CN117467226A - Composition, sensing film, sensor, preparation method and application - Google Patents
Composition, sensing film, sensor, preparation method and application Download PDFInfo
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- CN117467226A CN117467226A CN202311823705.9A CN202311823705A CN117467226A CN 117467226 A CN117467226 A CN 117467226A CN 202311823705 A CN202311823705 A CN 202311823705A CN 117467226 A CN117467226 A CN 117467226A
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- sensor
- carbon nanotube
- polymer
- polyvinylbenzyl
- vinylbenzyl
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- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 61
- -1 tetrafluoroborate ion Chemical class 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 45
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 45
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 150000001450 anions Chemical class 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 7
- 150000001768 cations Chemical class 0.000 claims abstract description 5
- 239000002079 double walled nanotube Substances 0.000 claims abstract description 4
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 4
- MCMFEZDRQOJKMN-UHFFFAOYSA-N 1-butylimidazole Chemical compound CCCCN1C=CN=C1 MCMFEZDRQOJKMN-UHFFFAOYSA-N 0.000 claims abstract description 3
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 claims abstract description 3
- KGWVFQAPOGAVRF-UHFFFAOYSA-N 1-hexylimidazole Chemical compound CCCCCCN1C=CN=C1 KGWVFQAPOGAVRF-UHFFFAOYSA-N 0.000 claims abstract description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 claims abstract description 3
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical compound CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 238000000935 solvent evaporation Methods 0.000 claims 1
- 235000010269 sulphur dioxide Nutrition 0.000 claims 1
- 239000004291 sulphur dioxide Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 17
- 239000010408 film Substances 0.000 description 44
- 239000002608 ionic liquid Substances 0.000 description 39
- 239000000243 solution Substances 0.000 description 32
- 239000007789 gas Substances 0.000 description 31
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 239000000178 monomer Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 12
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000002238 carbon nanotube film Substances 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- DOVIZUBCLACUJT-UHFFFAOYSA-M 1-[(4-ethenylphenyl)methyl]-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].C1=[N+](C)C=CN1CC1=CC=C(C=C)C=C1 DOVIZUBCLACUJT-UHFFFAOYSA-M 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000001548 drop coating Methods 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 238000002798 spectrophotometry method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- OQICTMBBVJYHIR-UHFFFAOYSA-N [Cl].C(C1=CC=CC=C1)N1CN(C=C1)C Chemical compound [Cl].C(C1=CC=CC=C1)N1CN(C=C1)C OQICTMBBVJYHIR-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HBCNUSPKBMKRLV-UHFFFAOYSA-N 3-benzyl-1-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].C1=CN(C)C[NH+]1CC1=CC=CC=C1 HBCNUSPKBMKRLV-UHFFFAOYSA-N 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000007480 spreading Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000005463 sulfonylimide group Chemical group 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- KBRGFKHUFKDZIU-UHFFFAOYSA-N 1-[(4-ethenylphenyl)methyl]-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].C1=CN(C)C[NH+]1CC1=CC=C(C=C)C=C1 KBRGFKHUFKDZIU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-MICDWDOJSA-N 1-deuteriopropan-2-one Chemical compound [2H]CC(C)=O CSCPPACGZOOCGX-MICDWDOJSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BRJOSKVWCIARTJ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide 1-butyl-3-[(4-ethenylphenyl)methyl]imidazol-3-ium Chemical compound FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.CCCCn1cc[n+](Cc2ccc(C=C)cc2)c1 BRJOSKVWCIARTJ-UHFFFAOYSA-N 0.000 description 2
- NNTOJPXOCKCMKR-UHFFFAOYSA-N boron;pyridine Chemical compound [B].C1=CC=NC=C1 NNTOJPXOCKCMKR-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- ZHBVYEFSLQQVFQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide 1-[(4-ethenylphenyl)methyl]-3-methylimidazol-3-ium Chemical compound FC(S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F)(F)F.C[N+]1=CN(C=C1)CC1=CC=C(C=C1)C=C ZHBVYEFSLQQVFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229960002523 mercuric chloride Drugs 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention relates to the field of sensing detection, in particular to a composition for a sensing film, the sensing film, a sensor, a preparation method and application, wherein the composition comprises a composite polymer and a carbon nano tube; the cation of the polymer is at least one of polyvinylbenzyl 3-methylimidazolium, polyvinylbenzyl 3-ethylimidazolium, polyvinylbenzyl 3-propylimidazolium, polyvinylbenzyl 3-butylimidazolium and polyvinylbenzyl 3-hexylimidazolium; the anion of the polymer is at least one of chloride ion, tetrafluoroborate ion, hexafluorophosphate ion and bistrifluoromethane sulfonyl imide ion; the carbon nanotube is at least one of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube. The composition and the sensing film obtained by the invention can improve the durability of the sulfur dioxide sensor and prolong the service life of the sulfur dioxide sensor.
Description
Technical Field
The invention relates to the field of sensing detection, in particular to a composition for a sensing film, the sensing film, a sensor, a preparation method and application; in particular to a sensor for detecting the sulfur dioxide content in air, a related composition, a sensing film, a preparation method and the like thereof.
Background
Sulfur dioxide is a common pollutant hazard in workplace air. The traditional sulfur dioxide collecting method is a solution absorbing method, and according to different selected absorbing solutions, the subsequent adopted analysis methods comprise spectrophotometry, electrochemical method, chromatography, chemiluminescence method, capillary electrophoresis and the like, and various analysis methods have long, but the analysis methods need to be tested by using a large chemical detection instrument.
