanol aniline group3,5- dual-trifluoromethyl phenol groupsIn it is any one
Kind；The conducting polymer monomer N1R in general structure (II)2Further preferably hexafluoroisopropanol group
Preferably, the conducting polymer monomer N2For 3,4- ethylenedioxy thiophenesTrimethylene dioxy thiophenePyrrolesIn any one；The conducting polymer monomer N2Further preferably 3,4- enedioxies thiophene
Pheno
The present invention also provides the preparation methods of the sensor of chemical gas, it is characterised in that：Include the following steps：
Step 1)：Conducting polymer is dissolved in solvent, certain density solution is made into；
Step 2)：Conductive polymer solution obtained by step 1) is coated on to the interdigital electrode substrate table of special process processing
Face is dried in vacuo 24 hours；
Preferably, the preparation method of a kind of sensor of chemical gas, it is characterised in that：The solvent is water, first
Any one in alcohol, ethyl alcohol, isopropanol, acetone, N,N-dimethylformamide, acetonitrile, tetrahydrofuran, chloroform, toluene, n-hexane
Or a variety of mixed solvents；Described a certain concentration is 1ug/ml~50mg/ml；The special process is at low temperature plasma surface
Reason；The vacuum drying temperature is 20 DEG C~100 DEG C.
Compared with prior art, the sensor of chemical gas that prepared by the present invention to organic phosphorus compound and its high sensitivity,
Gas-selectively is good, room temperature detects in real time, senses that power consumption is extremely low, portability is excellent, at the same preparation process it is simple, it is easy to process,
It is of low cost, it is that one kind having potential sensor of chemical gas very much.
Description of the drawings
Present invention will be further explained below with reference to the attached drawings and examples.
The optical photograph of Fig. 1 conducting polymers I-1 coating interdigital electrodes.
The electron scanning micrograph of gas sensor prepared by Fig. 2 conducting polymers I-1 coating interdigital electrodes：A) it puts down
Film pattern；B) nano dot pattern；C) nano chain pattern；D) nanometer network pattern.
Gas sensor prepared by Fig. 3 conducting polymers I-1 coating interdigital electrodes is at normal temperatures to organic phosphorus compound methyl
The sensitivity of dimethyl phosphonate and selectivity test result.
Specific implementation mode
In order to make the present invention more obvious and understandable, it is hereby described in detail below with preferred embodiment.
Experimental raw
The preparation of conducting polymer：
Preparation example A1
Using electrochemical polymerization, by 225mg functionalization conducting polymer monomer II-1 (1mmol), 1.44g dodecyl sulphurs
Electrolytic cell is added in sour sodium (5mmol), 636mg lithium chlorides (15mmol), 50ml ultra-pure waters, using gold electrode as working electrode, with Ag/
AgCl is reference electrode, is to electrode with platinum electrode, and polymerization potential is 1.13V, the polymerisation 60s under air at room temperature environment,
Using acetone collected polymer, repeatedly, appropriate anhydrous magnesium sulfate water removal, the holes 220nm will be added in polymer/acetone soln
Diameter polytetrafluoroethylene (PTFE) membrane filtration, revolving solution are concentrated into 0.5ml.Concentrated solution is dripped to dropwise in 40ml chloroforms, is shaken, centrifugation,
Supernatant liquor is removed, chloroform is added, is centrifuged, repeatedly.Above-mentioned dissolving-centrifugal process 2-3 times is repeated, by black precipitate room temperature
Vacuum drying 24 hours, that is, be prepared 90mg functionalization conducting polymers I-1.
Preparation example A2
Using electrochemical polymerization, 188mg functionalization conducting polymer monomer II-2 (0.9mmol), 15mg are copolymerized conductive
Electrolytic cell is added in polymer monomer III-2 (0.1mmol), 636mg lithium chlorides (15mmol), 50ml acetonitriles, using gold electrode as work
Make electrode, with Ag+/ Ag is reference electrode, is to electrode with platinum electrode, polymerization potential is 1.25V, is gathered under air at room temperature environment
Reaction 60s is closed repeatedly, to remove appropriate anhydrous magnesium sulfate is added in polymer/acetone soln using acetone collected polymer
Water, the apertures 220nm polytetrafluoroethylene (PTFE) membrane filtration, revolving solution are concentrated into 0.5ml.Concentrated solution is dripped to dropwise in 40ml chloroforms,
Supernatant liquor is removed in concussion, centrifugation, and chloroform is added, and centrifuges, repeatedly.Above-mentioned dissolving-centrifugal process 2-3 times is repeated, it will be black
Color, which precipitates normal-temperature vacuum, to be dried 24 hours, that is, 105mg functionalization conducting polymers I-2 is prepared.
