CN115772284B - Acetic acid gas sensitive film and preparation method and application thereof - Google Patents
Acetic acid gas sensitive film and preparation method and application thereof Download PDFInfo
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- CN115772284B CN115772284B CN202211460616.8A CN202211460616A CN115772284B CN 115772284 B CN115772284 B CN 115772284B CN 202211460616 A CN202211460616 A CN 202211460616A CN 115772284 B CN115772284 B CN 115772284B
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 327
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 33
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 18
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 18
- RKVIAZWOECXCCM-UHFFFAOYSA-N 2-carbazol-9-yl-n,n-diphenylaniline Chemical compound C1=CC=CC=C1N(C=1C(=CC=CC=1)N1C2=CC=CC=C2C2=CC=CC=C21)C1=CC=CC=C1 RKVIAZWOECXCCM-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000003792 electrolyte Substances 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000001514 detection method Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 6
- 239000007983 Tris buffer Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
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- 230000004044 response Effects 0.000 abstract description 34
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- 230000000694 effects Effects 0.000 abstract description 6
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- 239000007789 gas Substances 0.000 description 68
- 230000000052 comparative effect Effects 0.000 description 25
- 238000012360 testing method Methods 0.000 description 24
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 14
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 14
- -1 tetrabutylammonium hexafluorophosphate Chemical compound 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 229910052760 oxygen Inorganic materials 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 125000004151 quinonyl group Chemical group 0.000 description 2
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- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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Landscapes
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention provides an acetic acid gas sensitive film, a preparation method and application thereof. The film comprises a conductive polymer film layer and a metal oxide film layer deposited on the surface of the conductive polymer layer; the raw materials of the conductive polymer layer comprise poly-4, 4' -tri (carbazole-9-yl) triphenylamine. The acetic acid gas sensitive film can realize the effect of generating resistance change on acetic acid gas in room temperature environment, and further realize the specific detection on the acetic acid gas, and the preparation method is simple and feasible, has high sensitivity, can detect the acetic acid gas with the concentration as low as 50ppm, and has short response time.
Description
Technical Field
The invention belongs to the technology of high polymer materials, and particularly relates to an acetic acid gas sensitive film, a preparation method and application thereof.
Background
The gas-sensitive resistance sensor is made by using the change of resistance value of a sensitive element caused by oxidation-reduction reaction of gas on the surface of a semiconductor, and is a sensor which converts detected gas components and concentration into resistance signals, and information of the gas existing in the environment can be obtained according to the strength of the signals, so that the monitoring or alarming function is realized. Currently, resistive gas sensors are dominant in the field of commercial gas sensors. The gas sensor has the disadvantage that it needs to be attached to a heating element for operation. Acetic acid, also known as acetic acid, is one of the common harmful air pollutants. When the acetic acid concentration in the air exceeds 80ppb, there is a risk of gastroesophageal reflux. When the acetic acid concentration in the air exceeds 100ppm, cultural relics such as coins, sculptures, lacquerware and the like in the museum can be slowly deteriorated. Therefore, detection of low concentration acetic acid vapor is of practical significance. Most of the reported devices for detecting the acetic acid steam in the literature have higher use temperature, and even if the devices for detecting the acetic acid can be realized in a room temperature environment, the preparation method is more complicated and does not meet the practical use requirements of carbon reduction and energy saving, so that the development of the device for detecting the acetic acid steam at room temperature has a certain significance.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the first aspect of the invention provides an acetic acid gas sensitive film, which can realize the corresponding high-selectivity resistance change of acetic acid gas in room temperature environment.
The second aspect of the invention provides a preparation method of the acetic acid gas sensitive film.
A third aspect of the present invention proposes an acetic acid gas detection sensor.
The fourth aspect of the invention provides an application of the acetic acid gas sensitive film in acetic acid gas detection.
According to a first aspect of the present invention, there is provided an acetic acid gas-sensitive film comprising a conductive polymer film layer and a metal oxide film layer deposited on a surface of the conductive polymer film layer; the conductive polymer film layer contains poly-4, 4' -tri (carbazole-9-yl) triphenylamine.
In some embodiments of the invention, the conductive polymer film layer has a thickness of 200nm to 1000nm.
In some embodiments of the invention, the metal oxide film layer has a thickness of 500nm to 1500nm.
In some embodiments of the present invention, the metal oxide film layer includes one of ZnO and CuO.
In some preferred embodiments of the present invention, the metal oxide film layer contains ZnO in the form of a wurtzite crystal.
