CN115772284A - 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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- CN115772284A CN115772284A CN202211460616.8A CN202211460616A CN115772284A CN 115772284 A CN115772284 A CN 115772284A CN 202211460616 A CN202211460616 A CN 202211460616A CN 115772284 A CN115772284 A CN 115772284A
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- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 30
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- 150000004706 metal oxides Chemical class 0.000 claims abstract description 19
- 238000001514 detection method Methods 0.000 claims abstract description 18
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
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- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention provides an acetic acid gas sensitive film and 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 film layer; the raw material of the conductive polymer layer includes poly 4,4' -tris (carbazol-9-yl) triphenylamine. The acetic acid gas sensitive film can realize the resistance change effect on the acetic acid gas in the room temperature environment, further realize the specificity detection of the acetic acid gas, has simple and easy preparation method, high sensitivity, short response time and capability of detecting the acetic acid gas with the concentration as low as 50 ppm.
Description
Technical Field
The invention belongs to the high polymer material technology, and particularly relates to an acetic acid gas sensitive film, and a preparation method and application thereof.
Background
The gas-sensitive resistance sensor is made by utilizing the change of the resistance value of a sensitive element caused by the oxidation-reduction reaction of gas on the surface of a semiconductor, is a sensor for converting detected gas components and concentration into resistance signals, and can obtain the information of the gas existing in the environment according to the strength of the signals, thereby realizing the monitoring or alarming function. At present, the resistance-type gas sensor is dominant in the field of commercial gas sensors. The gas-sensitive resistive sensor also has a disadvantage that the gas-sensitive resistive sensor needs to be attached to a heating element to work. Acetic acid, also known as acetic acid, is one of the common harmful air pollutants. When the concentration of acetic acid in the air exceeds 80ppb, one is at risk of developing gastroesophageal reflux. When the concentration of acetic acid in the air exceeds 100ppm, the cultural relics such as coins, sculptures and lacquerwares in the museum are slowly deteriorated. Therefore, detection of low concentration acetic acid vapor is of practical significance. Most of the reported documents have high use temperature of devices for detecting acetic acid vapor, and even if the devices can realize acetic acid detection in a room temperature environment, the preparation method is complex and does not meet the practical use requirement of carbon reduction and energy saving, so that the development of devices for detecting acetic acid vapor at room temperature has certain significance.
Disclosure of Invention
The present invention has been made to solve at least one of the above-mentioned problems occurring in the prior art. Therefore, the invention provides an acetic acid gas sensitive film, which can realize high selectivity resistance change response to acetic acid gas in a room temperature environment.
The second aspect of the invention provides a preparation method of an acetic acid gas sensitive film.
A third aspect of the present invention provides an acetic acid gas detection sensor.
The fourth aspect of the invention provides an application of the acetic acid gas sensitive film in the detection of the acetic acid gas.
According to a first aspect of the present invention, an acetic acid gas-sensitive film is provided, the film comprising 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.
In some embodiments of the present invention, the conductive polymer film layer has a thickness of 200nm to 1000nm.
In some embodiments of the present 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 comprises one of ZnO and CuO.
In some preferred embodiments of the present invention, the metal oxide film layer contains ZnO in a hexagonal wurtzite crystal form.
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 electropolymerization electrolyte;
s2: placing a three-electrode system which is formed by taking ITO (indium tin oxide) as a working electrode, a counter electrode and a reference electrode in the electropolymerization electrolyte S1, and electropolymerizing at a constant potential to obtain ITO with a surface deposited with a conductive polymer film layer;
s3: and (3) taking the ITO with the conductive polymer film layer deposited on the surface of the S2 as a working electrode, placing a three-electrode system consisting of the ITO with a counter electrode and a reference electrode into an aqueous solution containing metal salt, and depositing a metal oxide film layer on the surface of the conductive polymer film layer at a constant potential to obtain the acetic acid gas sensitive film.
In the invention, electropolymerization is carried out on the conductive monomer 4,4' -tri (carbazole-9-yl) triphenylamine in an electrochemical mode to obtain a conductive polymer film layer of a conjugated micropore, and then the conductive polymer film layer is compounded with a metal oxide film layer to obtain an acetic acid gas sensitive film; the conductive polymer reduces the initial resistance of the metal oxide at room temperature, and can realize the resistance change response to the acetic acid gas which cannot be realized by the non-recombination of the metal oxide and the metal oxide film under the action of the heterojunction formed by the conductive polymer and the metal oxide film.
In some embodiments of the invention, the electrolyte of S1 comprises a co-electrolyte, dichloromethane, tetrahydrofuran, and acetonitrile.