Preparation example A3
Using electrochemical polymerization, 176mg functionalization conducting polymer monomer II-3 (0.7mmol), 43mg are copolymerized conductive
Electrolytic cell is added in polymer monomer III-3 (0.3mmol), 636mg lithium chlorides (15mmol), 50ml dichloromethane, with gold electrode
For working electrode, with Ag+/ Ag is reference electrode, is to electrode with platinum electrode, polymerization potential is 1.23V, in air at room temperature environment
Using acetone collected polymer repeatedly, appropriate anhydrous slufuric acid will be added in lower polymerisation 60s in polymer/acetone soln
Magnesium removes water, the apertures 220nm polytetrafluoroethylene (PTFE) membrane filtration, and revolving solution is concentrated into 0.5ml.Concentrated solution is dripped to 40ml chloroforms dropwise
In, it shakes, supernatant liquor is removed in centrifugation, and chloroform is added, and centrifuges, repeatedly.Above-mentioned dissolving-centrifugal process 2-3 times is repeated,
Black precipitate normal-temperature vacuum is dried 24 hours, that is, 95mg functionalization conducting polymers I-3 is prepared.
Preparation example A4
Using electrochemical polymerization, 161mg functionalization conducting polymer monomer II-4 (0.5mmol), 78mg are copolymerized conductive
Polymer monomer III-4 (0.5mmol), 1.44g dodecyl sodium sulfates (5mmol), 636mg lithium chlorides (15mmol), 50ml
Electrolytic cell is added in ultra-pure water, is to electrode, polymerization with platinum electrode using Ag/AgCl as reference electrode using gold electrode as working electrode
Potential is 1.13V, the polymerisation 60s under air at room temperature environment, using acetone collected polymer, repeatedly, by polymer/
Appropriate anhydrous magnesium sulfate water removal, the apertures 220nm polytetrafluoroethylene (PTFE) membrane filtration are added in acetone soln, revolving solution is concentrated into
0.5ml.Concentrated solution is dripped to dropwise in 40ml chloroforms, is shaken, supernatant liquor is removed in centrifugation, and chloroform is added, and centrifugation repeats more
It is secondary.Above-mentioned dissolving-centrifugal process 2-3 times is repeated, black precipitate normal-temperature vacuum is dried 24 hours, that is, 143mg work(is prepared
Conducting polymer I-4 can be changed.
Preparation example A5
It is using electrochemical polymerization, 90mg functionalization conducting polymer monomer II-5 (0.4mmol), 94mg copolymerization is conductive poly-
Electrolytic cell is added in monomer adduct III-5 (0.6mmol), 636mg lithium chlorides (15mmol), 50ml acetonitriles, using gold electrode as work
Electrode, with Ag+/ Ag is reference electrode, is to electrode with platinum electrode, polymerization potential is 1.23V, is polymerize under air at room temperature environment
Reaction 60s repeatedly, is removed using acetone collected polymer by appropriate anhydrous magnesium sulfate is added in polymer/acetone soln
Water, the apertures 220nm polytetrafluoroethylene (PTFE) membrane filtration, revolving solution are concentrated into 0.5ml.Concentrated solution is dripped to dropwise in 40ml chloroforms,
Supernatant liquor is removed in concussion, centrifugation, and chloroform is added, and centrifuges, repeatedly.Above-mentioned dissolving-centrifugal process 2-3 times is repeated, it will be black
Color, which precipitates normal-temperature vacuum, to be dried 24 hours, that is, 121mg functionalization conducting polymers I-5 is prepared.
Preparation example A6
It is using electrochemical polymerization, 61mg functionalization conducting polymer monomer II-6 (0.4mmol), 85mg copolymerization is conductive poly-
Electrolytic cell is added in monomer adduct III-6 (0.6mmol), 636mg lithium chlorides (15mmol), 50ml dichloromethane, is with gold electrode
Working electrode, with Ag+/ Ag is reference electrode, is to electrode with platinum electrode, polymerization potential is 1.26V, under air at room temperature environment
Using acetone collected polymer repeatedly, appropriate anhydrous magnesium sulfate will be added in polymerisation 60s in polymer/acetone soln
Water removal, the apertures 220nm polytetrafluoroethylene (PTFE) membrane filtration, revolving solution are concentrated into 0.5ml.Concentrated solution is dripped to 40ml chloroforms dropwise
In, it shakes, supernatant liquor is removed in centrifugation, and chloroform is added, and centrifuges, repeatedly.Above-mentioned dissolving-centrifugal process 2-3 times is repeated,
Black precipitate normal-temperature vacuum is dried 24 hours, that is, 81mg functionalization conducting polymers I-6 is prepared.