According to a second aspect of the present invention, there is provided a method for producing an acetic acid gas-sensitive film according to the first aspect, comprising the steps of:
s1: mixing the electrolyte with 4,4' -tris (carbazole-9-yl) triphenylamine to obtain an electropolymerized electrolyte;
s2: placing a three-electrode system consisting of an ITO (indium tin oxide) serving as a working electrode, a counter electrode and a reference electrode in the electropolymerization electrolyte S1, and performing potentiostatic electropolymerization to obtain ITO with a conductive polymer film deposited on the surface;
s3: and (2) taking ITO with the surface deposited with the conductive polymer film layer as a working electrode, placing a three-electrode system consisting of a counter electrode and a reference electrode in a water solution containing metal salt, and depositing a metal oxide film layer on the surface of the conductive polymer film layer in a constant potential manner to obtain the acetic acid gas sensitive film.
In the invention, electro-polymerization of conductive monomer 4,4' -tri (carbazole-9-yl) triphenylamine is carried out in an electrochemical mode to obtain a conjugated microporous conductive polymer film layer, and then the conjugated microporous conductive polymer film layer is compounded with a metal oxide film layer, so that an acetic acid gas sensitive film is obtained; the conductive polymer reduces the initial resistance of the metal oxide at room temperature, and simultaneously can realize the resistance change response to acetic acid gas which cannot be realized by uncomplexed under the heterojunction effect formed by the conductive polymer and the metal oxide film layer.
In some embodiments of the invention, the electrolyte of S1 comprises a co-electrolyte, methylene chloride, tetrahydrofuran, and acetonitrile.
In some embodiments of the invention, the concentration of the co-electrolyte in the electrolyte of S1 is from 0.01mol/L to 0.5mol/L.
In some embodiments of the invention, the auxiliary electrolyte is at least one selected from tetrabutylammonium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, and ammonium fluoroborate.
In some embodiments of the present invention, the volume ratio of the dichloromethane, the tetrahydrofuran and the acetonitrile is (1 to 8): 1: (1-8).
In some embodiments of the invention, the concentration of 4,4',4 "-tris (carbazol-9-yl) triphenylamine in the electropolymerized electrolyte in S1 is from 0.2mg/mL to 2mg/mL.
In some embodiments of the invention, the counter electrode in S2 is selected from one of a platinum electrode, a silver electrode, a graphite electrode, and a titanium electrode.
In some embodiments of the invention, the reference electrode in S2 is an Ag/Ag electrode.
In some embodiments of the invention, the potentiostatic in S2 is between-1.1V and-1.4V.
In some embodiments of the invention, the potentiostatic electropolymerization in S2 takes from 5min to 15min.
In some preferred embodiments of the invention, the potentiostatic electropolymerization in S2 takes from 500S to 700S.
In some preferred embodiments of the present invention, the potentiostatic electropolymerization of S2 further comprises: sequentially cleaning with tetrahydrofuran for 5-10 min, deionized water for 5-10 min, and drying; the drying temperature is 50-65 ℃ and the drying time is 20-25 h.
In some preferred embodiments of the invention, the reference electrode in S3 is a saturated KCl electrode.
In some preferred embodiments of the present invention, the concentration of the aqueous solution containing a metal salt in S3 is 0.01mol/L to 0.15mol/L.
In some preferred embodiments of the present invention, the metal salt in S3 is selected from Zn (NO 3 ) 2 、ZnSO 4 、CuSO 4 At least one of them.
In some preferred embodiments of the invention, the potentiostatic in S3 is 1.6V to 2V.
In some preferred embodiments of the invention, the potentiostatic deposition in S3 is for a period of 10min to 15min.
In some preferred embodiments of the invention, the potentiostatic deposition in S3 takes from 700S to 900S.
In some more preferred embodiments of the present invention, the potentiostatic deposition step in S3 further comprises: washing with deionized water for 5-10 min, and drying; the drying temperature is 50-65 ℃ and the drying time is 20-25 h.
According to a third aspect of the present invention, there is provided an acetic acid gas detection sensor equipped with the acetic acid gas-sensitive membrane of the first aspect.
According to a fourth aspect of the present invention, there is provided the use of an acetic acid gas-sensitive membrane in the detection of acetic acid gas.
In some embodiments of the invention, the acetic acid gas detection requires an ambient humidity of 40% to 80%.
In the invention, the sensitivity of the metal oxide to humidity is higher, and the phenomenon of the sensor sensitivity reduction at lower humidity and higher humidity can be explained by an electron-proton conduction mechanism, and the water vapor in the air is adsorbed on the surface of the metal oxide in different ways and reacts with active oxygen ions on the surface of the metal oxide: o (O) 2 (g) Becomes O 2 (ads)，O 2 (ads) obtaining electrons to O 2 - (ads), water vapor H 2 O and O 2 - (ads) formation of 2OH - And releases electrons.