In some embodiments of the present invention, the concentration of the co-electrolyte in the electrolyte solution of S1 is 0.01mol/L to 0.5mol/L.
In some embodiments of the present invention, the above-mentioned co-electrolyte is selected from at least one of tetrabutylammonium hexafluorophosphate, lithium perchlorate, lithium tetrafluoroborate, ammonium fluoroborate.
In some embodiments of the present invention, the volume ratio of dichloromethane, tetrahydrofuran and acetonitrile is (1-8): 1: (1-8).
In some embodiments of the invention, the concentration of 4,4',4 "-tris (carbazol-9-yl) triphenylamine in the electropolymerization electrolyte in S1 is 0.2mg/mL to 2mg/mL.
In some embodiments of the present 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 constant potential in S2 is between-1.1V and-1.4V.
In some embodiments of the invention, the time for the potentiostatic electropolymerization in S2 is from 5min to 15min.
In some preferred embodiments of the present invention, the time for the potentiostatic electropolymerization in S2 is from 500S to 700S.
In some preferred embodiments of the present invention, the potentiostatic electropolymerization in S2 further comprises: washing with tetrahydrofuran for 5-10 min, washing with 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 (1).
In some preferred embodiments of the present invention, the constant potential in S3 is 1.6V to 2V.
In some preferred embodiments of the present invention, the potentiostatic deposition time in S3 is from 10min to 15min.
In some preferred embodiments of the present invention, the time of potentiostatic deposition in S3 is 700S to 900S.
In some more preferred embodiments of the present invention, the potentiostatic deposition 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 present invention, the sensitivity of metal oxide to humidity is high, and the phenomenon of sensitivity decrease of the sensor at low and high humidity can be explained by the electron-proton conduction mechanism, and water vapor in the air can be adsorbed on the surface of the metal oxide in different ways and reacts with active oxygen ions on the surface: o is 2 (g) Is changed into O 2 (ads)，O 2 (ads) obtaining electrons to O 2 - (ads), steam H 2 O and O 2 - (ads) formation of 2OH - And releaseAnd (4) electrons.
Under the environment with lower humidity, water vapor in the air is adsorbed on the surface of the acetic acid gas sensitive membrane material in a chemical adsorption mode, and due to the lower concentration of the water vapor in the air, the reaction of the water vapor and active oxygen ions generates less hydroxide radicals, and the emitted electrons are less, namely the number of electrons transferred to the conductive polymer membrane layer is less, which macroscopically shows that the initial resistance of the sensor is higher under the environment with lower humidity. In a high-humidity environment, water vapor in the air is adsorbed on the surface of the material in a physical adsorption mode, and due to the high concentration of the water vapor, a large amount of hydroxyl radicals generated by the reaction of the water vapor and active oxygen ions emit a large amount of electrons and are transferred to the conductive polymer film layer, and meanwhile, the water vapor is gathered in the grain boundary of the metal oxide in the form of water molecules and forms a water layer due to high humidity, so that the conductivity of the sensor is further increased.
The behavior of sensing acetic acid vapor is actually a joint response to acetic acid vapor and water vapor, which are competing in the process. When the humidity of the air is low, the reaction of water vapor and active oxygen ions generates less hydroxide radicals, so that H ionized by acetic acid vapor under the same concentration is generated + Can quickly consume OH - The sensor can smoothly contact with an electron depletion layer on the surface of the metal oxide and react to release electrons, the surface depletion layer is weakened, the resistance of the sensor is reduced, and the corresponding response time is shorter. In contrast, in a high humidity environment, H is ionized by acetic acid vapor + Can not rapidly consume OH - And because the existence of the water layer on the surface of the metal oxide further prevents acetic acid vapor from contacting the electron depletion layer, the corresponding response time is longer, and even under the environment of 90% humidity, the phenomenon of resistance reduction does not occur.