Preparation example A7
It is using electrochemical polymerization, 70mg functionalization conducting polymer monomer II-7 (0.3mmol), 47mg copolymerization is conductive poly-
Electrolytic cell is added in monomer adduct III-7 (0.7mmol), 636mg lithium chlorides (15mmol), 50ml dichloromethane, is with gold electrode
Working electrode, with Ag+/ Ag is reference electrode, is to electrode with platinum electrode, polymerization potential is 1.24V, under air at room temperature environment
Using acetone collected polymer repeatedly, appropriate anhydrous magnesium sulfate will be added in polymerisation 60s in polymer/acetone soln
Water removal, the apertures 220nm polytetrafluoroethylene (PTFE) membrane filtration, revolving solution are concentrated into 0.5ml.Concentrated solution is dripped to 40ml chloroforms dropwise
In, it shakes, supernatant liquor is removed in centrifugation, and chloroform is added, and centrifuges, repeatedly.Above-mentioned dissolving-centrifugal process 2-3 times is repeated,
Black precipitate normal-temperature vacuum is dried 24 hours, that is, 56mg functionalization conducting polymers I-7 is prepared.
Preparation example A8
It is polymerize using solution oxide, reaction, which is added, in 216mg anhydrous ferric chlorides (1.33mol), 5ml anhydrous chloroforms steals bottle
In, ultrasonic disperse 2h under 50w power is placed in room temperature, be added 275mg functionalization conducting polymer monomer II-8 (0.9mmol),
6.7mg is copolymerized conducting polymer monomer III-8 (0.1mmol), and under room temperature under nitrogen environment, stirring polymerisation is for 24 hours.It uses
220nm polytetrafluoroethylene (PTFE) filtering with microporous membrane reaction solutions use methanol, ultra-pure water, isopropanol, chloroform to rinse filter residue respectively, will
Black filter residue normal-temperature vacuum is dried 24 hours, that is, 184mg functionalization conducting polymers I-8 is prepared.
Preparation example A9
It is polymerize using solution oxide, reaction, which is added, in 216mg anhydrous ferric chlorides (1.33mol), 5ml anhydrous chloroforms steals bottle
In, ultrasonic disperse 2h under 50w power is placed in room temperature, be added 275mg functionalization conducting polymer monomer II-9 (0.6mmol),
6.7mg is copolymerized conducting polymer monomer III-9 (0.4mmol), and under room temperature under nitrogen environment, stirring polymerisation is for 24 hours.It uses
220nm polytetrafluoroethylene (PTFE) filtering with microporous membrane reaction solutions use methanol, ultra-pure water, isopropanol, chloroform to rinse filter residue respectively, will
Black filter residue normal-temperature vacuum is dried 24 hours, that is, 184mg functionalization conducting polymers I-9 is prepared.
Preparation example A10
It is polymerize using solution oxide, reaction, which is added, in 216mg anhydrous ferric chlorides (1.33mol), 5ml anhydrous chloroforms steals bottle
In, ultrasonic disperse 2h under 50w power is placed in room temperature, be added 206mg functionalization conducting polymer monomer II-10 (0.5mmol),
71mg is copolymerized conducting polymer monomer III-10 (0.5mmol), and under room temperature under nitrogen environment, stirring polymerisation is for 24 hours.It uses
220nm polytetrafluoroethylene (PTFE) filtering with microporous membrane reaction solutions use methanol, ultra-pure water, isopropanol, chloroform to rinse filter residue respectively, will
Black filter residue normal-temperature vacuum is dried 24 hours, that is, 135mg functionalization conducting polymers I-10 is prepared.
Preparation example A11
It is polymerize using solution oxide, reaction, which is added, in 216mg anhydrous ferric chlorides (1.33mol), 5ml anhydrous chloroforms steals bottle
In, ultrasonic disperse 2h under 50w power is placed in room temperature, be added 173mg functionalization conducting polymer monomer II-11 (0.45mmol),
86mg is copolymerized conducting polymer monomer III-11 (0.55mmol), and under room temperature under nitrogen environment, stirring polymerisation is for 24 hours.It uses
220nm polytetrafluoroethylene (PTFE) filtering with microporous membrane reaction solutions use methanol, ultra-pure water, isopropanol, chloroform to rinse filter residue respectively, will
Black filter residue normal-temperature vacuum is dried 24 hours, that is, 165mg functionalization conducting polymers I-11 is prepared.
Preparation example A12
It is polymerize using solution oxide, reaction, which is added, in 216mg anhydrous ferric chlorides (1.33mol), 5ml anhydrous chloroforms steals bottle
In, ultrasonic disperse 2h under 50w power is placed in room temperature, be added 177mg functionalization conducting polymer monomer II-12 (0.4mmol),
94mg is copolymerized conducting polymer monomer III-12 (0.6mmol), and under room temperature under nitrogen environment, stirring polymerisation is for 24 hours.It uses
220nm polytetrafluoroethylene (PTFE) filtering with microporous membrane reaction solutions use methanol, ultra-pure water, isopropanol, chloroform to rinse filter residue respectively, will
Black filter residue normal-temperature vacuum is dried 24 hours, that is, 182mg functionalization conducting polymers I-12 is prepared.
