CN108663412B - Chemical gas sensor and preparation method thereof - Google Patents
Chemical gas sensor and preparation method thereof Download PDFInfo
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- CN108663412B CN108663412B CN201810519513.1A CN201810519513A CN108663412B CN 108663412 B CN108663412 B CN 108663412B CN 201810519513 A CN201810519513 A CN 201810519513A CN 108663412 B CN108663412 B CN 108663412B
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Abstract
The invention discloses a chemical gas sensor and a preparation method thereof. The conductive polymer contains any one of a hexafluoroisopropanol group, a hexafluoroisopropanol aniline group and a3, 5-bis (trifluoromethyl) phenol group. Compared with the existing chemical gas sensor, the gas sensor has the characteristics of high sensitivity to organic phosphide, good gas selectivity, normal-temperature real-time detection, extremely low sensing power consumption, excellent portability, simple preparation process, easy processing, low cost and the like.
Description
Technical Field
The invention belongs to the field of gas sensors, relates to a gas sensor based on impedance real-time detection, and particularly relates to an interdigital electrode sensing device based on functionalized conductive polymer impedance real-time detection and a preparation method for preparing a gas sensor on an interdigital electrode substrate by coating a conductive polymer solution.
Background
The research and development of portable organic phosphide detection sensors capable of real-time detection at normal temperature is a research hotspot at home and abroad at present. The chemical sensor based on the conductive polymer has the advantages of high sensitivity, good repeatability, small volume, low power consumption and the like, and becomes a development trend of real-time and on-site detection of organic phosphide. Sunghun Cho et al, a gas sensor based on polyaniline-prepared nanoparticles, nanorods, nanofibers, showed excellent sensitivity to the organophosphate dimethyl methyl phosphate (DMMP), with nanofibers having a minimum detection concentration of 5ppb for DMMP (Journal of Materials Chemistry A,2013,1(18): 5679-. The surface hydroxyl group functionalized sea urchin-shaped polypyrrole nanoparticles prepared by Jun Seop Lee and other technologies by electrospray and thermal stirring have a high specific surface area (SBET is 227m 2/g), and a gas sensor prepared based on the method has the advantages that the specific surface area and the effective conduction area are greatly increased compared with polyaniline, so that the minimum concentration of DMMP detection is greatly increased and is 0.1ppb (Acs Nano,2013,7(11): 10139-47.). Oh Seok Kwon et al prepared hydroxyl-functionalized poly (3, 4-ethylenedioxythiophene) nanotubes using PMMA nanofibers as templates using chemical vapor deposition, and the gas sensors prepared based thereon achieved a response of 10ppt scale to organic phosphors (Nano Letters,2012,12, (6): 2797.). Although the gas sensors based on the nano conductive polymers can realize real-time response of trace concentration to DMMP, the gas sensors still face the problem that high sensitivity and high selectivity are difficult to be compatible, for example, unfunctionalized polyaniline and monohydroxy functionalized poly (3, 4-ethylenedioxythiophene) have quite high sensitivity to DMMP, but the selectivity is often poor, particularly the gas sensors are very sensitive to water vapor and alcohol vapor in the air, cannot be applied to outdoor complex gas atmosphere, and easily have the side effect of false alarm, and are difficult to be widely applied, so that the development of chemical gas sensors with high sensitivity and high selectivity has received extensive attention.
Disclosure of Invention
In order to solve the problems, the invention discloses a chemical gas sensor and a preparation method thereof, and the prepared gas sensor has excellent comprehensive detection performance on organic phosphide, including high sensitivity and high gas selectivity.
In order to achieve the above object, the present invention provides a chemical gas sensor, characterized in that: the gas sensor comprises a conductive polymer sensitive film and an interdigital electrode substrate.
Preferably, the sensing principle of the gas sensor is an impedance real-time detection technology, the used voltage is 1mV-10V, the used voltage frequency is 0.1 Hz-1000000 Hz, and the use temperature is-30 ℃ to 60 ℃.
Preferably, the conductive polymer has the following structural formula (i):
wherein:
M1represents a monomer unit derived from a conductive polymer monomer N1. Conductive polymer monomer N1Has the following structural general formula (II):
wherein P is1Represents a main part in a monomer and is functionalized 3, 4-ethylenedioxythiopheneBody
Functionalized trimethylene dioxythiophene hosts
Functionalized pyrrole hosts
Any one of them.
R1Represents a group comprising C1-C12 alkylene or wherein 1to 3 alkyl groups are substituted by one or more-O-, -NH-, -C (O) -groups, -C (O) NH-groups, -C (O) O-groups, phenyl ring groups.
R2Represents a proton-donating functional group comprising hexafluoroisopropanol groups
Hexafluoroisopropanol aniline group
3, 5-bis-trifluoromethylphenol group
Any one of them.
M2Represents a copolymerized monomer unit derived from the monomer N of the conductive polymer2. Conductive polymer monomer N2Is 3, 4-ethylenedioxythiophene
Trimethylene dioxythiophene
Azole compounds
Any one of them.
m is a positive integer, and n is 0 or a positive integer.