The national occupational health standard detection method is formaldehyde buffer solution, pararosaniline hydrochloride spectrophotometry and potassium mercuric chloride, pararosaniline hydrochloride spectrophotometry. Although the two detection methods are accurate and reliable; however, in the detection process, highly toxic chemicals such as mercury chloride and formaldehyde with high toxicity are required, an absorption liquid is required to be used for sample collection, and then the sample is brought back to a laboratory for spectrophotometry analysis, so that the requirements on time and temperature are strict in the color development process, and when the number of samples is large, the spectrophotometry is difficult to reach the quality requirement, and the operation is complex and the efficiency is low.
Therefore, the existing gas sensor is an effective method for detecting sulfur dioxide in real time. For conventional metal oxide semiconductor chemiresistor sensors, it is difficult to distinguish common gases, such as SO, by themselves 2 With NO 2 The specificity is not strong to hardly carry out work under room temperature, lead to its sensor self consumption to be high, be difficult to match the demand of thing networking real-time supervision. SO for commercial use at present 2 Sensor, mainly SO from alpha sense company in UK 2 BF Sulfur dioxide sensor, FECS43-20 of Figaro Co., japan, gas sensor for detecting sulfur dioxide, SO 2 The detection limit of the BF sulfur dioxide sensor is 20ppm, and the SO is detected by the FECS43-20 gas sensor 2 The detection limit of (2) was 0.5ppm. At present for SO 2 It is still difficult to realize a detection sensor for sub ppb SO 2 Is detected.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the technical problem to be solved by the present invention is to improve the durability and prolong the service life of the sulfur dioxide sensor.
In order to achieve the above object, the present invention adopts a technical scheme that a composition is provided for a sensing film, which comprises a composite polymer and carbon nanotubes;
the cation of the polymer is at least one of polyvinylbenzyl 3-methylimidazolium, polyvinylbenzyl 3-ethylimidazolium, polyvinylbenzyl 3-propylimidazolium, polyvinylbenzyl 3-butylimidazolium and polyvinylbenzyl 3-hexylimidazolium;
the anion of the polymer is at least one of chloride ion, tetrafluoroborate ion, hexafluorophosphate ion and bistrifluoromethane sulfonyl imide ion;
the carbon nanotube is at least one of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube.
Optionally, the molar ratio of cations to anions in the polymer is 1:1.
Optionally, the mass ratio of the polymer to the carbon nanotubes is 10:1-1:1.
Optionally, the mass ratio of the polymer to the carbon nanotubes is 5:1.
The application also provides a second scheme, namely a sensing film prepared from the composition.
The application also provides a third scheme and a preparation method of the sensing film, wherein the preparation method comprises the steps of preparing a precursor solution of a polymer and carbon nano tube compound, coating the precursor solution, and volatilizing the solvent to obtain the sensing film.
Optionally, the solvent is at least one of toluene, xylene, chlorobenzene, dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone.
The present application also provides a fourth solution, namely a sensor comprising the aforementioned sensing film.
The application also provides a fifth scheme, namely a preparation method of the sensor, which comprises the steps of coating the precursor solution of the prepared polymer and carbon nano tube compound on the surface of a sensor device, and obtaining the sensor after the solvent volatilizes.
The application also provides a sixth scheme, namely application of the sensor, wherein the sensor can detect sulfur dioxide gas molecules in the air.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the composition of the sensing film of the sensor after the specific carbon nano tube and the specific polymer are compounded can be used for effectively modifying the carbon nano tube, and meanwhile, the obtained composite material has specific recognition and selectivity to sulfur dioxide, so that the detection sensitivity is improved. The application utilizes specific polymers to be compounded with the carbon nano tube in a non-covalent interaction manner to form a chemiresistance sensing film layer, utilizes an electrode sensing device to construct a chemiresistance gas sensor for efficiently sensing sulfur dioxide, and can only be used for SO 2 Has good specificity sensing. Compared with the traditional electrochemical gas sensor utilizing ionic liquid, the chemiresistor sensor directly takes a polymer and carbon nano tube composite product as a sensitive material, the polymer and the carbon nano tube are well combined, the obtained composite is not easy to be interfered by other gases, and the action environment is not limited by other restrictions. Therefore, the sensor obtained by the application is little affected by the environment (shown in the figure 25), the detection limit (shown in the figures 21-24) and the durability are improved, and the service life is prolonged (shown in the figure 29).