Preparation example A13
It is polymerize using solution oxide, 144mg iodine (1.33mol), 5ml toluene is added reaction and stolen in bottle, is surpassed under 50w power
Sound disperses 2h, is placed in room temperature, and it is conductive poly- that 148mg functionalization conducting polymer monomer II-13 (0.5mmol), 34mg copolymerization is added
Monomer adduct III-13 (0.5mmol), under 80 DEG C of nitrogen environments, stirring polymerisation is for 24 hours.Use 220nm polytetrafluoroethylene (PTFE)
Filtering with microporous membrane reaction solution uses methanol, ultra-pure water, isopropanol, chloroform to rinse filter residue, by black filter residue normal-temperature vacuum respectively
It is 24 hours dry, that is, 97mg functionalization conducting polymers I-13 is prepared.
Preparation example A14
It is polymerize using solution oxide, 144mg iodine (1.33mol), 5ml toluene is added reaction and stolen in bottle, is surpassed under 50w power
Sound disperses 2h, is placed in room temperature, and it is conductive poly- that 194mg functionalization conducting polymer monomer II-14 (0.6mmol), 27mg copolymerization is added
Monomer adduct III-14 (0.4mmol), under 90 DEG C of nitrogen environments, stirring polymerisation is for 24 hours.Use 220nm polytetrafluoroethylene (PTFE)
Filtering with microporous membrane reaction solution uses methanol, ultra-pure water, isopropanol, chloroform to rinse filter residue, by black filter residue normal-temperature vacuum respectively
It is 24 hours dry, that is, 110mg functionalization conducting polymers I-14 is prepared.
Preparation example A15
It is polymerize using solution oxide, 144mg iodine (1.33mol), 5ml toluene is added reaction and stolen in bottle, is surpassed under 50w power
Sound disperses 2h, is placed in room temperature, and it is conductive poly- that 269mg functionalization conducting polymer monomer II-15 (0.7mmol), 43mg copolymerization is added
Monomer adduct III-15 (0.3mmol), under 100 DEG C of nitrogen environments, stirring polymerisation is for 24 hours.Use 220nm polytetrafluoroethylene (PTFE)
Filtering with microporous membrane reaction solution uses methanol, ultra-pure water, isopropanol, chloroform to rinse filter residue, by black filter residue normal-temperature vacuum respectively
It is 24 hours dry, that is, 213mg functionalization conducting polymers I-15 is prepared.
Preparation example A16
Using vapor deposition polymerization, by 144mg iodine (1.33mol), 414mg functionalization conducting polymer monomers II-16
(1mmol) is added reaction and steals in bottle, under 50 DEG C of nitrogen environments, air pressure 760Torr, polymerisation 5h.Use 220nm poly- four
Fluoride microporous filtering film filtering reacting liquid uses methanol, ultra-pure water, isopropanol, chloroform to rinse filter residue respectively, and black filter residue is normal
Temperature vacuum drying 24 hours, that is, be prepared 243mg functionalization conducting polymers I-16.
Preparation example A17
Using vapor deposition polymerization, by 144mg iodine (1.33mol), 159mg functionalization conducting polymer monomers II-17
(0.4mmol), 85mg, which are copolymerized conducting polymer monomer III-17 (0.6mmol) and are added, to react in surreptitiously bottle, in 50 DEG C of nitrogen environments
Under, air pressure 760Torr, polymerisation 5h.Using 220nm polytetrafluoroethylene (PTFE) filtering with microporous membrane reaction solutions, first is used respectively
Alcohol, ultra-pure water, isopropanol, chloroform rinse filter residue, and black filter residue normal-temperature vacuum is dried 24 hours, that is, 112mg work(is prepared
Conducting polymer I-17 can be changed.
Preparation example A18
Using vapor deposition polymerization, by 144mg iodine (1.33mol), 237mg functionalization conducting polymer monomers II-18
(0.5mmol), 78mg, which are copolymerized conducting polymer monomer III-18 (0.5mmol) and are added, to react in surreptitiously bottle, in 90 DEG C of nitrogen environments
Under, air pressure 760Torr, polymerisation 5h.Using 220nm polytetrafluoroethylene (PTFE) filtering with microporous membrane reaction solutions, first is used respectively
Alcohol, ultra-pure water, isopropanol, chloroform rinse filter residue, and black filter residue normal-temperature vacuum is dried 24 hours, that is, 156mg work(is prepared
Conducting polymer I-18 can be changed.
Preparation example A19
Using vapor deposition polymerization, by 144mg iodine (1.33mol), 155mg functionalization conducting polymer monomers II-19
(0.5mmol), 34mg, which are copolymerized conducting polymer monomer III-19 (0.5mmol) and are added, to react in surreptitiously bottle, in 90 DEG C of nitrogen environments
Under, air pressure 1Torr, polymerisation 5h.Using 220nm polytetrafluoroethylene (PTFE) filtering with microporous membrane reaction solutions, respectively use methanol,
Ultra-pure water, isopropanol, chloroform rinse filter residue, and black filter residue normal-temperature vacuum is dried 24 hours, that is, 88mg functionalization is prepared
Conducting polymer I-19.