Preferably, the interdigital electrode material of the interdigital electrode substrate comprises gold, platinum, aluminum, copper, iron and silver, and the interdigital distance is 0.5-50 microns.
Preferably, m: n in the structural general formula (I) is 100: 0-1: 99; in view of controlling the molecular weight and solubility of the polymer, m: n is more preferably 99: 1to 1: 3; and considering reducing the interaction of adjacent functional monomers, the m: n is most preferably 2: 1-1: 3.
Preferably, the conductive polymer monomer N1P in the general structural formula (II)1Is a functionalized 3, 4-ethylenedioxythiophene main body
Functionalized trimethylene dioxythiophene hosts
Functionalized pyrrole hosts
Any one of the above; the conductive polymer monomer N1P in the general structural formula (II)1More preferably a functionalized 3, 4-ethylenedioxythiophene host
Preferably, the conductive polymer monomer N1In the general structural formula (II)1Is an alkylene group of C1 to C12; considering the influence of the chain length of the side chain on the electron delocalization of the main chain of the polymer, the conductive polymer monomer N1In the general structural formula (II)1is-CH2-。
Preferably, the conductive polymer monomer N1In the general structural formula (II)2Is a hexafluoroisopropanol group
Hexafluoroisopropanol aniline group
3, 5-bis (trifluoromethyl) benzenePhenol group
Any one of the above; the conductive polymer monomer N1In the general structural formula (II)2Further preferred is a hexafluoroisopropanol group
Preferably, the conductive polymer monomer N2Is 3, 4-ethylenedioxythiophene
Trimethylene dioxythiophene
Azole compounds
Any one of the above; the conductive polymer monomer N2More preferably 3, 4-ethylenedioxythiophene
The invention also provides a preparation method of the chemical gas sensor, which is characterized by comprising the following steps: the method comprises the following steps:
step 1): dissolving a conductive polymer in a solvent to prepare a solution with a certain concentration;
step 2): coating the conductive polymer solution obtained in the step 1) on the surface of the interdigital electrode substrate treated by a specific process, and carrying out vacuum drying for 24 hours;
preferably, the method for manufacturing a chemical gas sensor is characterized in that: the solvent is any one or more mixed solvents of water, methanol, ethanol, isopropanol, acetone, N-dimethylformamide, acetonitrile, tetrahydrofuran, chloroform, toluene and N-hexane; the certain concentration is 1ug/ml to 50 mg/ml; the specific process is low-temperature plasma surface treatment; the vacuum drying temperature is 20-100 ℃.
Compared with the prior art, the chemical gas sensor prepared by the invention has the advantages of high sensitivity to organic phosphide and organic phosphide, good gas selectivity, normal-temperature real-time detection, extremely low sensing power consumption, excellent portability, simple preparation process, easy processing and low cost, and is a chemical gas sensor with great potential.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 optical photograph of conductive polymer I-1 coated interdigitated electrodes.
FIG. 2 scanning electron micrograph of gas sensor prepared by coating interdigital electrode with conducting polymer I-1: a) the shape of a flat membrane; b) the shape of the nano-dots; c) the shape of the nanochain; d) and (4) nano network morphology.
FIG. 3 shows the results of the sensitivity and selectivity test of the gas sensor prepared by coating the interdigital electrode with the conductive polymer I-1 to the organophosphorus compound dimethyl methylphosphonate at normal temperature.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below.
Experimental materials
Preparation of conductive polymer:
preparation A1
Adopting electrochemical polymerization, adding 225mg of functionalized conductive polymer monomer II-1(1mmol), 1.44g of sodium dodecyl sulfate (5mmol), 636mg of lithium chloride (15mmol) and 50ml of ultrapure water into an electrolytic tank, taking a gold electrode as a working electrode, Ag/AgCl as a reference electrode and a platinum electrode as a counter electrode, carrying out polymerization reaction for 60s in room-temperature air environment at a polymerization potential of 1.13V, collecting the polymer by using acetone, repeating the steps for many times, adding a proper amount of anhydrous magnesium sulfate into the polymer/acetone solution to remove water, filtering by using a 220 nm-aperture polytetrafluoroethylene membrane, and concentrating the rotary evaporation solution to 0.5 ml. And dropwise adding the concentrated solution into 40ml of chloroform, shaking, centrifuging, pouring out supernatant, adding chloroform, centrifuging, and repeating for multiple times. The dissolving-centrifuging process is repeated for 2-3 times, and the black precipitate is vacuum dried for 24 hours at normal temperature, so that 90mg of the functionalized conductive polymer I-1 is prepared.