Drawings
FIG. 1 is a synthetic monomer 1- (4-vinylbenzyl) -3-alkylimidazolium chloride at D 2 Nuclear magnetic hydrogen spectrum of O. Nuclear magnetic 1H NMR (600 MHz, deuterium Oxide) delta 7.52 (d, j=7.9 Hz, 1H), 7.42 (q, j=2.1 Hz, 1H), 7.36 (d, j=7.8 Hz, 1H), 6.76 (dd, j=17.7, 10.9 Hz, 1H), 5.86 (d, j=17.7 Hz, 1H), 5.45-5.24 (m, 2H), 3.86 (s, 1H);
FIG. 2 is poly (1-methyl-3- (4-vinylbenzyl) imidazolium chloride) in DMSO-d6, nuclear magnetic 1H NMR (500 MHz, DMSO-d 6) delta 10.06 (s, 1H), 8.08 (s, 1H), 7.80 (s, 1H), 7.38 (s, 2H), 6.34 (s, 2H), 5.57 (s, 2H), 3.84 (s, 3H), 1.96-0.79 (m, 3H);
FIG. 3 is a GPC image of poly (1-methyl-3- (4-vinylbenzyl) imidazolium chloride), as shown: the horizontal axis is the molecular weight, and the arrangement is from small to large; the ordinate is divided into left and right sides, the left side represents the signal intensity of each molecular weight of the signal, the higher represents the more molecules of the molecular weight, the right side represents the accumulated integral result, namely a curve gradually rising from 0% to 100% in the graph, which is called an accumulated integral curve, and the ratio of molecules in any molecular weight interval in the total molecules can be estimated directly in the graph by using the accumulated integral curve; mn=6390, mw=20902, mp= 19866, mz=38900;
FIG. 4 is a nuclear magnetic resonance spectrum of the synthetic monomer 1- (p-vinylbenzyl) -3-methylimidazolium tetrafluoroborate in dimethyl sulfoxide-d 6. Nuclear magnetic 1H NMR (600 MHz, DMSO-d 6) δ9.29 (d, j=18.9 Hz, 1H), 7.76 (dt, j=47.2, 2.0 Hz, 3H), 7.41 (d, j=8.0 Hz, 3H), 6.74 (dd, j=17.6, 10.9 Hz, 1H), 5.42 (s, 2H), 5.30 (d, j=10.9 Hz, 1H), 3.35 (s, 4H), 2.50 (p, j=1.8 Hz, 3H);
FIG. 5 is a diagram of poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate ] in DMSO-d6, nuclear magnetic 1H NMR (500 MHz, DMSO-d 6) delta 9.08 (s, 1H), 7.72-7.34 (m, 2H), 7.08 (s, 2H), 6.49 (d, J=58.9 Hz, 2H), 5.26 (d, J=28.5 Hz, 2H), 3.83 (d, J=21.3 Hz, 3H), 1.69-0.97 (m, 2H);
fig. 6 is a poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate ] GPC image, mn=6205, mw=6227, mp=6141, mz=6249;
FIG. 7 is a nuclear magnetic resonance spectrum of the synthetic monomer 1-methyl-3- (4-vinylbenzyl) imidazolium hexafluorophosphate in acetone-d 6. Nuclear magnetic 1H NMR (600 MHz, actone-d 6) δ9.14 (s, 1H), 7.75 (d, j=1.9 Hz, 1H), 7.55 (d, j=8.1 Hz, 2H), 7.48 (d, j=8.0 Hz, 2H), 6.79 (dd, j=17.6, 11.0 Hz, 1H), 5.87 (d, j=17.7 Hz, 1H), 5.58 (s, 3H), 5.31 (d, j=11.0 Hz, 1H), 4.08 (s, 3H), 1.28 (ddd, j=19.8, 15.2, 6.8 Hz, 0H);
FIG. 8 is poly [1- (4-vinylbenzyl) -3-methylimidazolium hexafluorophosphate ] in DMSO-d6, nuclear magnetic 1H NMR (500 MHz, DMSO-d 6) δ9.11 (s, 1H), 7.66 (d, J=20.2 Hz, 1H), 7.39 (d, J=15.8 Hz, 0H), 6.96 (s, 1H), 6.38 (s, 1H), 5.19 (s, 2H), 3.84 (d, J=14.8 Hz, 3H), 1.57-1.07 (m, 2H);
fig. 9 is a GPC image of poly [1- (4-vinylbenzyl) -3-methylimidazolium hexafluorophosphate ] with mn=6304, mw=6335, mp=6375, mz=6366;
FIG. 10 shows the nuclear magnetic resonance spectrum of the synthetic monomer 1- (4-vinylbenzyl) -3-butylimidazolium bis (trifluoromethane) sulphonimide in acetone-d 6. Nuclear magnetic 1H NMR (600 MHz, DMSO-d 6) δ9.27-9.17 (m, 1H), 7.99 (dd, j=12.9, 8.2 Hz, 1H), 7.80 (dt, j=16.9, 1.8 Hz, 1H), 7.56-7.46 (m, 2H), 7.40 (dd, j=15.1, 7.0 Hz, 2H), 6.99 (s, 5H), 5.88 (d, j=17.7 Hz, 1H), 5.40 (d, j=9.7 Hz, 2H), 5.21 (s, 6H), 3.93-3.79 (m, 12H), 1.99 (s, 1H);
FIG. 11 is poly [1- (4-vinylbenzyl) -3-methylimidazolium bis (trifluoromethane) sulfonylimide ] in DMSO-d6, nuclear magnetic 1H NMR (500 MHz, DMSO-d 6) δ9.09 (s, 1H), 7.67-7.55 (m, 1H), 7.38 (d, J=27.9 Hz, 1H), 6.94 (s, 2H), 6.37 (s, 2H), 5.18 (s, 2H), 3.84 (d, J=14.9 Hz, 3H), 1.56-1.17 (m, 3H);
fig. 12 is a GPC image of poly [1- (4-vinylbenzyl) -3-methylimidazolium bis (trifluoromethane) sulfonylimide salt ], mn=5995, mw=6017, mp=6020, mz=6040;
FIG. 13 is a scanning electron micrograph of an inventive polymer ionic liquid poly (1-methyl-3- (4-vinylbenzyl) imidazolium chloride) compounded with single-walled carbon nanotubes after drop coating;
FIG. 14 is a scanning electron micrograph of an inventive polymer ionic liquid poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate ] compounded with single-walled carbon nanotubes after drop coating;