In a lower humidity environment, water vapor in the air is adsorbed on the surface of the acetic acid gas sensitive film material in a chemical adsorption mode, and because the concentration of the water vapor in the air is lower, fewer hydroxyl ions are generated by the reaction of the water vapor and active oxygen ions, fewer electrons are emitted, namely, fewer electrons are transferred to the conductive polymer film layer, and the macroscopic appearance is that the initial resistance of the sensor is higher in the lower humidity environment. In the environment with higher humidity, the water vapor in the air is adsorbed on the surface of the material in a physical adsorption mode, and due to the higher concentration of the water vapor, a large amount of hydroxyl radicals generated by the reaction of the water vapor and active oxygen ions are released, a large amount of electrons are transferred to the conductive polymer film layer, and meanwhile, due to the high humidity, the water vapor is accumulated in the grain boundary of the metal oxide in the form of water molecules, and a water layer is formed, so that the conductivity of the sensor is further increased.
For sensing acetic acid vapor, this is in fact a co-response to acetic acid vapor and water vapor, which are in competing relationship in the process. When the air humidity is lower, the reaction of the water vapor and the active oxygen ions generates fewer hydroxyl radicals, so that H ionized by the acetic acid vapor under the same concentration + Can rapidly consume OH - And the surface depletion layer is weakened, the resistance of the sensor is reduced, and the corresponding response time is shorter. Whereas in high humidity environment, H is ionized by acetic acid vapor + Can not rapidly consume OH - And the existence of the water layer on the surface of the metal oxide further prevents acetic acid steam from contacting the electron depletion layer, so that the corresponding response time is long, and even in a 90% humidity environment, the phenomenon of resistance reduction does not occur.
The beneficial effects of the invention are as follows:
the acetic acid gas sensitive film can realize the specific detection of acetic acid gas in room temperature environment, and the preparation method is simple and feasible, has high sensitivity, the detection limit is 50ppm, and the response time is as low as 5s.
Drawings
The invention is further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is a schematic view of a process for preparing an acetic acid gas-sensitive film according to example 1 of the present invention;
FIG. 2 is a schematic diagram showing the process of detecting the gas-sensitive performance of an acetic acid gas-sensitive film sample according to example 1 of the present invention;
FIG. 3 is a graph showing resistance change of the film prepared in example 1 of the present invention against 200ppm acetic acid gas;
FIG. 4 is a graph showing the response of the films prepared in example 1 and comparative examples 1 to 2 of the present invention to 200ppm acetic acid gas;
FIG. 5A is a graph showing the response curves of the film prepared in example 1 of the present invention to acetic acid vapors of different concentrations at room temperature, and B is a graph showing the fit of acetic acid gas concentration to film sensitivity;
FIG. 6 is a graph showing the results of a 200ppm acetic acid performance test for a continuous 3 cycle period for the film prepared in example 1;
FIG. 7 is a graph showing the results of testing the stability of the film prepared in example 1 against 200ppm acetic acid vapor response over 30 days;
FIG. 8 is a graph showing the resistance change response of the film prepared in example 1 to 1000ppm of different organic solution vapors;
FIG. 9 is a graph showing the sensitivity of the films prepared in examples 1 to 3 and comparative examples 3 to 5 to 200ppm acetic acid vapor;
FIG. 10 is a graph showing the comparison of the resistance values in the initial state of the films prepared in examples 1 to 3 and comparative examples 3 to 5;
FIG. 11 is a graph showing the response time versus recovery time of the films prepared in examples 1-3 and comparative examples 3-5 to 200ppm acetic acid vapor;
FIG. 12 is a graph showing the X-ray diffraction results of the thin film prepared in example 1;
FIG. 13 (a) is an infrared schematic view of TCTA monomer and PTCTA film, (b) is a detailed enlarged view of critical wavenumber range, respectively;
FIG. 14 (a) is an infrared schematic view of film samples of example 1, comparative example 1 and comparative example 2, (b) is a drawing, and (c) is an enlarged detail view of the critical wavenumber range, respectively;
FIG. 15 is a schematic diagram showing the mechanism of detecting acetic acid vapor by the acetic acid gas-sensitive film (PTCTA & ZnO film) of the present invention;
FIG. 16 is a graph comparing the sensitivity of the film prepared in example 1 to 200ppm acetic acid vapor at various air humidities;
FIG. 17 is a plot of the response of the film prepared in example 1 to 200ppm acetic acid vapor at 90% air humidity;
fig. 18 (a) is a nitrogen element diagram of the X-ray photoelectron spectrum of the film prepared in comparative example 1, (b) is a nitrogen element diagram of the X-ray photoelectron spectrum of the film prepared in example 1, (c) is an oxygen element diagram of the X-ray photoelectron spectrum of the film prepared in comparative example 2, and (d) is an oxygen element diagram of the X-ray photoelectron spectrum of the film prepared in example 1.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention. The starting materials used in the examples below, unless otherwise specified, were all commercially available from conventional sources; the processes used are all conventional in the art unless otherwise specified. The TCTA structure used is as shown below and can be prepared by methods well known in the art.