Preparation A2
Adopting electrochemical polymerization, 188mg of functionalized conductive polymer monomer II-2(0.9mmol), 15mg of copolymerized conductive polymer monomer III-2(0.1mmol), 636mg of lithium chloride (15mmol) and 50ml of acetonitrile are added into an electrolytic bath, a gold electrode is taken as a working electrode, Ag is taken as a working electrode+And the polymerization reaction is carried out for 60s at room temperature and air environment by using the platinum electrode as a reference electrode and the polymerization potential as 1.25V, acetone is used for collecting the polymer, the steps are repeated for many times, a proper amount of anhydrous magnesium sulfate is added into the polymer/acetone solution for removing water, a polytetrafluoroethylene membrane with the aperture of 220nm is used for filtering, and the rotary evaporation solution is concentrated to 0.5 ml. And dropwise adding the concentrated solution into 40ml of chloroform, shaking, centrifuging, pouring out supernatant, adding chloroform, centrifuging, and repeating for multiple times. The dissolving-centrifuging process is repeated for 2-3 times, and the black precipitate is vacuum dried for 24 hours at normal temperature to prepare 105mg of the functionalized conductive polymer I-2.
Preparation A3
Adopting electrochemical polymerization, adding 176mg of functionalized conductive polymer monomer II-3(0.7mmol), 43mg of copolymerized conductive polymer monomer III-3(0.3mmol), 636mg of lithium chloride (15mmol) and 50ml of dichloromethane into an electrolytic bath, taking a gold electrode as a working electrode and Ag as a working electrode+And the polymerization reaction is carried out for 60s at room temperature and air environment by using the platinum electrode as a reference electrode and the polymerization potential of 1.23V, the polymer is collected by using acetone, the operation is repeated for many times, a proper amount of anhydrous magnesium sulfate is added into the polymer/acetone solution for removing water, a polytetrafluoroethylene membrane with the aperture of 220nm is filtered, and the rotary evaporation solution is concentrated to 0.5 ml. And dropwise adding the concentrated solution into 40ml of chloroform, shaking, centrifuging, pouring out supernatant, adding chloroform, centrifuging, and repeating for multiple times. The dissolving-centrifuging process is repeated for 2-3 times, and the black precipitate is vacuum dried for 24 hours at normal temperature, thus obtaining 95mg of the functionalized conductive polymer I-3.
Preparation A4
Adopting electrochemical polymerization, adding 161mg of functionalized conductive polymer monomer II-4(0.5mmol), 78mg of copolymerized conductive polymer monomer III-4(0.5mmol), 1.44g of sodium dodecyl sulfate (5mmol), 636mg of lithium chloride (15mmol) and 50ml of ultrapure water into an electrolytic bath, taking a gold electrode as a working electrode, Ag/AgCl as a reference electrode and a platinum electrode as a counter electrode, wherein the polymerization potential is 1.13V, carrying out polymerization reaction for 60s in an air environment at room temperature, collecting the polymer by using acetone, repeating for multiple times, adding a proper amount of anhydrous magnesium sulfate into a polymer/acetone solution to remove water, filtering by using a polytetrafluoroethylene membrane with a pore diameter of 220nm, and concentrating a rotary evaporation solution to 0.5 ml. And dropwise adding the concentrated solution into 40ml of chloroform, shaking, centrifuging, pouring out supernatant, adding chloroform, centrifuging, and repeating for multiple times. The dissolving-centrifuging process is repeated for 2-3 times, and the black precipitate is vacuum dried for 24 hours at normal temperature, so that 143mg of the functionalized conductive polymer I-4 is prepared.
Preparation A5
By adopting electrochemical polymerization, 90mg of functionalized conductive polymer monomer II-5(0.4mmol), 94mg of copolymerized conductive polymer monomer III-5(0.6mmol), 636mg of lithium chloride (15mmol) and 50ml of acetonitrile are added into an electrolytic bath, a gold electrode is taken as a working electrode, and Ag is taken as a working electrode+And the polymerization reaction is carried out for 60s at room temperature and air environment by using the platinum electrode as a reference electrode and the polymerization potential of 1.23V, the polymer is collected by using acetone, the operation is repeated for many times, a proper amount of anhydrous magnesium sulfate is added into the polymer/acetone solution for removing water, a polytetrafluoroethylene membrane with the aperture of 220nm is filtered, and the rotary evaporation solution is concentrated to 0.5 ml. And dropwise adding the concentrated solution into 40ml of chloroform, shaking, centrifuging, pouring out supernatant, adding chloroform, centrifuging, and repeating for multiple times. The dissolving-centrifuging process is repeated for 2-3 times, and the black precipitate is vacuum dried for 24 hours at normal temperature to prepare 121mg of the functionalized conductive polymer I-5.