FIG. 15 is a scanning electron micrograph of an inventive polymer ionic liquid poly [1- (4-vinylbenzyl) -3-methylimidazolium hexafluorophosphate ] compounded with single-walled carbon nanotubes after drop coating;
FIG. 16 is a scanning electron micrograph of an inventive polymer ionic liquid poly [1- (4-vinylbenzyl) -3-methylimidazolium bis (trifluoromethane) sulfonimide salt ] compounded with single wall carbon nanotubes after drop coating;
FIG. 17 is a Raman spectrum of several polymer ionic liquids and single-walled carbon nanotube composite films of the invention;
FIG. 18 is an X-ray photoelectron spectrum of several polymer ionic liquids and single wall carbon nanotube composite films of the invention;
FIG. 19 is a C1s energy spectrum comparison of the X-ray photoelectron spectra of several polymer ionic liquids of the invention and single-walled carbon nanotube composite films;
FIG. 20 is an infrared spectrum comparison of a sensing film made of poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate ] of the invention with single-walled carbon nanotubes and carbon nanotube films before and after sensing sulfur dioxide;
FIG. 21 is a graph of the change in sensor signal for sulfur dioxide for a sensor film made of poly (1-methyl-3- (4-vinylbenzyl) imidazolium chloride) and single-walled carbon nanotubes;
FIG. 22 is a graph of the change in sensor signal for sulfur dioxide for a sensor film made of poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate ] and single-walled carbon nanotubes;
FIG. 23 is a graph of the change in sensor signal for sulfur dioxide for a sensor film made of poly [1- (4-vinylbenzyl) -3-methylimidazolium hexafluorophosphate ] and single-walled carbon nanotubes;
FIG. 24 is a graph of the change in sensor signal for sulfur dioxide for a sensing film made of poly [1- (4-vinylbenzyl) -3-methylimidazolium bis (trifluoromethane) sulfonimide salt ] and single-walled carbon nanotubes;
FIG. 25 is a plot of the response intensity of the inventive polymer ionic liquid for different gases at the same concentration of 10 ppm;
FIG. 26 is a comparative 1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate]Carbon nanotube composite sensor for 8ppm SO 2 Is a sensing curve of (2);
FIG. 27 is a graph comparing 1-benzyl-3-methylimidazole chloride-carbon nanotube complex sensors for 8ppm SO 2 Is a sensing curve of (2);
FIG. 28 is a comparative poly [1- (4-vinylbenzyl) -pyridine tetrafluoroborate]Carbon nanotube composite sensor for 8ppm SO 2 Is a sensing curve of (2);
fig. 29 is a graph of sulfur dioxide gas that the sensor was still able to detect 512ppt after 14 days of continuous testing.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1: synthesizing polyimidazolyl ionic liquid, and performing ion exchange and polymerization processes
The detailed procedure may be described by adding N-methylimidazole (8.2 g), 4-vinylbenzyl chloride (15.2 g) and the inhibitor 2, 6-di-tert-butyl-p-cresol (0.10 g) to the flask. The reaction mixture was stirred under nitrogen at 40 ℃ for 24 hours to give very viscous liquid 1- (4-vinylbenzyl) -3-methylimidazole chloride. This compound was washed with diethyl ether and ethyl acetate and dried under vacuum overnight at room temperature to give a clear yellow viscous liquid, 1- (p-vinylbenzyl) -3-methylimidazolium chloride, nuclear magnetism as shown in fig. 1, 1H NMR (600 MHz, deuterium Oxide) delta 7.52 (d, j=7.9 Hz, 1H), 7.42 (q, j=2.1 Hz, 1H), 7.36 (d, j=7.8 Hz, 1H), 6.76 (dd, j=17.7, 10.9 Hz, 1H), 5.86 (d, j=17.7 Hz, 1H), 5.45-5.24 (m, 2H), 3.86 (s, 1H).
1.1 Synthesis of Poly (1-methyl-3- (4-vinylbenzyl) imidazolium chloride) (PIL-Cl)
The monomers and the radical initiator azobisisobutyronitrile were polymerized in an aqueous solution with stirring at 60℃for 24 hours. Acetone is then added and the polymeric ionic liquid poly (1-methyl-3- (4-vinylbenzyl) imidazolium chloride) is precipitated as a yellow amorphous solid. In fig. 2, the nuclear magnetism is 1H NMR (500 MHz, DMSO-d 6) δ10.06 (s, 1H), 8.08 (s, 1H), 7.80 (s, 1H), 7.38 (s, 2H), 6.34 (s, 2H), 5.57 (s, 2H), 3.84 (s, 3H), 1.96-0.79 (m, 3H), GPC image in fig. 3, mn=6390, mw=20202, mp=19866, mz=38900.