Monomer and structural formula used in preparation example 1-19 are as shown in table 1.
Table 1
II units and the molar ratio of III units are as shown in table 2 in preparation example 1-19 reaction conditions and product.Table 2：
Chemical sensor prepares embodiment：
Embodiment 1
Conducting polymer I-1 is dissolved in acetone, a concentration of 4mg/ml is adjusted.In the 400w processing of low temperature plasma surface
Conducting polymer I-1 sensitive thin films are prepared using spin-coating method in 10 minutes golden interdigital electrodes (the interdigital spacing of 3um), are controlled
Rotating speed is 6000rpm, and the duration is 60 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas sensing
The polymer film thickness of device is 25nm, and surface topography is nano dot pattern, and sensor resistance is 35 kilo-ohms.This gas at 25 DEG C
Sensor is 25ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.In same 1% saturated vapor at 25 DEG C
This gas sensor is 21 times to vapor response to dimethyl methyl phosphonate response under concentration.
Embodiment 2
Conducting polymer I-2 is dissolved in acetone, a concentration of 4mg/ml is adjusted.In the 400w processing of low temperature plasma surface
Conducting polymer I-2 sensitive thin films are prepared using spin-coating method in 10 minutes golden interdigital electrodes (the interdigital spacing of 3um), are controlled
Rotating speed is 3000rpm, and the duration is 60 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas sensing
The polymer film thickness of device is 23nm, and surface topography is nano dot pattern, and sensor resistance is 30 kilo-ohms.This gas at 25 DEG C
Sensor is 30ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.In same 1% saturated vapor at 25 DEG C
This gas sensor is 19 times to vapor response to dimethyl methyl phosphonate response under concentration.
Embodiment 3
Conducting polymer I-3 is dissolved in acetone, a concentration of 4mg/ml is adjusted.In the 200w processing of low temperature plasma surface
Conducting polymer I-3 sensitive thin films are prepared using spin-coating method in 10 minutes golden interdigital electrodes (the interdigital spacing of 3um), are controlled
Rotating speed is 6000rpm, and the duration is 60 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas sensing
The polymer film thickness of device is 20nm, and surface topography is nano dot pattern, and sensor resistance is 40 kilo-ohms.This gas at 25 DEG C
Sensor is 32ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.In same 1% saturated vapor at 25 DEG C
This gas sensor is 18 times to vapor response to dimethyl methyl phosphonate response under concentration.
Embodiment 4
Conducting polymer I-4 is dissolved in acetone, a concentration of 4mg/ml is adjusted.In the 200w processing of low temperature plasma surface
Conducting polymer I-4 sensitive thin films are prepared using spin-coating method in 5 minutes golden interdigital electrodes (the interdigital spacing of 3um), are controlled
Rotating speed is 6000rpm, and the duration is 60 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas sensing
The polymer film thickness of device is 30nm, and surface topography is nano dot pattern, and sensor resistance is 31 kilo-ohms.This gas at 40 DEG C
Sensor is 50ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.In same 1% saturated vapor at 40 DEG C
This gas sensor is 23 times to vapor response to dimethyl methyl phosphonate response under concentration.
Embodiment 5
Conducting polymer I-5 is dissolved in acetone, a concentration of 4mg/ml is adjusted.In the 100w processing of low temperature plasma surface
Conducting polymer I-5 sensitive thin films are prepared using spin-coating method in 5 minutes golden interdigital electrodes (the interdigital spacing of 3um), are controlled
Rotating speed is 3000rpm, and the duration is 90 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas sensing
The polymer film thickness of device is 31nm, and surface topography is nano dot pattern, and sensor resistance is 42 kilo-ohms.This gas at 50 DEG C
Sensor is 60ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.In same 1% saturated vapor at 50 DEG C
This gas sensor is 20 times to vapor response to dimethyl methyl phosphonate response under concentration.
Embodiment 6
Conducting polymer I-6 is dissolved in acetone, a concentration of 4mg/ml is adjusted.In golden interdigital electrode (the 3um forks of no processing
Refer to spacing) on using spin-coating method prepare conducting polymer I-6 sensitive thin films, control rotating speed is 3000rpm, and the duration is
90 seconds, spin coating temperature was 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.The polymer film thickness of this gas sensor is
27nm, surface topography are flat membrane pattern, 36 kilo-ohms of sensor resistance.This gas sensor is to organic phosphorus compound methylphosphine at 50 DEG C
The minimal detectable concentration of dimethyl phthalate is 64ppb.At 50 DEG C under same 1% saturated vapor concentration this gas sensor to methyl
Dimethyl phosphonate response is 15 times to vapor response.