Preparation A6
Adopting electrochemical polymerization, adding 61mg of functionalized conductive polymer monomer II-6(0.4mmol), 85mg of copolymerized conductive polymer monomer III-6(0.6mmol), 636mg of lithium chloride (15mmol) and 50ml of dichloromethane into an electrolytic bath, taking a gold electrode as a working electrode and Ag as a working electrode+Ag as reference electrode, platinum electrode as counter electrode, polymerization potential of 1.26V, polymerization reaction for 60s in room temperature air environment, collecting polymer with acetone, and weighingRepeating the steps for many times, adding a proper amount of anhydrous magnesium sulfate into the polymer/acetone solution to remove water, filtering by using a polytetrafluoroethylene membrane with the aperture of 220nm, and concentrating the rotary evaporation solution to 0.5 ml. And dropwise adding the concentrated solution into 40ml of chloroform, shaking, centrifuging, pouring out supernatant, adding chloroform, centrifuging, and repeating for multiple times. The dissolving-centrifuging process is repeated for 2-3 times, and the black precipitate is vacuum dried for 24 hours at normal temperature, thus obtaining 81mg of the functionalized conductive polymer I-6.
Preparation A7
By adopting electrochemical polymerization, 70mg of functionalized conductive polymer monomer II-7(0.3mmol), 47mg of copolymerized conductive polymer monomer III-7(0.7mmol), 636mg of lithium chloride (15mmol) and 50ml of dichloromethane are added into an electrolytic bath, a gold electrode is taken as a working electrode, and Ag is taken as a working electrode+And the polymerization reaction is carried out for 60s at room temperature and air environment by using the platinum electrode as a reference electrode and the polymerization potential as 1.24V, acetone is used for collecting the polymer, the steps are repeated for many times, a proper amount of anhydrous magnesium sulfate is added into the polymer/acetone solution for removing water, a polytetrafluoroethylene membrane with the aperture of 220nm is used for filtering, and the rotary evaporation solution is concentrated to 0.5 ml. And dropwise adding the concentrated solution into 40ml of chloroform, shaking, centrifuging, pouring out supernatant, adding chloroform, centrifuging, and repeating for multiple times. The dissolving-centrifuging process is repeated for 2-3 times, and the black precipitate is vacuum dried for 24 hours at normal temperature to prepare 56mg of the functionalized conductive polymer I-7.
Preparation A8
Adopting solution oxidation polymerization, adding 216mg of anhydrous ferric chloride (1.33mol) and 5ml of anhydrous chloroform into a reaction stolen bottle, ultrasonically dispersing for 2h under 50w of power, placing at normal temperature, adding 275mg of functionalized conductive polymer monomer II-8(0.9mmol) and 6.7mg of copolymerized conductive polymer monomer III-8(0.1mmol), and stirring for polymerization reaction for 24h under the nitrogen environment at room temperature. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing filter residues by using methanol, ultrapure water, isopropanol and chloroform, and drying the black filter residues for 24 hours at normal temperature in vacuum to obtain 184mg of the functionalized conductive polymer I-8.
Preparation A9
Adopting solution oxidation polymerization, adding 216mg of anhydrous ferric chloride (1.33mol) and 5ml of anhydrous chloroform into a reaction stolen bottle, ultrasonically dispersing for 2h under 50w of power, placing at normal temperature, adding 275mg of functionalized conductive polymer monomer II-9(0.6mmol) and 6.7mg of copolymerized conductive polymer monomer III-9(0.4mmol), and stirring for polymerization reaction for 24h under the nitrogen environment at room temperature. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing filter residues by using methanol, ultrapure water, isopropanol and chloroform, and drying the black filter residues for 24 hours at normal temperature in vacuum to obtain 184mg of the functionalized conductive polymer I-9.
Preparation A10
Adopting solution oxidation polymerization, adding 216mg of anhydrous ferric chloride (1.33mol) and 5ml of anhydrous chloroform into a reaction stolen bottle, ultrasonically dispersing for 2h under 50w of power, placing at normal temperature, adding 206mg of functionalized conductive polymer monomer II-10(0.5mmol) and 71mg of copolymerized conductive polymer monomer III-10(0.5mmol), and stirring for polymerization reaction for 24h under the nitrogen environment at room temperature. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing filter residues by using methanol, ultrapure water, isopropanol and chloroform, and drying the black filter residues for 24 hours at normal temperature in vacuum to obtain 135mg of the functionalized conductive polymer I-10.
Preparation A11
Adopting solution oxidation polymerization, adding 216mg of anhydrous ferric chloride (1.33mol) and 5ml of anhydrous chloroform into a reaction stolen bottle, ultrasonically dispersing for 2h under 50w of power, placing at normal temperature, adding 173mg of functionalized conductive polymer monomer II-11(0.45mmol) and 86mg of copolymerized conductive polymer monomer III-11(0.55mmol), and stirring for polymerization reaction for 24h under the nitrogen environment at room temperature. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing filter residues by using methanol, ultrapure water, isopropanol and chloroform, and drying the black filter residues for 24 hours at normal temperature in vacuum to obtain 165mg of the functionalized conductive polymer I-11.
Preparation A12
Adopting solution oxidation polymerization, adding 216mg of anhydrous ferric chloride (1.33mol) and 5ml of anhydrous chloroform into a reaction stolen bottle, ultrasonically dispersing for 2h under 50w of power, placing at normal temperature, adding 177mg of functionalized conductive polymer monomer II-12(0.4mmol) and 94mg of copolymerized conductive polymer monomer III-12(0.6mmol), and stirring for polymerization reaction for 24h under the nitrogen environment at room temperature. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing filter residues by using methanol, ultrapure water, isopropanol and chloroform, and drying the black filter residues for 24 hours at normal temperature in vacuum to obtain 182mg of the functionalized conductive polymer I-12.