1.2 Synthesis of Poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate ] (PIL-BF 4)
1.22 g of sodium tetrafluoroborate dissolved in 15 ml of anhydrous acetone are added to 15 ml of anhydrous acetone containing 2.76 g of 1- (p-vinylbenzyl) -3-alkylimidazolium chloride and 30 mg of 2, 6-di-tert-butyl-p-cresol. After stirring for 60 hours, the solution was filtered and the filtrate was evaporated under reduced pressure to give a yellow waxy solid. The crude product was further purified by washing with water and diethyl ether to obtain 1- (p-vinylbenzyl) -3-methylimidazolium tetrafluoroborate, in fig. 4, the nuclear magnetism was shown as 1H NMR (600 MHz, DMSO-d 6) δ9.29 (d, j=18.9 Hz, 1H), 7.76 (dt, j=47.2, 2.0 Hz, 3H), 7.41 (d, j=8.0 Hz, 3H), 6.74 (dd, j=17.6, 10.9 Hz, 1H), 5.42 (s, 2H), 5.30 (d, j=10.9 Hz, 1H), 3.35 (s, 4H), 2.50 (p, j=1.8 Hz, 3H). 1- (p-vinylbenzyl) -3-methylimidazolium tetrafluoroborate (1 g) and azobisisobutyronitrile (10 mg) obtained above were dissolved in 2 ml dimethylformamide solvent and stirred under nitrogen at 60℃for 24 hours. Thereafter, the mixture was poured into methanol to generate a precipitate. The precipitate was collected by filtration, washed thoroughly with methanol and then dried in vacuo at 50℃to give the polymer ionic liquid poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate ] as a pale yellow solid. The nuclear magnetism of fig. 5 shows 1H NMR (500 MHz, DMSO-d 6) δ9.08 (s, 1H), 7.72-7.34 (m, 2H), 7.08 (s, 2H), 6.49 (d, j=58.9 Hz, 2H), 5.26 (d, j=28.5 Hz, 2H), 3.83 (d, j=21.3 Hz, 3H), 1.69-0.97 (m, 2H). FIG. 6 is a GPC image of poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate ] as shown: the horizontal axis is the molecular weight, and the arrangement is from small to large; the ordinate is divided into left and right sides, the left side represents the signal intensity of each molecular weight of the signal, the higher represents the more molecules of the molecular weight, the right side represents the accumulated integral result, namely a curve gradually rising from 0% to 100% in the graph, which is called an accumulated integral curve, and the ratio of molecules in any molecular weight interval in the total molecules can be estimated directly in the graph by using the accumulated integral curve; mn=6205, mw=6227, mp=6141, mz=6249.
1.3 Synthesis of Poly [1- (4-vinylbenzyl) -3-methylimidazolium hexafluorophosphate ] (PIL-PF 6)
A 1.1 gram (5 mmol) aqueous solution of 1- (4-vinylbenzyl) -3-alkylimidazolium chloride and sodium hexafluorophosphate in a flask was mixed at room temperature for 60 hours to give 1-methyl-3- (4-vinylbenzyl) imidazolium hexafluorophosphate, which in fig. 7, showed 1H NMR (600 MHz, actone-d 6) delta 9.14 (s, 1H), 7.75 (d, j=1.9 Hz, 1H), 7.55 (d, j=8.1 Hz, 2H), 7.48 (d, j=8.0 Hz, 2H), 6.79 (dd, j=17.6, 11.0 Hz, 1H), 5.87 (d, j=17.7 Hz, 1H), 5.58 (s, 3H), 5.31 (d, j=11.0 Hz, 1H), 4.08 (s, 3H), 1.28.56, 19.8 (d, 8.8.9, 19.56, 2H). The resulting white solid was washed several times with excess deionized water and dried. 1mg of azobisisobutyronitrile (1 mole%) was added as a free radical initiator, and 20 ml of acetonitrile as a solvent to a 50ml round bottom flask. The system was purged with nitrogen. The reaction mixture was stirred with a magnetic stirrer for 72 hours at 65 ℃. The product was precipitated in cold methanol. Both polymers were further purified by dissolution in acetonitrile followed by precipitation in cold methanol and dried under vacuum to give purified polymeric ionic liquid poly [1- (4-vinylbenzyl) -3-methylimidazolium hexafluorophosphate ]. In fig. 8, the nuclear magnetism is shown as 1H NMR (500 MHz, DMSO-d 6) δ9.11 (s, 1H), 7.66 (d, j=20.2 Hz, 1H), 7.39 (d, j=15.8 Hz, 0H), 6.96 (s, 1H), 6.38 (s, 1H), 5.19 (s, 2H), 3.84 (d, j=14.8 Hz, 3H), 1.57-1.07 (m, 2H). Fig. 9 is a GPC image of poly [1- (4-vinylbenzyl) -3-methylimidazolium hexafluorophosphate ] with mn=6304, mw=6335, mp=6375, mz=6366.
1.4 Synthesis of Poly [1- (4-vinylbenzyl) -3-methylimidazolium bis (trifluoromethane) sulfonimide salt ] (PIL-Tf 2N)
1- (4-vinylbenzyl) -3-methylimidazole chloride was dissolved in deionized water (200 ml). Lithium bis (trifluoromethane) sulfonyl imide (30.4 g, 105.8 mmol) was added to the aqueous solution. Added to the aqueous solution, the bottom of the flask immediately appeared as an oily liquid. The reaction was allowed to stir at room temperature for 24 hours. The oil was then added to ethyl acetate (200 mL) and washed with deionized water (3×50 mL). The organic phase is dried over anhydrous magnesium sulfate, filtered and the solvent is removed by rotary evaporation. The excess solvent was removed in vacuo to give a very viscous liquid, 1- (4-vinylbenzyl) -3-methylimidazolium bis (trifluoromethane) sulphonimide, shown in fig. 10 as 1H NMR (600 MHz, DMSO-d 6) δ9.27-9.17 (m, 1H), 7.99 (dd, j=12.9, 8.2 Hz, 1H), 7.80 (dt, j=16.9, 1.8 Hz, 1H), 7.56-7.46 (m, 2H), 7.40 (dd, j=15.1, 7.0 Hz, 2H), 6.99 (s, 5H), 5.88 (d, j=17.7 Hz, 1H), 5.40 (d, j=9.7 Hz, 2H), 5.21 (s, 6H), 3.93-3.79 (m, 12H), 1.99 (s, 1H). 1- (4-vinylbenzyl) -3-butylimidazolium bis (trifluoromethane) sulfonimide (1.9 mmol,1.0 g), azobisisobutyronitrile (2 mg, 11. Mu. Mol) and acetonitrile (5 mL) were charged into a flask. This was placed in an oil bath at a constant temperature of 70℃and stirred for 24 hours, the solvent was removed, and the solution was washed three times with ethyl acetate to obtain a transparent colloidal amorphous polymer ionic liquid poly [1- (4-vinylbenzyl) -3-methylimidazolium bis (trifluoromethane) sulfonimide salt ]. In fig. 11, the nuclear magnetism is shown as 1H NMR (500 MHz, DMSO-d 6) δ9.09 (s, 1H), 7.67-7.55 (m, 1H), 7.38 (d, j=27.9 Hz, 1H), 6.94 (s, 2H), 6.37 (s, 2H), 5.18 (s, 2H), 3.84 (d, j=14.9 Hz, 3H), 1.56-1.17 (m, 3H). Fig. 12 is a GPC image of poly [1- (4-vinylbenzyl) -3-methylimidazolium bis (trifluoromethane) sulfonylimide salt ], mn=5995, mw=6017, mp=6020, mz=6040.