The invention has the beneficial effects that:
the acetic acid gas sensitive film can realize the specific detection of the acetic acid gas in the room temperature environment, and has the advantages of simple and easy preparation method, high sensitivity, detection limit of 50ppm and response time as low as 5s.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic view of a process for producing an acetic acid gas-sensitive film according to example 1 of the present invention;
FIG. 2 is a schematic diagram of a process for detecting gas-sensitive properties of an acetic acid gas-sensitive film sample according to example 1 of the present invention;
FIG. 3 is a graph showing the resistance change of the film prepared in example 1 of the present invention against 200ppm acetic acid gas;
FIG. 4 is a graph comparing the response of the films prepared in example 1 of the present invention and comparative examples 1 to 2 to 200ppm acetic acid gas;
FIG. 5 is a graph A showing the response of the film prepared in example 1 of the present invention to different concentrations of acetic acid vapor at room temperature, and a graph B showing the fitted curve of acetic acid gas concentration and film sensitivity;
FIG. 6 is a graph of the results of a continuous 3 cycle 200ppm acetic acid performance test on films prepared in example 1;
FIG. 7 is a graph showing the results of testing the stability of the 200ppm acetic acid vapor response of the film prepared in example 1 over 30 days;
FIG. 8 is a graph showing the response of the films prepared in example 1 to resistance change for 1000ppm vapors of different organic solutions;
FIG. 9 is a graph comparing 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 a comparison of the resistance values of the films prepared in examples 1 to 3 and comparative examples 3 to 5 in the initial state;
FIG. 11 is a graph of response time versus recovery time for 200ppm acetic acid vapor for films prepared in examples 1-3 and comparative examples 3-5;
FIG. 12 is a graph showing the results of X-ray diffraction of the thin film prepared in example 1;
FIG. 13 (a) is an infrared schematic of TCTA monomer and PTCTA film, (b) and (c) are detailed magnifications of the key wavenumber ranges, respectively;
FIG. 14 is (a) an infrared schematic of film samples of example 1, comparative example 1 and comparative example 2, (b) and (c) detailed magnifications of key wavenumber ranges, respectively;
FIG. 15 is a diagram illustrating a 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 different air humidities;
FIG. 17 is a graph of the response of the film prepared in example 1 to 200ppm acetic acid vapor at 90% air humidity;
in FIG. 18, (a) is a nitrogen element diagram of an X-ray photoelectron spectrum of a thin film prepared in comparative example 1, (b) is a nitrogen element diagram of an X-ray photoelectron spectrum of a thin film prepared in example 1, (c) is an oxygen element diagram of an X-ray photoelectron spectrum of a thin film prepared in comparative example 2, and (d) is an oxygen element diagram of an X-ray photoelectron spectrum of a thin film prepared in example 1.
Detailed Description
The idea of the invention and the resulting technical effects will be clearly and completely described below in connection with the embodiments, so that the objects, features and effects of the invention can be fully understood. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the processes used are conventional in the art unless otherwise specified. The TCTA used has the formula shown below and can be prepared by methods well known in the art.
Example 1
The embodiment prepares the acetic acid gas sensitive film, and the specific process is as follows:
(1) 0.1937g of tetrabutylammonium hexafluorophosphate, 3mL of tetrahydrofuran, 1.5mL of dichloromethane, 0.5mL of acetonitrile, and 3mg of TCTA (4, 4' -tris (carbazol-9-yl) triphenylamine) were mixed to obtain 5mL of an electropolymerization electrolyte.
(2) Soaking ITO glass subjected to ultrasonic washing and drying in isopropanol, deionized water and ITO washing liquor in sequence to serve as a working electrode, soaking the working electrode, a silver-silver ion electrode and a platinum sheet electrode together serving as a three-electrode system in electropolymerization electrolyte prepared in the step (1), setting the potential to be 1.62V, performing electropolymerization in a constant potential mode for 600s, then respectively soaking the ITO working electrode in tetrahydrofuran and deionized water for 5min to clean impurities such as unpolymerized monomers, and performing vacuum drying at 60 ℃ for 24h to obtain ITO with a surface deposited conductive polymer film (PTCTA).
(3) The ITO with the conductive polymer film deposited on the surface obtained in the step (2) is taken as a working electrode, a platinum electrode is taken as a counter electrode, a saturated KCl electrode is taken as a reference electrode to form a three-electrode system together, and the three-electrode system is soaked in Zn (NO) with the concentration of 0.1mol/L 3 ) 2 The temperature of the aqueous solution is raised to 65 ℃, znO is deposited on the surface of the PTCTA in a constant potential electrodeposition mode with the potential of-1.2V, the deposition time is 800s, then the aqueous solution is soaked in deionized water for 10min to clean ions attached to the film, and then vacuum drying is carried out for 24h at 60 ℃ to obtain the acetic acid gas sensitive film (PTCTA)&ZnO film).
Example 2
The embodiment prepares the acetic acid gas sensitive film, and the specific process is as follows:
(1) 0.1937g of tetrabutylammonium hexafluorophosphate, 3mL of tetrahydrofuran, 1.5mL of dichloromethane, 0.5mL of acetonitrile, and 3mg of TCTA (4, 4' -tris (carbazol-9-yl) triphenylamine) were mixed to give 5mL of an electropolymerization electrolyte.