Preparation A13
Adopting solution oxidation polymerization, adding 144mg iodine (1.33mol) and 5ml toluene into a reaction stolen bottle, performing ultrasonic dispersion for 2h under 50w of power, placing at normal temperature, adding 148mg of functionalized conductive polymer monomer II-13(0.5mmol) and 34mg of copolymerized conductive polymer monomer III-13(0.5mmol), and stirring and polymerizing for 24h under the nitrogen environment at 80 ℃. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing filter residues by using methanol, ultrapure water, isopropanol and chloroform, and drying black filter residues for 24 hours at normal temperature in vacuum to obtain 97mg of the functionalized conductive polymer I-13.
Preparation A14
Adopting solution oxidation polymerization, adding 144mg iodine (1.33mol) and 5ml toluene into a reaction stolen bottle, performing ultrasonic dispersion for 2h under 50w of power, placing at normal temperature, adding 194mg of functionalized conductive polymer monomer II-14(0.6mmol) and 27mg of copolymerized conductive polymer monomer III-14(0.4mmol), and stirring and polymerizing for 24h under the nitrogen environment at 90 ℃. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing filter residues by using methanol, ultrapure water, isopropanol and chloroform, and drying the black filter residues for 24 hours at normal temperature in vacuum to obtain 110mg of the functionalized conductive polymer I-14.
Preparation A15
Adopting solution oxidation polymerization, adding 144mg iodine (1.33mol) and 5ml toluene into a reaction stolen bottle, ultrasonically dispersing for 2h under 50w of power, placing at normal temperature, adding 269mg of functionalized conductive polymer monomer II-15(0.7mmol) and 43mg of copolymerized conductive polymer monomer III-15(0.3mmol), and stirring for polymerization reaction for 24h under the nitrogen environment at 100 ℃. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing filter residues by using methanol, ultrapure water, isopropanol and chloroform, and drying the black filter residues for 24 hours at normal temperature in vacuum to obtain 213mg of the functionalized conductive polymer I-15.
Preparation A16
By adopting vapor deposition polymerization, 144mg of iodine (1.33mol) and 414mg of functionalized conductive polymer monomer II-16(1mmol) are added into a reaction stolen bottle, and polymerization reaction is carried out for 5 hours under the nitrogen environment at 50 ℃ and the gas pressure of 760 Torr. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing the filter residue by using methanol, ultrapure water, isopropanol and chloroform, and vacuum-drying the black filter residue for 24 hours at normal temperature to obtain 243mg of the functionalized conductive polymer I-16.
Preparation A17
By vapor deposition polymerization, 144mg of iodine (1.33mol), 159mg of the functionalized conductive polymer monomer II-17(0.4mmol) and 85mg of the copolymerized conductive polymer monomer III-17(0.6mmol) were added to a reaction flask, and polymerization was carried out for 5 hours at 50 ℃ under a nitrogen atmosphere and a gas pressure of 760 Torr. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing filter residues by using methanol, ultrapure water, isopropanol and chloroform, and drying the black filter residues for 24 hours at normal temperature in vacuum to obtain 112mg of the functionalized conductive polymer I-17.
Preparation A18
By vapor deposition polymerization, 144mg of iodine (1.33mol), 237mg of the functionalized conductive polymer monomer II-18(0.5mmol) and 78mg of the copolymerized conductive polymer monomer III-18(0.5mmol) were added to a reaction flask, and polymerization was carried out for 5 hours at 90 ℃ under a nitrogen atmosphere and a gas pressure of 760 Torr. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing filter residues by using methanol, ultrapure water, isopropanol and chloroform, and drying the black filter residues for 24 hours at normal temperature in vacuum to obtain 156mg of the functionalized conductive polymer I-18.
Preparation A19
By vapor deposition polymerization, 144mg of iodine (1.33mol), 155mg of the functionalized conductive polymer monomer II-19(0.5mmol) and 34mg of the copolymerized conductive polymer monomer III-19(0.5mmol) were added to a reaction flask, and polymerization was carried out at 90 ℃ under a nitrogen atmosphere and a gas pressure of 1Torr for 5 hours. Filtering the reaction solution by using a 220nm polytetrafluoroethylene microporous filter membrane, respectively washing filter residues by using methanol, ultrapure water, isopropanol and chloroform, and drying the black filter residues for 24 hours at normal temperature in vacuum to obtain 88mg of the functionalized conductive polymer I-19.
The monomers and structural formulas used in preparation examples 1-19 are shown in Table 1.