Example 2: preparation of Polymer Ionic liquid and carbon nanotube Complex SO 2 Sensor film
We fabricated 4mm x 8mm sensor devices using a 4 inch silicon wafer by lift-off process to prepare the sensor electrodes. We prepared 5mL of 0.01mg/mL DMSO solution from PIL-Cl, 0.01mg/mL DMF solution, 0.05mg/mL DMF solution, 0.1mg/mL DMF solution from PIL-BF4, PIL-PF6, PIL-Tf2N, respectively; then adding 0.05mg single-wall carbon nanotube SWCNTs powder into the four solutions respectively, and performing ultrasonic treatment to obtain four SO 2 The mass ratio of the precursor solution of the sensor to the polymer ionic liquid to the carbon nano tube is 1:1, 5:1 and 10:1 respectively; respectively dripping 2 microliters of solution on the electrode, volatilizing the solution in vacuum to obtain a plurality of film-based SO 2 The chemiresistor sensor is characterized in that a sensing film exists on the surface of an electrode, and two pins are connected with an external circuit below the chemiresistor sensor. Then, the resistance of the sensor was preliminarily tested by adding 0.05mg of double-walled carbon nanotubes and multi-walled carbon nanotubes in comparison, and found that the self film resistance thereof did not match the test circuit, and therefore,the single-walled carbon nanotubes were used for the sensing test afterwards. For different mass ratios of polymer ionic liquid and carbon nano tubes, the range of initial resistance values is also different, and when the ratio of the polymer ionic liquid is increased, the resistance value is also increased. The scanning electron microscope characterization is carried out on the carbon nano tube composite, the carbon nano tube composite can be mutually stacked to form a nest-shaped three-dimensional film form, and the carbon nano tube composite is in a two-dimensional or three-dimensional state as shown in fig. 13-16, the film state formed after the film is dripped is sparse according to the composition of the carbon nano tube between the electrodes, the effective contact of gas and materials is facilitated, and the effective action area of sensing is increased. The sparse carbon nanotubes can form an approximately two-dimensional plane state, the nest-shaped carbon nanotube stacking state can form a three-dimensional porous state, and the manufactured chemical resistance sensor mainly utilizes polymer ionic liquid-carbon nanotube composite materials to adsorb sulfur dioxide to generate surface resistance signal change for detecting sulfur dioxide.
Example 3: characterization of Polymer Ionic liquid and carbon nanotube Complex SO 2 Sensor film
For the polymer ionic liquid and carbon nanotube composite SO in example 2 2 The sensor film uses Raman spectrum and X-ray photoelectron spectrum to perform related characterization, and the polymer and the carbon nano tube are characterized to form a good electron transmission channel, and the electron channel is used for sensing SO 2 Has important function. In fig. 17, the G-peak of the raman spectrum of several composite films moves in the direction of increasing wavenumber, which is shown by the decrease of electrons on the carbon nanotubes, and the efficient transfer of electrons to the polymer ionic liquid, so that the stable film is formed by the efficient recombination of carbon nanotubes by the polymer ionic liquid. In fig. 18, the element state of the composite film is represented by the X-ray photoelectron spectrum, and it is obvious in the figure that the N peak is increased at 400eV and the F peak is increased at 700eV in the composite film compared with the single-wall carbon nanotube, and the surface of the carbon nanotube is presented with the polymer ionic liquid. In fig. 19, the C1s peak forms a shift toward a high binding energy direction, which is manifested in that the carbon nanotube surface forms an effective electron transport channel with the polymer ionic liquid, causing electrons to be transferred to the polymer ionic liquid. Finally, it is expressed as carbonThe nanotubes and the polymer ionic liquid effectively form a stable film, and the film has an effective electron transmission channel which is a signal transmission channel in the sensing process.
In FIG. 20, the polymer ionic liquid and carbon nanotube composite SO is obtained by infrared spectroscopy 2 Sensor film sensing SO 2 Characterization was performed back and forth, primarily with respect to poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate]Films constructed with single-walled carbon nanotubes (PIL-BF 4-SWCNTs) exhibited 1013cm -1 Vibration of B-F located key, 1162 cm -1 ,1450 cm -1 ,1532 cm -1 The vibration of the C-N chemical bond on imidazole is changed in the sensing process, which is expressed as the effective adsorption of SO on the sensing ion pair unit on the polymer ionic liquid 2 After that, a change in the sensing signal is caused. The film-based material can effectively play the advantages of the sensing material, and can directly contact gas molecules to cause the change of the whole sensing signal.