Embodiment 7
Conducting polymer I-7 is dissolved in acetone, a concentration of 6.8mg/ml is adjusted.At the 400w of low temperature plasma surface
Conducting polymer I-7 sensitive thin films are prepared using spin-coating method in 10 minutes golden interdigital electrodes (the interdigital spacing of 3um) of reason, are controlled
Rotating speed processed is 6000rpm, and the duration is 60 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas passes
The polymer film thickness of sensor is 50nm, and surface topography is nano chain pattern, 25 kilo-ohms of sensor resistance.This gas at 25 DEG C
Sensor is 34ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.In same 1% saturated vapor at 25 DEG C
This gas sensor is 18 times to vapor response to dimethyl methyl phosphonate response under concentration.
Embodiment 8
Conducting polymer I-8 is dissolved in acetone, a concentration of 6.8mg/ml is adjusted.At the 400w of low temperature plasma surface
Conducting polymer I-8 sensitive thin films are prepared using spin-coating method in 10 minutes golden interdigital electrodes (the interdigital spacing of 3um) of reason, are controlled
Rotating speed processed is 6000rpm, and the duration is 60 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas passes
The polymer film thickness of sensor is 63nm, and surface topography is nano chain pattern, 25 kilo-ohms of sensor resistance.This gas at 25 DEG C
Sensor is 40ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.In same 1% saturated vapor at 25 DEG C
This gas sensor is 13 times to vapor response to dimethyl methyl phosphonate response under concentration.
Embodiment 9
Conducting polymer I-9 is dissolved in acetone, a concentration of 6.8mg/ml is adjusted.At the 200w of low temperature plasma surface
Conducting polymer I-9 sensitive thin films are prepared using spin-coating method in 10 minutes golden interdigital electrodes (the interdigital spacing of 3um) of reason, are controlled
Rotating speed processed is 6000rpm, and the duration is 60 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas passes
The polymer film thickness of sensor is 72nm, and surface topography is nano chain pattern, 24 kilo-ohms of sensor resistance.This gas at 25 DEG C
Sensor is 42ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.In same 1% saturated vapor at 25 DEG C
This gas sensor is 22 times to vapor response to dimethyl methyl phosphonate response under concentration.
Embodiment 10
Conducting polymer I-10 is dissolved in acetone, a concentration of 6.8mg/ml is adjusted.In low temperature plasma surface 100w
Conducting polymer I-10 sensitive thin films are prepared using spin-coating method in the golden interdigital electrode (the interdigital spacing of 3um) of processing 5 minutes,
Control rotating speed is 6000rpm, and the duration is 60 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas
The polymer film thickness of sensor is 62nm, and surface topography is nano chain pattern, 28 kilo-ohms of sensor resistance.This gas at 25 DEG C
Body sensor is 50ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.It is steamed in same 1% saturation at 25 DEG C
This gas sensor is 18 times to vapor response to dimethyl methyl phosphonate response under vapour concentration.
Embodiment 11
Conducting polymer I-11 is dissolved in acetone, a concentration of 6.8mg/ml is adjusted.In the golden interdigital electrode of no processing
Conducting polymer I-11 sensitive thin films are prepared using spin-coating method in (the interdigital spacing of 3um), control rotating speed is 4000rpm, is held
The continuous time is 90 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.The polymer thin film thickness of this gas sensor
Degree is 59nm, and surface topography is flat membrane pattern, 23 kilo-ohms of sensor resistance.This gas sensor is to organic phosphorus compound first at 25 DEG C
The minimal detectable concentration of base dimethyl phosphonate is 63ppb.At 25 DEG C under same 1% saturated vapor concentration this gas sensor pair
Dimethyl methyl phosphonate response is 12 times to vapor response.
Embodiment 12
Conducting polymer I-12 is dissolved in acetone, a concentration of 8mg/ml is adjusted.At the 400w of low temperature plasma surface
Conducting polymer I-12 sensitive thin films are prepared using spin-coating method in 10 minutes golden interdigital electrodes (the interdigital spacing of 3um) of reason,
Control rotating speed is 3000rpm, and the duration is 90 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas
The polymer film thickness of sensor is 80nm, and surface topography is nano chain pattern, 14 kilo-ohms of sensor resistance.This gas at 25 DEG C
Body sensor is 70ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.It is steamed in same 1% saturation at 25 DEG C
This gas sensor is 17 times to vapor response to dimethyl methyl phosphonate response under vapour concentration.
Embodiment 13
Conducting polymer I-13 is dissolved in methanol, a concentration of 8mg/ml is adjusted.At the 200w of low temperature plasma surface
Conducting polymer I-13 sensitive thin films are prepared using spin-coating method in 10 minutes golden interdigital electrodes (the interdigital spacing of 3um) of reason,
Control rotating speed is 2000rpm, and the duration is 60 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas
The polymer film thickness of sensor is 82nm, and surface topography is nano chain pattern, 13 kilo-ohms of sensor resistance.This gas at 40 DEG C
Body sensor is 75ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.It is steamed in same 1% saturation at 40 DEG C
This gas sensor is 19 times to vapor response to dimethyl methyl phosphonate response under vapour concentration.