Example 1
The embodiment prepares the acetic acid gas sensitive film, which comprises the following specific processes:
(1) 0.1937g of tetrabutylammonium hexafluorophosphate, 3mL of tetrahydrofuran, 1.5mL of methylene chloride, 0.5mL of acetonitrile and 3mg of TCTA (4, 4',4 "-tris (carbazol-9-yl) triphenylamine) were mixed to obtain 5mL of an electropolymerized electrolyte.
(2) Immersing ultrasonic-washed and dried ITO glass sequentially in isopropanol, deionized water and ITO washing liquid to serve as a working electrode, immersing the working electrode, the silver-silver ion electrode and the platinum sheet electrode together as a three-electrode system in the electropolymerization electrolyte prepared in the step (1), setting the potential to be 1.62V, electropolymerizing in a constant potential mode for 600s, immersing the ITO working electrode in tetrahydrofuran and deionized water for 5min respectively to clean impurities such as unpolymerized monomers, and then vacuum-drying at 60 ℃ for 24h to obtain the ITO with the surface deposited conductive polymer film (PTCTA).
(3) Taking ITO of the surface deposited conductive polymer film obtained in the step (2) as a working electrode, a platinum electrode as a counter electrode and a saturated KCl electrode as a reference electrode to form a three-electrode system together, soaking in Zn (NO) with the concentration of 0.1mol/L 3 ) 2 Is water-soluble in (2)Heating to 65deg.C, depositing ZnO on PTCTA surface by constant potential electrodeposition with potential of-1.2V for 800s, soaking in deionized water for 10min to clean ions adhered on the film, and vacuum drying at 60deg.C for 24 hr to obtain acetic acid gas sensitive film (PTCTA&ZnO film).
Example 2
The embodiment prepares the acetic acid gas sensitive film, which comprises the following specific processes:
(1) 0.1937g of tetrabutylammonium hexafluorophosphate, 3mL of tetrahydrofuran, 1.5mL of methylene chloride, 0.5mL of acetonitrile and 3mg of TCTA (4, 4',4 "-tris (carbazol-9-yl) triphenylamine) were mixed to obtain 5mL of an electropolymerized electrolyte.
(2) Immersing ultrasonic-washed and dried ITO glass sequentially in isopropanol, deionized water and ITO washing liquid to serve as a working electrode, immersing the working electrode, the silver-silver ion electrode and the platinum sheet electrode together as a three-electrode system in the electropolymerization electrolyte prepared in the step (1), setting the potential to be 1.62V, electropolymerizing in a constant potential mode for 500 seconds, immersing the ITO working electrode in tetrahydrofuran and deionized water for 5 minutes respectively to clean impurities such as unpolymerized monomers, and then vacuum-drying at 60 ℃ for 24 hours to obtain the ITO with the surface deposited conductive polymer film (PTCTA).
(3) Taking ITO of the surface deposited conductive polymer film obtained in the step (2) as a working electrode, a platinum electrode as a counter electrode and a saturated KCl electrode as a reference electrode to form a three-electrode system together, soaking in Zn (NO) with the concentration of 0.1mol/L 3 ) 2 Heating to 65deg.C, depositing ZnO on PTCTA surface by potentiostatic electrodeposition with potential of-1.2V for 800s, soaking in deionized water for 10min to clean ions adhered to the film, and vacuum drying at 60deg.C for 24 hr to obtain acetic acid gas sensitive film (PTCTA)&ZnO film).
Example 3
The embodiment prepares the acetic acid gas sensitive film, which comprises the following specific processes:
(1) 0.1937g of tetrabutylammonium hexafluorophosphate, 3mL of tetrahydrofuran, 1.5mL of methylene chloride, 0.5mL of acetonitrile and 3mg of TCTA (4, 4',4 "-tris (carbazol-9-yl) triphenylamine) were mixed to obtain 5mL of an electropolymerized electrolyte.