Example 4: chemiresistor sensor testing
4.1 sensor device set-up
For sensing SO 2 Is tested using a keysight 34461a digital multimeter. Injecting 50ml of SO with different concentrations at a flow rate of 60ml/min at 25deg.C by using a glass syringe 2 After the gas is injected into the gas chamber, a relatively closed space with the same concentration is formed, and in the space, the sensing device contacts SO 2 Molecules, forming effective contact, adsorbing SO 2 And obtaining the resistance signal change.
And (3) adopting a plurality of sensors prepared in the embodiment 2, connecting pins of each sensor to a digital multimeter, placing the sensors into a gas chamber, and introducing configured sulfur dioxide gas into the gas chamber to perform a sensing experiment. As the polymer ionic liquid-single-walled carbon nanotubes are specific to SO 2 The gas has adsorption effect, and the adsorption can cause the change of the electrical property of the surface of the compound, thereby causing the change of the resistance of the sensor film. Real-time change of measuring resistance of digital multimeter is displayed on screen, and gas concentration can be judged by resistance signalDegree. The sensor resistance versus gas concentration (one for each anion) test curves are shown in fig. 21-24, with high stability, low detectable gas detection limits to sub ppb levels, and sensor rise ratios greater than three times signal to noise ratio.
FIG. 29 is a graph showing the change in resistance of a sensor after 14 days of continuous testing for poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate ] and single wall carbon nanotube structured films (PIL-BF 4-SWCNTs) while still being able to detect 512ppt of sulfur dioxide gas. In fig. 29, it is shown that the sensor was still able to test 512ppt of sulfur dioxide gas after 14 days of continuous testing.
4.2 Polymer-carbon nanotube film sensor SO 2 Sensing test
The invention researches the sensing performance of PIL-SWCNT material and discovers that the PIL-SWCNT material has the sensitivity to SO 2 With good sensing results, PIL-SWCNTs sensors were tested with a digital multimeter, as shown in fig. 17-20 (one for each anion). PIL-SWCNTs sensor was tested with digital multimeter and found to be a PIL-BF4-SWCNTs sensor versus SO at room temperature 2 Is superior to the sensors of SWCNTs, PIL-Cl-SWCNTs, PIL-PF6-SWCNTs and PIL-Tf2N-SWCNTs, and can stably sense SO in a short time under the same conditions 2 . SWCNTs, PIL-Cl-SWCNTs, PIL-PF6-SWCNTs and PIL-Tf2N-SWCNTs can stably induce SO at room temperature 2 And can be continuously used in a short time, and the actual test SO of the sensor thereof 2 The gas reached 512ppt with a response of 8% and the performance of PIL-Cl-SWCNT, PIL-PF6-SWCNT and PIL-Tf2N-SWCNT sensors were compared. In FIGS. 17-20, the lower detection limits for PIL-Cl-SWCNT, PIL-PF6-SWCNT, and PIL-Tf2N-SWCNT are much greater than PIL-BF4-SWCNT.
4.3 Polymer-carbon nanotube film sensor interferent testing
The invention detects several gases that interfere with sulfur dioxide: nitrogen dioxide, hydrogen sulfide, oxygen, ammonia, and the like. Response As shown in FIG. 25, sulfur dioxide was compared with nitrogen dioxide, hydrogen sulfide, oxygen, ammonia at the same concentration of 10ppm, PIL-BF4-SWCNT transmissionThe response value of the sensing film to sulfur dioxide is highest, and the sensing film has obvious specific sensing effect to sulfur dioxide gas. As depicted in fig. 25, the multiple common gases have small sensing interference for the sensor of the present invention, and for the gas sensor, it is beneficial to specifically sense SO in complex environments 2 。
Example 5: contrast with different ionic liquid carbon nanotube film sensors
5.1 comparison with Ionic liquid monomer
The present invention compares monomers and uses the same way to compare 1- (p-vinylbenzyl) -3-alkylimidazolium chloride, 1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate]1- (4-vinylbenzyl) -3-methylimidazolium hexafluorophosphate and 1- (4-vinylbenzyl) -3-methylimidazolium bis (trifluoromethane) sulfonylimide salt were composited with single-walled carbon nanotubes. Firstly, 5mL of ionic liquid DMF solution with the concentration of 1mg/mL is prepared, 0.5mg of single-walled carbon nanotube is added, 0.1mg/mL of single-walled carbon nanotube solution is prepared, and then the mixture is uniformly mixed, so that four bottles of precursor solution for mixing monomer ionic liquid and single-walled carbon nanotube are obtained. Respectively dripping the solution onto sensor electrode, dripping 3 microliter, spreading the solution over the whole electrode, vacuum drying to obtain complete monomer ionic liquid-single-walled carbon nanotube film device, connecting device pins with digital multimeter, and testing SO 2 And (3) sensing effect of the gas. Test for sensory Effect for 8ppm SO 2 At this concentration, as shown in FIG. 26, the optimal sensor is 1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate]-a carbon nanotube composite sensor having a resistivity increase of 2.78% and a resistivity decrease of less than 3%.
Therefore, for the polymer ionic liquid carbon nanotube film sensor prepared in the invention, the wrapping of the polymer ionic liquid carbon nanotube film sensor itself depends on a long polymer chain, in comparative example 4, the detection limit of sulfur dioxide sensed by the polymer ionic liquid carbon nanotube film reaches 512ppt, and the monomer can only detect 8ppm of sulfur dioxide, which is shown that the monomer can not form a good electron transmission channel with the carbon nanotube, therefore, the polymer ionic liquid carbon nanotube provided by the invention has the following advantages that the polymer ionic liquid carbon nanotube film sensor can not form a good electron transmission channel with the carbon nanotube for SO 2 Has higher sensitivity and specificity.