Embodiment 14
Conducting polymer I-14 is dissolved in methanol, a concentration of 8mg/ml is adjusted.At the 100w of low temperature plasma surface
Conducting polymer I-14 sensitive thin films are prepared using spin-coating method in 10 minutes golden interdigital electrodes (the interdigital spacing of 3um) of reason,
Control rotating speed is 4000rpm, and the duration is 60 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas
The polymer film thickness of sensor is 86nm, and surface topography is nano chain pattern, 16 kilo-ohms of sensor resistance.This gas at 50 DEG C
Body sensor is 80ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.It is steamed in same 1% saturation at 50 DEG C
This gas sensor is 16 times to vapor response to dimethyl methyl phosphonate response under vapour concentration.
Embodiment 15
Conducting polymer I-15 is dissolved in methanol, a concentration of 8mg/ml is adjusted.In the golden interdigital electrode (3um of no processing
Interdigital spacing) on using spin-coating method prepare conducting polymer I-15 sensitive thin films, control rotating speed is 6000rpm, when continuing
Between be 60 seconds, spin coating temperature be 25 DEG C, it is subsequent 25 DEG C be dried in vacuo 24 hours.The polymer film thickness of this gas sensor is
82nm, surface topography are flat membrane pattern, 18 kilo-ohms of sensor resistance.This gas sensor is to organic phosphorus compound methylphosphine at 50 DEG C
The minimal detectable concentration of dimethyl phthalate is 73ppb.At 50 DEG C under same 1% saturated vapor concentration this gas sensor to methyl
Dimethyl phosphonate response is 21 times to vapor response.
Embodiment 16
Conducting polymer I-16 is dissolved in methanol, a concentration of 8mg/ml is adjusted.At the 400w of low temperature plasma surface
Conducting polymer I-16 sensitive thin films are prepared using spin-coating method in 5 minutes golden interdigital electrodes (the interdigital spacing of 3um) of reason, are controlled
Rotating speed processed is 6000rpm, and the duration is 60 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas passes
The polymer film thickness of sensor is 121nm, and surface topography is nano chain pattern, 6 kilo-ohms of sensor resistance.This gas at 25 DEG C
Sensor is 88ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.In same 1% saturated vapor at 25 DEG C
This gas sensor is 19 times to vapor response to dimethyl methyl phosphonate response under concentration.
Embodiment 17
Conducting polymer I-17 is dissolved in acetonitrile, a concentration of 10mg/ml is adjusted.At the 200w of low temperature plasma surface
Conducting polymer I-17 sensitive thin films are prepared using spin-coating method in 10 minutes golden interdigital electrodes (the interdigital spacing of 3um) of reason,
Control rotating speed is 6000rpm, and the duration is 90 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.This gas
The polymer film thickness of sensor is 112nm, and surface topography is nanometer network pattern, 5.7 kilo-ohms of sensor resistance.At 25 DEG C
This gas sensor is 90ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate.It is full same 1% at 25 DEG C
It is 17 times to vapor response to dimethyl methyl phosphonate response with this gas sensor under vapour concentration.
Embodiment 18
Conducting polymer I-18 is dissolved in n,N-Dimethylformamide, a concentration of 10mg/ml is adjusted.In low-temperature plasma
In the golden interdigital electrode (the interdigital spacing of 3um) of body surface face 100w processing 10 minutes conducting polymer I- is prepared using spin-coating method
18 sensitive thin films, control rotating speed are 5000rpm, and the duration is 90 seconds, and spin coating temperature is 25 DEG C, subsequent 25 DEG C of vacuum drying 24
Hour.The polymer film thickness of this gas sensor is 120nm, and surface topography is nanometer network pattern, sensor resistance 7.2
Kilo-ohm.This gas sensor is 95ppb to the minimal detectable concentration of organic phosphorus compound dimethyl methyl phosphonate at 25 DEG C.At 25 DEG C
This gas sensor is to the 16 of vapor response to dimethyl methyl phosphonate response under same 1% saturated vapor concentration
Times.
Embodiment 19
Conducting polymer I-19 is dissolved in tetrahydrofuran, a concentration of 10mg/ml is adjusted.In the golden interdigital electrode of no processing
Conducting polymer I-19 sensitive thin films are prepared using spin-coating method in (the interdigital spacing of 3um), control rotating speed is 4000rpm, is held
The continuous time is 90 seconds, and spin coating temperature is 25 DEG C, and subsequent 25 DEG C are dried in vacuo 24 hours.The polymer thin film thickness of this gas sensor
Degree is 108nm, and surface topography is flat membrane pattern, 5.4 kilo-ohms of sensor resistance.This gas sensor is to organic phosphorus compound at 25 DEG C
The minimal detectable concentration of dimethyl methyl phosphonate is 100ppb.At 25 DEG C under same 1% saturated vapor concentration this gas sensing
Device is to 18 times that dimethyl methyl phosphonate response is to vapor response.
Claims (14)
1. a kind of sensor of chemical gas, it is characterised in that：It contains conducting polymer sensitive thin film, interdigital electrode substrate.