TABLE 1
Preparation examples 1to 19 the reaction conditions and the molar ratio of the units II to III in the product are shown in Table 2. Table 2:
chemical sensor preparation example:
example 1
The electroconductive polymer I-1 was dissolved in acetone to adjust the concentration to 4 mg/ml. A conductive polymer I-1 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of low-temperature plasma for 10 minutes at 400w by using a spin coating method, the rotating speed is controlled to be 6000rpm, the duration is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 25nm, the surface appearance is a nano-dot appearance, and the resistance of the sensor is 35 kilo-ohm. The gas sensor has a minimum detection concentration of 25ppb for the organophosphorus compound dimethyl methylphosphonate at 25 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 21 times of the response value to water vapor.
Example 2
The electroconductive polymer I-2 was dissolved in acetone to adjust the concentration to 4 mg/ml. A conductive polymer I-2 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of low-temperature plasma for 10 minutes at 400w by using a spin coating method, the rotating speed is controlled to be 3000rpm, the duration is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 23nm, the surface appearance is a nano-dot appearance, and the resistance of the sensor is 30 kilo-ohm. The gas sensor has a minimum detection concentration of 30ppb for the organophosphorus compound dimethyl methylphosphonate at 25 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 19 times of the response value to water vapor.
Example 3
The electroconductive polymer I-3 was dissolved in acetone to adjust the concentration to 4 mg/ml. A conductive polymer I-3 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of a low-temperature plasma for 10 minutes at 200w by using a spin coating method, the rotating speed is controlled to be 6000rpm, the duration is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 20nm, the surface appearance is a nano-dot appearance, and the resistance of the sensor is 40 kilo-ohm. The gas sensor has a minimum detection concentration of 32ppb for the organophosphorus compound dimethyl methylphosphonate at 25 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 18 times of the response value to water vapor.
Example 4
The electroconductive polymer I-4 was dissolved in acetone to adjust the concentration to 4 mg/ml. A conductive polymer I-4 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of low-temperature plasma for 5 minutes at 200w by using a spin coating method, the rotating speed is controlled to be 6000rpm, the duration is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 30nm, the surface appearance is a nano-dot appearance, and the resistance of the sensor is 31 kilo-ohm. The gas sensor has a minimum detection concentration of 50ppb for the organophosphorus compound dimethyl methylphosphonate at 40 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 40 ℃ under the same concentration of 1% saturated steam is 23 times of that to water vapor.
Example 5
The electroconductive polymer I-5 was dissolved in acetone to adjust the concentration to 4 mg/ml. A conductive polymer I-5 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of a low-temperature plasma by 100w for 5 minutes by using a spin coating method, the rotating speed is controlled to be 3000rpm, the duration is 90 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 31nm, the surface appearance is a nano-dot appearance, and the resistance of the sensor is 42 kilo-ohm. The gas sensor has a minimum detection concentration of 60ppb for the organophosphorus compound dimethyl methylphosphonate at 50 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 50 ℃ under the same concentration of 1% saturated steam is 20 times of that to water vapor.
Example 6
The electroconductive polymer I-6 was dissolved in acetone to adjust the concentration to 4 mg/ml. A conductive polymer I-6 sensitive film is prepared on a gold interdigital electrode without treatment (3um interdigital distance) by using a spin coating method, the rotating speed is controlled to be 3000rpm, the duration time is controlled to be 90 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at the temperature of 25 ℃. The thickness of the polymer film of the gas sensor is 27nm, the surface appearance is flat film appearance, and the sensor resistance is 36 kilo ohm. The gas sensor has a minimum detection concentration of 64ppb for the organophosphorus compound dimethyl methylphosphonate at 50 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 50 ℃ under the same concentration of 1% saturated steam is 15 times of the response value to water vapor.
Example 7
The electroconductive polymer I-7 was dissolved in acetone to adjust the concentration to 6.8 mg/ml. A conductive polymer I-7 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of low-temperature plasma for 10 minutes at 400w by using a spin coating method, the rotating speed is controlled to be 6000rpm, the duration is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 50nm, the surface appearance is a nano-chain appearance, and the resistance of the sensor is 25 kilo ohms. The gas sensor has a minimum detection concentration of 34ppb for the organophosphorus compound dimethyl methylphosphonate at 25 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 18 times of the response value to water vapor.
Example 8
The electroconductive polymer I-8 was dissolved in acetone to adjust the concentration to 6.8 mg/ml. A conductive polymer I-8 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of low-temperature plasma for 10 minutes at 400w by using a spin coating method, the rotating speed is controlled to be 6000rpm, the duration is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 63nm, the surface appearance is a nano-chain appearance, and the resistance of the sensor is 25 kilo ohms. The gas sensor has a minimum detection concentration of 40ppb for the organophosphorus compound dimethyl methylphosphonate at 25 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 13 times of the response value to water vapor.
Example 9
The electroconductive polymer I-9 was dissolved in acetone to adjust the concentration to 6.8 mg/ml. A conductive polymer I-9 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of a low-temperature plasma for 10 minutes at 200w by using a spin coating method, the rotating speed is controlled to be 6000rpm, the duration is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 72nm, the surface appearance is a nano-chain appearance, and the resistance of the sensor is 24 kilo ohms. The gas sensor has a minimum detection concentration of 42ppb for the organophosphorus compound dimethyl methylphosphonate at 25 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 22 times of that to water vapor.