5.2 comparison with 1-benzyl-3-methylimidazole chloride
1-benzyl-3-methylimidazole chloride is used as ionic liquid to prepare the sensor. Compounding 1-benzyl-3-methylimidazole chloride salt and single-wall carbon nano tubes: firstly, 5mL of 1-benzyl-3-methylimidazole chlorine salt DMF solution is prepared, 0.5mg of single-walled carbon nanotube is added, 0.1mg/mL of single-walled carbon nanotube solution is prepared, and then the mixture is uniformly mixed to obtain a bottle of mixed precursor solution of 1-benzyl-3-methylimidazole chlorine salt and single-walled carbon nanotube. And (3) dripping the solution onto the sensor electrode, dripping 3 microliters of the solution, spreading the whole electrode, and then performing vacuum drying to obtain the complete monomer ionic liquid-single-walled carbon nanotube film sensor.
It was tested for SO using the same test sensing as in example 4 2 And (3) sensing effect of the gas.
The sensing effect was tested as in FIG. 27 for SO at a concentration of 8ppm 2 The resistance increase rate of (2) is less than 1%. It can be seen that the thin film sensor prepared from 1-benzyl-3-methylimidazole chlorine salt is sensitive to SO 2 Is poor in sensitivity and poor in specificity.
5.3 comparison with Poly [1- (4-vinylbenzyl) -pyridine tetrafluoroborate ]
Since the sensing effect of poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate ] was optimal in the interferent test of example 4, the present invention selects boron tetrafluoride ion as an anion to prepare poly [1- (4-vinylbenzyl) -pyridine tetrafluoroborate ]. Unlike poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate ], the cationic position is a pyridine group.
Poly [1- (4-vinylbenzyl) -pyridine tetrafluoroborate]Compounding with single-wall carbon nanotube. Firstly, preparing 5mL of 1-benzyl-3-methylimidazole chlorine salt DMF solution with the concentration of 0.1mg/mL, adding 0.5mg of single-walled carbon nanotube, preparing 0.1mg/mL of single-walled carbon nanotube solution, and uniformly mixing to obtain poly [1- (4-vinylbenzyl) -pyridine tetrafluoroborate]Mixing the precursor solution with single-wall carbon nano tube (the ratio is 1:1) to obtain a bottle. Drop-coating the solution onto the sensor electrode, drop-coating 3Microliter, spreading the solution over the whole electrode, vacuum drying to obtain the complete monomer ionic liquid-single-wall carbon nanotube film sensor, connecting the pins with a digital multimeter, and testing the sensor for SO 2 And (3) sensing effect of the gas. As shown in FIG. 28, the sensing effect was tested for SO at a concentration of 8ppm 2 The resistance increase rate of (C) was 36%, the detection limit was 64ppb, which was weaker than that of poly [1- (4-vinylbenzyl) -3-methylimidazolium tetrafluoroborate]The detection limit of the single-walled carbon nanotube composite sensor. Thus, relative to the polymer ionic liquid carbon nanotube film sensor prepared in example 4, which itself relies on long polymer chains for carbon nanotube encapsulation, the sensing process also relies on ion pairs, where the ion pairs are changed to pyridine-boron tetrafluoride, methylimidazole-boron tetrafluoride, pyridine-boron tetrafluoride for SO in comparative example 4 2 The sensing sensitivity of (2) was reduced by a factor of 3.5, and only 64ppb was tested for the final detection limit.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should be covered by the protection scope of the present invention by making equivalents and modifications to the technical solution and the inventive concept thereof.
Claims (10)
1. A composition for a sensing film comprising a composite polymer and carbon nanotubes;
the cation of the polymer is at least one of polyvinylbenzyl 3-methylimidazolium, polyvinylbenzyl 3-ethylimidazolium, polyvinylbenzyl 3-propylimidazolium, polyvinylbenzyl 3-butylimidazolium and polyvinylbenzyl 3-hexylimidazolium;
the anion of the polymer is at least one of chloride ion, tetrafluoroborate ion, hexafluorophosphate ion and bistrifluoromethane sulfonyl imide ion;
the carbon nanotube is at least one of a single-walled carbon nanotube, a double-walled carbon nanotube and a multi-walled carbon nanotube.
2. The composition of claim 1 wherein the molar ratio of cations to anions in the polymer is 1:1.
3. The composition of claim 1, wherein the mass ratio of polymer to carbon nanotubes is 10:1 to 1:1.
4. The composition of claim 1, wherein the mass ratio of polymer to carbon nanotubes is 5:1.
5. A sensing film prepared from the composition of any one of claims 1 to 4.
6. The method for preparing a sensing film according to claim 5, wherein the method comprises preparing a precursor solution of a polymer and carbon nanotube composite, and coating the precursor solution, wherein the sensing film is obtained after solvent evaporation.
7. The method according to claim 6, wherein the solvent is at least one of toluene, xylene, chlorobenzene, dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.
8. A sensor comprising the sensing film of claim 5.
9. The method for preparing a sensor according to claim 8, wherein the method comprises the steps of coating a precursor solution of the prepared polymer and carbon nanotube composite on the surface of a sensor electrode, and obtaining the sensor after the solvent volatilizes.
10. Use of a sensor according to claim 8, wherein the sensor is adapted to detect molecules of sulphur dioxide gas in air.
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