(2) The ITO glass which is soaked, ultrasonically washed and dried by isopropanol, deionized water and ITO washing liquid is used as a working electrode, the working electrode, a silver-silver ion electrode and a platinum sheet electrode are used as a three-electrode system to be soaked in the electropolymerization electrolyte prepared in the step (1), the electric potential is set to be 1.62V, electropolymerization is carried out in a constant potential mode, the polymerization time is 700s, then the ITO working electrode is soaked in tetrahydrofuran and deionized water for 5min respectively, so as to clean unpolymerized monomers, auxiliary electrolyte and other impurities, and then the ITO with a surface deposited conductive polymer film (PTCTCTA) is obtained by vacuum drying for 24h at 60 ℃.
(3) Taking ITO of the surface deposited conductive polymer film obtained in the step (2) as a working electrode, a platinum electrode as a counter electrode and a saturated KCl electrode as a reference electrode to form a three-electrode system together, soaking in Zn (NO) with the concentration of 0.1mol/L 3 ) 2 Heating to 65deg.C, depositing ZnO on PTCTA surface by potentiostatic electrodeposition with potential of-1.2V for 800s, soaking in deionized water for 10min to clean ions adhered to the film, and vacuum drying at 60deg.C for 24 hr to obtain acetic acid gas sensitive film (PTCTA)&ZnO film).
Comparative example 1
This comparative example produced a TCTA film, which was different from example 1 in that it was not complexed with ZnO (i.e., lacked step (3)), and was prepared by:
(1) 0.1937g of tetrabutylammonium hexafluorophosphate, 3mL of tetrahydrofuran, 1.5mL of methylene chloride, 0.5mL of acetonitrile and 3mg of TCTA (4, 4',4 "-tris (carbazol-9-yl) triphenylamine) were mixed to obtain 5mL of an electropolymerized electrolyte.
(2) Immersing ultrasonic-washed and dried ITO glass sequentially in isopropanol, deionized water and ITO washing liquid to serve as a working electrode, immersing the working electrode, the silver-silver ion electrode and the platinum sheet electrode together as a three-electrode system in the electropolymerization electrolyte prepared in the step (1), setting the potential to be 1.62V, electropolymerizing in a constant potential mode for 600s, immersing the ITO working electrode in tetrahydrofuran and deionized water for 5min respectively to clean impurities such as unpolymerized monomers, and then vacuum-drying at 60 ℃ for 24h to obtain the ITO with the surface deposited conductive polymer film (PTCTA).
Comparative example 2
This comparative example produced a ZnO film differing from example 1 in that it was not complexed with TCTA (i.e., lacking step (2)), otherwise referred to example 1.
Comparative example 3
An acetic acid gas-sensitive film was prepared in this comparative example, which was different from example 1 in the time of the electropolymerization in step (2) and the polymerization time was 200s, otherwise referring to example 1.
Comparative example 4
An acetic acid gas-sensitive film was prepared in this comparative example, which was different from example 1 in the time of the electropolymerization in step (2) and the polymerization time was 300s, otherwise referring to example 1.
Comparative example 5
An acetic acid gas-sensitive film was prepared in this comparative example, which was different from example 1 in the time of the electropolymerization in step (2) and the polymerization time of this comparative example was 400s, otherwise refer to example 1.
Test examples
1. The films prepared in example 1 and comparative examples 1 to 2 were subjected to detection of 200ppm acetic acid gas resistance change, and the specific steps were:
the prepared gas sensor performance was tested on a WS-30A gas sensor test system. The test voltage is fixed at 5V, and a 10MΩ load resistor card is adopted to adjust the heating voltage to 0V, and the test is carried out at room temperature. In the test process, an internal circulating fan is required to be always started, a film is clamped on a base and is installed in a test system, a sealing cover is covered to start a test after a heating evaporation chamber is opened, the system operates for 50S to obtain a film stable base line, the tested liquid is quantitatively injected from an injection hole, heating is closed after the liquid is volatilized, the cover is uncovered after the liquid is reacted stably, air is introduced to restore the base line position, the sensitivity S (S=Rgas/Rair) and the response and recovery time are calculated, and in addition, a high-temperature thermometer is required to directly test the corresponding working temperature of a ceramic tube under different heating voltages.