Example 10
The electroconductive polymer I-10 was dissolved in acetone to adjust the concentration to 6.8 mg/ml. A conductive polymer I-10 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of a low-temperature plasma by 100w for 5 minutes by using a spin coating method, the rotating speed is controlled to be 6000rpm, the duration is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 62nm, the surface appearance is a nano-chain appearance, and the sensor resistance is 28 kilo ohms. The gas sensor has a minimum detection concentration of 50ppb for the organophosphorus compound dimethyl methylphosphonate at 25 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 18 times of the response value to water vapor.
Example 11
The electroconductive polymer I-11 was dissolved in acetone to adjust the concentration to 6.8 mg/ml. A conductive polymer I-11 sensitive film is prepared on a gold interdigital electrode without treatment (3um interdigital distance) by using a spin coating method, the rotating speed is controlled to be 4000rpm, the duration time is 90 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at the temperature of 25 ℃. The thickness of the polymer film of the gas sensor is 59nm, the surface appearance is flat film appearance, and the sensor resistance is 23 kilo ohm. The lowest detection concentration of the gas sensor to the organophosphorus compound methyl phosphonic acid dimethyl ester at 25 ℃ is 63 ppb. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 12 times of that to water vapor.
Example 12
The electroconductive polymer I-12 was dissolved in acetone to adjust the concentration to 8 mg/ml. A conductive polymer I-12 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of low-temperature plasma for 10 minutes at 400w by using a spin coating method, the rotating speed is controlled to be 3000rpm, the duration is 90 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 80nm, the surface appearance is a nano-chain appearance, and the resistance of the sensor is 14 kilo ohms. The gas sensor has a minimum detection concentration of 70ppb for the organophosphorus compound dimethyl methylphosphonate at 25 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 17 times of the response value to water vapor.
Example 13
The electroconductive polymer I-13 was dissolved in methanol to adjust the concentration to 8 mg/ml. A conductive polymer I-13 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of a low-temperature plasma for 10 minutes at 200w by using a spin coating method, the rotating speed is controlled to be 2000rpm, the duration is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 82nm, the surface appearance is a nano-chain appearance, and the resistance of the sensor is 13 kilo-ohms. The gas sensor has a minimum detection concentration of 75ppb for the organophosphorus compound dimethyl methylphosphonate at 40 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 40 ℃ under the same concentration of 1% saturated steam is 19 times of the response value to water vapor.
Example 14
The electroconductive polymer I-14 was dissolved in methanol to adjust the concentration to 8 mg/ml. A conductive polymer I-14 sensitive film is prepared on a gold interdigital electrode (3um interdigital spacing) processed on the surface of a low-temperature plasma by 100w for 10 minutes by using a spin coating method, the rotating speed is controlled to be 4000rpm, the duration is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 86nm, the surface appearance is a nano-chain appearance, and the resistance of the sensor is 16 kilo ohms. The gas sensor has a minimum detection concentration of 80ppb for the organophosphorus compound dimethyl methylphosphonate at 50 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 50 ℃ under the same concentration of 1% saturated steam is 16 times of that to water vapor.
Example 15
The electroconductive polymer I-15 was dissolved in methanol to adjust the concentration to 8 mg/ml. A conductive polymer I-15 sensitive film is prepared on a gold interdigital electrode without treatment (3um interdigital distance) by using a spin coating method, wherein the rotating speed is controlled to be 6000rpm, the duration time is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at the temperature of 25 ℃. The thickness of the polymer film of the gas sensor is 82nm, the surface appearance is flat film appearance, and the sensor resistance is 18 kilo ohms. The gas sensor has a minimum detection concentration of 73ppb for the organophosphorus compound dimethyl methylphosphonate at 50 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 50 ℃ under the same concentration of 1% saturated steam is 21 times of the response value to water vapor.
Example 16
The electroconductive polymer I-16 was dissolved in methanol to adjust the concentration to 8 mg/ml. A conductive polymer I-16 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of low-temperature plasma for 5 minutes at 400w by using a spin coating method, the rotating speed is controlled to be 6000rpm, the duration is 60 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 121nm, the surface appearance is a nano-chain appearance, and the resistance of the sensor is 6 kilo-ohms. The lowest detection concentration of the gas sensor to the organophosphorus compound methyl phosphonic acid dimethyl ester at 25 ℃ is 88 ppb. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 19 times of the response value to water vapor.
Example 17
The conductive polymer I-17 was dissolved in acetonitrile and adjusted to a concentration of 10 mg/ml. A conductive polymer I-17 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of a low-temperature plasma for 10 minutes at 200w by using a spin coating method, the rotating speed is controlled to be 6000rpm, the duration is 90 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of the polymer film of the gas sensor is 112nm, the surface appearance is the appearance of a nano network, and the resistance of the sensor is 5.7 kilo ohms. The gas sensor has a minimum detection concentration of 90ppb for the organophosphorus compound dimethyl methylphosphonate at 25 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 17 times of the response value to water vapor.