2. a kind of sensor of chemical gas according to claim 1, it is characterised in that：The sensing of the gas sensor is former
Reason is the real-time detection technique of impedance, and applied voltage 1mV-10V, applied voltage frequency is 0.1Hz ~ 1000000Hz.
3. a kind of sensor of chemical gas according to claim 1, it is characterised in that：The gas sensor uses temperature
Degree is -30 DEG C ~ 60 DEG C.
4. a kind of sensor of chemical gas according to claim 1, it is characterised in that：The conducting polymer has formula
（Ⅰ）Shown general structure：
（Ⅰ）
Wherein：
M1A kind of monomeric unit is represented, conducting polymer monomer N is come from1, conducting polymer monomer N1It has the following structure logical
Formula（Ⅱ）：
（Ⅱ）
Wherein P1The main part in a monomer is represented, is functionalization 3,4-ethylene dioxythiophene main body, functionalization
Trimethylene dioxy thiophene main body, functionalization pyrroles's main bodyIn any one；
R1A group is represented, including the alkylidene of C1-C12 or wherein 1 to 3 alkyl groups are by-O- ,-NH- ,-C (O)-
Group ,-C (O) NH-group ,-C (O) O- groups, the substitution of benzene radicals one or more；
R2One is represented to Protic functional groups, including hexafluoroisopropanol group, hexafluoroisopropanol aniline group, 3,5- dual-trifluoromethyl phenol groupsIn any one；
M2A kind of monomeric unit of copolymerization is represented, conducting polymer monomer N is come from2, conducting polymer monomer N2For 3,4- second
Support dioxy thiophene, trimethylene dioxy thiophene, pyrrolesIn any one, m is positive integer, and n is
0 or positive integer.
5. a kind of sensor of chemical gas according to claim 1, it is characterised in that：The interdigital electrode substrate it is interdigital
Electrode material includes gold, platinum, aluminium, copper, iron, silver, and interdigital spacing is 0.5 micron ~ 50 microns.
6. a kind of sensor of chemical gas according to right 1, it is characterised in that：The conducting polymer structures general formula（Ⅰ）
Middle m:N is 100:0~1:99.
7. a kind of sensor of chemical gas according to right 1, it is characterised in that：The conducting polymer monomer N1Structure is logical
Formula（Ⅱ）Middle P1For functionalization 3,4- ethylenedioxy thiophene main bodys, functionalization trimethylene dioxy thiophene main body, functionalization pyrroles's main bodyIn any one.
8. a kind of sensor of chemical gas according to right 1, it is characterised in that：The conducting polymer monomer N1Structure is logical
Formula（Ⅱ）Middle P1For functionalization 3,4- ethylenedioxy thiophene main bodys。
9. a kind of sensor of chemical gas according to right 1, it is characterised in that：The conducting polymer monomer N1Structure is logical
Formula（Ⅱ）Middle R1For the alkylidene of C1 ~ C12.
10. a kind of sensor of chemical gas according to right 1, it is characterised in that：The conducting polymer monomer N1Structure is logical
Formula（Ⅱ）Middle R1For-CH2-。
11. a kind of sensor of chemical gas according to right 1, it is characterised in that：The conducting polymer monomer N1Structure is logical
Formula（Ⅱ）Middle R2For hexafluoroisopropanol group, hexafluoroisopropanol aniline group, 3,5- bis- three
Methyl fluoride phenolic groupsIn any one.
12. a kind of sensor of chemical gas according to right 1, it is characterised in that：The conducting polymer monomer N1Structure is logical
Formula（Ⅱ）Middle R2For hexafluoroisopropanol group。
13. a kind of sensor of chemical gas according to right 1, it is characterised in that：The conducting polymer monomer N2For 3,4-
Ethylenedioxy thiophene, trimethylene dioxy thiophene, pyrrolesIn any one.
14. the preparation method of the sensor of chemical gas described in a kind of any one of claim 1-13, it is characterised in that：Including
Following steps：
Step 1)：Conducting polymer is dissolved in water, methanol, ethyl alcohol, isopropanol, acetone, N,N-dimethylformamide, acetonitrile, four
Any one or more in the mixed solvent in hydrogen furans, chloroform, toluene, n-hexane, is made into the molten of 1ug/ml ~ 50mg/ml concentration
Liquid；
Step 2)：By step 1）Gained conductive polymer solution is coated on cold-plasma surfaces treated or without the interdigital of processing
Electrode basement surface, 20oC~100oC is dried in vacuo 24 hours.
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| CN103159781A (en) * | 2013-03-28 | 2013-06-19 | 江西科技师范大学 | Monomer and polymer of carboxyl-functionalized (3,4-ethylenedioxythiophene) and preparation method thereof |
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2018
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| CN1271096A (en) * | 1999-04-16 | 2000-10-25 | 电子科技大学 | Nitrogen oxide sensor made of doped polyaniline and its making process |
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