The test container is a closed space with the volume of 18L, a small electric fan for assisting in dispersing gas molecules is arranged in the test container, a test table connected with a gas sensor is also arranged in the test container, the gas molecules to be tested are injected through an air inlet on the wall, and the space is an environment which is kept at the same atmospheric pressure, temperature, humidity and air with the outside. The signal of the gas sensor is presented in the form of an electrical signal. The test procedure was as follows: the gas to be tested is selected first, and the test can be started after stable test data are collected, because the sensor is in a stable tested state at this time, so that systematic errors of the test are avoided. Then, a certain amount of measured gas is injected into the container according to the required test concentration, at this time, the gas sensor can generate resistance change due to adsorption of measured gas molecules, the change can be recorded and displayed on the acquisition system software of the computer, after the resistance value is stabilized, the resistance value under the atmosphere of the measured gas can be obtained, the ratio of the resistance value to the resistance value when the gas is not injected is defined as the sensitivity of the gas sensor to the concentration of the measured gas, the time required by the resistance change is response time, finally, the measured gas is extracted, the resistance of the sensor is restored to the original resistance value, the time required by the change is restoration time, and thus, the three most important data of the gas-sensitive test can be obtained through the data acquired by the computer, and the three data are respectively: sensitivity, response time, and recovery time. The test results are shown in fig. 3 and 4.
Fig. 3 is a graph showing the resistance change of the film prepared in example 1 to 200ppm acetic acid gas, and it can be seen from fig. 3 that when acetic acid gas is added, the resistance signal of the sensor changes obviously in a very short time, and the trend of slightly increasing and then decreasing instantaneously is shown, namely the resistance change shows response to acetic acid steam, and the resistance change can be applied to detection of acetic acid steam.
FIG. 4 is a graph showing the response of the films prepared in example 1 and comparative examples 1 to 2 to 200ppm acetic acid gas (Ra/Rg, i.e., the ratio of resistance in the initial state to response resistance). As can be seen from fig. 4, after the acetic acid gas is added, the PTCTA film of comparative example 1 and the ZnO film of comparative example 2 remain near the base line 1 without significant change in response ratio, while the PTCTA & ZnO film of examples shows significant change and can be basically restored to the original state, which means that only the PTCTA and ZnO are compounded, and the oxidation reaction of acetic acid vapor is realized at the interface by forming a special structure of heterojunction, thereby causing the change of the overall conductivity of the material, i.e., the detection of acetic acid vapor is realized.
2. The films prepared in example 1 were tested for different concentrations of acetic acid gas response by the following steps:
the film is clamped on a base, the film is arranged in a test system, the test is started after a sealing cover is covered, an initial baseline of the film is obtained after the system operates for 50 seconds, acetic acid solutions with different volumes (4.7 mu L of acetic acid is added every 100 ppm) are injected on a heating table in the test system by a microsampler to be heated and volatilized, the resistance of the film in acetic acid steam in a sealing environment is changed, then the film is converted into a resistance signal to be displayed on a computer of the test system, and the signal is basically restored to an initial state after the cover is opened for ventilation.
The results are shown in fig. 5, wherein a is a response curve of the PTCTA & ZnO film prepared in example 1 to acetic acid vapor with different concentrations continuously at room temperature, the response time and recovery time of the composite film at 1500ppm of acetic acid vapor are respectively 500s and 600s, and the detection limit of the material to acetic acid vapor is 50ppm as shown in the data, the sensitivity of the PTCTA & ZnO film has obvious dependency on the concentration of acetic acid vapor and shows a strong linear relationship, and the specific concentration of acetic acid vapor can be obtained by inputting a sensitivity value by fitting a curve theoretically.
3. The film prepared in example 1 was subjected to a 200ppm acetic acid performance test for a continuous 3-cycle period, specifically, after the response in acetic acid vapor reached the maximum, the cover was opened and the air was vented, and the signal was restored to the original state substantially, and the process was regarded as one cycle, and the results are shown in fig. 6. From fig. 6, it can be seen that the film still maintains 90% of the detection performance after continuous 3-cycle test, which means that acetic acid vapor can be smoothly adsorbed and desorbed from the film even in a room temperature environment, and the sensitivity is maintained at a higher level, i.e., the cycle performance of the film is better.
4. The film prepared in example 1 was tested for stability to 200ppm acetic acid vapor response over 30 days and the results are shown in FIG. 7. From FIG. 7, the film can still maintain 75% of the performance after 30 days, the performance is not greatly reduced due to external reasons such as physical abrasion, air oxidation and the like, and the film has better stability.
5. The films prepared in example 1 were subjected to resistance change response conditions of 1000ppm of different organic solution vapors, and the results are shown in FIG. 8. From fig. 8, it can be seen that the film has a very low response to VOCs other than acetic acid, and the response to acetic acid is the highest, indicating that the film can achieve selective sensing of acetic acid vapor at room temperature.