Example 18
The electroconductive polymer I-18 was dissolved in N, N-dimethylformamide to adjust the concentration to 10 mg/ml. A conductive polymer I-18 sensitive film is prepared on a gold interdigital electrode (3um interdigital distance) processed on the surface of a low-temperature plasma by 100w for 10 minutes by using a spin coating method, the rotating speed is controlled to be 5000rpm, the duration is 90 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at 25 ℃. The thickness of a polymer film of the gas sensor is 120nm, the surface appearance is a nano network appearance, and the resistance of the sensor is 7.2 kilo ohms. The gas sensor has a minimum detection concentration of 95ppb for the organophosphorus compound dimethyl methylphosphonate at 25 ℃. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 16 times of that to water vapor.
Example 19
The electroconductive polymer I-19 was dissolved in tetrahydrofuran to adjust the concentration to 10 mg/ml. A conductive polymer I-19 sensitive film is prepared on a gold interdigital electrode without treatment (3um interdigital distance) by using a spin coating method, the rotating speed is controlled to be 4000rpm, the duration time is 90 seconds, the spin coating temperature is 25 ℃, and then vacuum drying is carried out for 24 hours at the temperature of 25 ℃. The thickness of the polymer film of the gas sensor is 108nm, the surface appearance is flat film appearance, and the resistance of the sensor is 5.4 kilo ohm. The lowest detection concentration of the gas sensor to the organophosphorus compound methyl phosphonic acid dimethyl ester at 25 ℃ is 100 ppb. The response value of the gas sensor to dimethyl methylphosphonate at 25 ℃ under the same concentration of 1% saturated steam is 18 times of the response value to water vapor.
Claims (9)
1. A chemical gas sensor, characterized by: the conductive polymer sensitive film and the interdigital electrode substrate are contained;
the conductive polymer has a general structural formula shown in a formula (I):
wherein:
M1represents a monomer unit derived from a conductive polymer monomer N1(ii) a Conductive polymer monomer N1Has the following structural general formula (II):
wherein P is1Represents a main body part in a monomer and is a functionalized 3, 4-ethylenedioxythiophene main body
Functionalized trimethylene dioxythiophene hosts
Functionalized pyrrole hosts
Any one of the above;
R1represents a group comprising C1-C12 alkylene or wherein 1to 3 alkyl groups are substituted by one or more-O-, -NH-, -C (O) -groups, -C (O) NH-groups, -C (O) O-groups, phenyl ring groups;
R2represents a proton-donating functional group comprising hexafluoroisopropanol groups
Hexafluoroisopropanol aniline group
3, 5-bis-trifluoromethylphenol group
Any one of the above;
M2represents a copolymerized monomer unit derived from the monomer N of the conductive polymer2(ii) a Conductive polymer monomer N2Is 3, 4-ethylenedioxythiophene
Trimethylene dioxythiophene
Azole compounds
Any one of the above;
m is a positive integer, and n is 0 or a positive integer.
2. A chemical gas sensor according to claim 1, wherein: the sensing principle of the gas sensor is an impedance real-time detection technology, the used voltage is 1mV-10V, and the used voltage frequency is 0.1 Hz-1000000 Hz.
3. A chemical gas sensor according to claim 1, wherein: the use temperature of the gas sensor is-30 ℃ to 60 ℃.
4. A chemical gas sensor according to claim 1, wherein: the interdigital electrode material of the interdigital electrode substrate comprises gold, platinum, aluminum, copper, iron and silver, and the interdigital distance is 0.5-50 microns.
5. A chemical gas sensor according to claim 1, wherein: in the general structural formula (I) of the conductive polymer, m: n is 100: 0-1: 99.
6. A chemical gas sensor according to claim 1, wherein: the conductive polymer monomer N1P in the general structural formula (II)1Is a functionalized 3, 4-ethylenedioxythiophene main body
7. A chemical gas sensor according to claim 1, wherein: the conductive polymer monomer N1In the general structural formula (II)1is-CH2-。
8. A chemical gas sensor according to claim 1, wherein: the conductive polymer monomer N1In the general structural formula (II)2Is a hexafluoroisopropanol group
9. A method for producing a chemical gas sensor according to any one of claims 1to 8, characterized in that: the method comprises the following steps:
step 1): dissolving a conductive polymer in any one or more mixed solvents of water, methanol, ethanol, isopropanol, acetone, N-dimethylformamide, acetonitrile, tetrahydrofuran, chloroform, toluene and N-hexane to prepare a solution with the concentration of 1ug/ml to 50 mg/ml;
step 2): coating the conductive polymer solution obtained in the step 1) on the surface of the interdigital electrode substrate which is treated or not treated by the low-temperature plasma, and drying for 24 hours in vacuum at the temperature of 20-100 ℃.
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