6. The PTCTA & ZnO composite films (examples 1 to 3, comparative examples 3 to 5) with different polymerization times have response charts and initial resistance values of 200ppm acetic acid as shown in FIGS. 9 and 10, respectively, the response time and recovery time are shown in FIG. 11, it can be seen from FIG. 9 that the obtained film has the highest sensing performance when the electropolymerization time of TCTA is 600s, which corresponds to the maximum initial resistance under the condition shown in FIG. 10, and it can be seen from FIG. 11 that the response time and recovery time of the film are greatly increased when the electropolymerization time is 700s or more, and that the prepared sensor has better performance and recovery time of the response time when electropolymerization is 500s to 700s.
7. The composite film prepared in example 1 was subjected to X-ray diffraction, and the results are shown in fig. 12. As can be seen from fig. 12, znO prepared by electrodeposition is a typical ZnO hexagonal wurtzite structure.
IR diagrams of TCTA molecules before and after electrochemical polymerization are shown in FIG. 13 (a), detail comparison diagrams are shown in FIG. 13 (b) and 13 (c), the TCTA energy spectrum before polymerization is compared, and 876cm of the TCTA molecules appear after polymerization -1 、811cm -1 This is a C-H out-of-plane bending vibration peak of 1,2, 4-trisubstituted benzene due to a structure formed by crosslinking carbazole groups with each other after electrochemical polymerization. Benzene structural characteristic peak 1478cm of N-Ph-N in TCTA -1 Vanishing and instead 1572cm -1 The characteristic peak of the quinone structure appears, which indicates that TCTA molecule is electropolymerizedAfter that, the degree of conjugation between polymers increases, and monomers are linked by a quinoid structure.
The IR pattern of PTCTA formed after electrochemical polymerization of TCTA molecule before and after addition of acetic acid gas is shown in FIG. 14 (a), the detailed comparison of FIG. 14 (b), 14 (c) shows that 3446cm of PTCTA appears after addition of acetic acid -1 Is the absorption peak of the typical imino-NH-structure, but 1572cm -1 The peak of the quinone structure characteristic is greatly weakened while 1390cm -1 The absorption peak of the Ph-N-Ph aromatic amine appears, which shows that the quinoid structure is greatly reduced due to the addition of acetic acid, the whole conjugated structure is weakened, the mobility of electrons is reduced, and the macroscopic appearance is increased.
10.PTCTA&The mechanism of the ZnO film sensing acetic acid steam is shown in figure 15. As can be seen from FIG. 15, oxygen in the air is adsorbed on the surface of ZnO, and electrons trapped in the conduction band of ZnO are ionized into active oxygen species O - (ads) causing the formation of a surface depletion layer, which is weakened and macroscopically manifested as a decrease in the resistance of the sensor, when acetic acid gas contacts the active oxygen species, both react to release electrons, producing carbon dioxide and water.
11. The response of example 1 to 200ppm acetic acid vapor was tested at different relative air humidities, as shown in fig. 16, and it can be seen from fig. 16 that room temperature sensing of acetic acid vapor can be achieved at air humidities ranging from 40% to 80%, where the detection effect is best at 70%, indicating that the film can maintain a higher detection effect at higher humidity.
12. The response Rg/Ra of example 1 to 200ppm at 90% humidity is shown in FIG. 17, and it can be seen from FIG. 16 that when the air humidity reaches 90%, the film no longer exhibits resistance decrease in acetic acid vapor, only the resistance increase phase occurs, indicating that acetic acid can only react with PTCTA to decrease conjugation degree and cannot react with active oxygen species to release electrons at this time under the environment of ultra-high air humidity, and the signal is represented as resistance increase, contrary to the response mode under other humidity environments.
13. XPS analysis was performed on the thin film materials prepared in examples (PTCTA & ZnO) and comparative examples 1 (PTCTA) and 2 (ZnO), and the results are shown in Table 1 and FIG. 18 below, wherein (a) in FIG. 18 is an N-element XPS analysis chart of PTCTA, (b) is an N-element XPS analysis chart of PTCTA & ZnO, (c) is a Zn-element analysis chart of ZnO, and (d) is a Zn-element analysis chart of PTCTA & ZnO.
TABLE 1
As is clear from Table 1, after the PTCTA is compounded with ZnO, the content of N atoms in the quaternary amine state is increased, which is advantageous for the active oxygen species O - (ads) thereby increasing the material surface O - (ads) content, thereby promoting the generation of an electron depletion layer.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (9)
1. An acetic acid gas sensitive film, wherein the film comprises a conductive polymer film layer and a metal oxide film layer deposited on the surface of the conductive polymer film layer; the conductive polymer film layer contains poly-4, 4' -tri (carbazole-9-yl) triphenylamine;
the acetic acid gas sensitive film is prepared by the preparation method comprising the following steps:
s1: mixing the electrolyte with 4,4' -tris (carbazole-9-yl) triphenylamine monomer to obtain an electropolymerized electrolyte;
s2: placing a three-electrode system consisting of an ITO working electrode, a counter electrode and a reference electrode in the electropolymerization electrolyte in the S1, and electropolymerizing at constant potential to obtain the ITO with the surface deposited with the conductive polymer film layer;
s3: placing a three-electrode system consisting of the ITO with the surface deposited with the conductive polymer film layer serving as a working electrode, a counter electrode and a reference electrode in a water solution containing metal salt, and depositing a metal oxide film layer on the surface of the conductive polymer film layer in a constant potential manner to obtain the acetic acid gas sensitive film;
the concentration of the 4,4' -tris (carbazole-9-yl) triphenylamine monomer in the electropolymerization electrolyte in the S1 is 0.2 mg/mL-2 mg/mL;
and S2, the time of the potentiostatic electropolymerization is 5-15 min.
2. The acetic acid gas-sensitive film according to claim 1, wherein the thickness of the conductive polymer film layer is 200nm to 1000nm.
3. The acetic acid gas-sensitive film according to claim 1, wherein the thickness of the metal oxide film layer is 500nm to 1500nm.
4. A method for producing an acetic acid gas-sensitive film according to any one of claims 1 to 3, comprising the steps of:
s1: mixing the electrolyte with 4,4' -tris (carbazole-9-yl) triphenylamine monomer to obtain an electropolymerized electrolyte;
s2: placing a three-electrode system consisting of an ITO working electrode, a counter electrode and a reference electrode in the electropolymerization electrolyte in the S1, and electropolymerizing at constant potential to obtain the ITO with the surface deposited with the conductive polymer film layer;
s3: placing a three-electrode system consisting of the ITO with the surface deposited with the conductive polymer film layer serving as a working electrode, a counter electrode and a reference electrode in a water solution containing metal salt, and depositing a metal oxide film layer on the surface of the conductive polymer film layer in a constant potential manner to obtain the acetic acid gas sensitive film;
the concentration of the 4,4' -tris (carbazole-9-yl) triphenylamine monomer in the electropolymerization electrolyte in the S1 is 0.2 mg/mL-2 mg/mL;
and S2, the time of the potentiostatic electropolymerization is 5-15 min.
5. The method according to claim 4, wherein the electrolyte solution S1 comprises a co-electrolyte, methylene chloride, tetrahydrofuran and acetonitrile; the concentration of the auxiliary electrolyte in the electrolyte is 0.01mol/L to 0.5mol/L.
6. The method according to claim 4, wherein the constant potential of S2 is 1.6V to 2V.
7. The method according to claim 4, wherein the constant potential in S3 is-1.1V to-1.4V; the constant potential deposition time is 10 min-15 min.
8. An acetic acid gas detection sensor equipped with the acetic acid gas-sensitive film according to any one of claims 1 to 3.
9. Use of the acetic acid gas-sensitive film according to any one of claims 1 to 3 in the detection of acetic acid gas.
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| CN108918600A (en) * | 2018-05-14 | 2018-11-30 | 安徽工业大学 | It is a kind of for detecting the highly selective composite air-sensitive material of acetic acid gas in air |
| CN109254076A (en) * | 2018-09-11 | 2019-01-22 | 南京理工大学 | The preparation method of volatile organic acids gas sensor |
| CN113921726A (en) * | 2020-07-10 | 2022-01-11 | Tcl科技集团股份有限公司 | Nano titanium dioxide film, preparation method thereof and preparation method of photoelectric device |
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| KR20140108051A (en) * | 2013-02-28 | 2014-09-05 | 포항공과대학교 산학협력단 | Conductive thin layer and electronic device comprising the same |
| CN104155414A (en) * | 2014-08-18 | 2014-11-19 | 电子科技大学 | Method for manufacturing polymer composite gas sensitive film |
| CN107369773A (en) * | 2017-06-21 | 2017-11-21 | 华南理工大学 | A kind of organic electroluminescence device and method based on multilayer electropolymerization film preparation |
| CN108918600A (en) * | 2018-05-14 | 2018-11-30 | 安徽工业大学 | It is a kind of for detecting the highly selective composite air-sensitive material of acetic acid gas in air |
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