(2) Soaking ITO glass subjected to ultrasonic washing and drying in isopropanol, deionized water and ITO washing liquor in sequence to serve as a working electrode, soaking the working electrode, a silver-silver ion electrode and a platinum sheet electrode together serving as a three-electrode system in electropolymerization electrolyte prepared in the step (1), setting the potential to be 1.62V, performing electropolymerization in a constant potential mode for 500s, then respectively soaking the ITO working electrode in tetrahydrofuran and deionized water for 5min to clean impurities such as unpolymerized monomers, and performing vacuum drying at 60 ℃ for 24h to obtain ITO with a surface deposited conductive polymer film (PTCTA).
(3) The ITO with the conductive polymer film deposited on the surface obtained in the step (2) is taken as a working electrode, a platinum electrode is taken as a counter electrode, a saturated KCl electrode is taken as a reference electrode to form a three-electrode system together, and the three-electrode system is soaked in Zn (NO) with the concentration of 0.1mol/L 3 ) 2 The temperature of the aqueous solution is raised to 65 ℃, znO is deposited on the surface of the PTCTA in a constant potential electrodeposition mode with the potential of-1.2V, the deposition time is 800s, then the aqueous solution is soaked in deionized water for 10min to clean ions attached to the film, and then vacuum drying is carried out for 24h at 60 ℃ to obtain the acetic acid gas sensitive film (PTCTA)&ZnO film).
Example 3
The embodiment prepares the acetic acid gas sensitive film, and the specific process is as follows:
(1) 0.1937g of tetrabutylammonium hexafluorophosphate, 3mL of tetrahydrofuran, 1.5mL of dichloromethane, 0.5mL of acetonitrile and 3mg of TCTA (4, 4' -tris (carbazol-9-yl) triphenylamine) were mixed to give 5mL of an electropolymerized electrolyte.
(2) Soaking ITO glass subjected to ultrasonic washing and drying in isopropanol, deionized water and ITO washing liquor in sequence to serve as a working electrode, soaking the working electrode, a silver-silver ion electrode and a platinum sheet electrode together serving as a three-electrode system in electropolymerization electrolyte prepared in the step (1), setting the potential to be 1.62V, performing electropolymerization in a constant potential mode for 700s, then respectively soaking the ITO working electrode in tetrahydrofuran and deionized water for 5min to clean impurities such as unpolymerized monomers and auxiliary electrolyte, and performing vacuum drying at 60 ℃ for 24h to obtain ITO with a surface deposited conductive polymer film (PTCTA).
(3) Using the ITO with the conductive polymer film deposited on the surface 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, and soaking the three-electrode system in Zn (NO) with the concentration of 0.1mol/L 3 ) 2 The temperature of the aqueous solution is raised to 65 ℃, znO is deposited on the surface of PTCTA in a constant potential electrodeposition mode with the potential of-1.2V, the deposition time is 800s, then the PTCTA is soaked in deionized water for 10min to clean ions attached to a film, and then vacuum drying is carried out for 24h at 60 ℃ to obtain the acetic acid gas sensitive filmMembrane (PTCTA)&ZnO film).
Comparative example 1
This comparative example prepared a TCTA film, which differed from example 1 in that it was not composited with ZnO (i.e., lacking step (3)), by the following specific procedure:
(1) 0.1937g of tetrabutylammonium hexafluorophosphate, 3mL of tetrahydrofuran, 1.5mL of dichloromethane, 0.5mL of acetonitrile, and 3mg of TCTA (4, 4' -tris (carbazol-9-yl) triphenylamine) were mixed to obtain 5mL of an electropolymerization electrolyte.
(2) Using ITO glass which is soaked in isopropanol, deionized water and ITO lotion in sequence and subjected to ultrasonic washing and drying as a working electrode, soaking the working electrode, the silver-silver ion electrode and a platinum sheet electrode together as a three-electrode system in electropolymerization electrolyte prepared in the step (1), setting the potential to be 1.62V, performing electropolymerization in a constant potential mode for 600s, then respectively soaking the ITO working electrode in tetrahydrofuran and deionized water for 5min to clean impurities such as unpolymerized monomers, and performing vacuum drying at 60 ℃ for 24h to obtain ITO with a surface deposited conductive polymer film (PTCTA).
Comparative example 2
This comparative example prepared a ZnO film, which differs from example 1 in that it was not composited with TCTA (i.e., step (2) was absent), otherwise referred to example 1.
Comparative example 3
This comparative example, which prepared an acetic acid gas-sensitive film, was different from example 1 in the time for the electropolymerization in step (2), and the polymerization time of this comparative example was 200s, and otherwise referred to example 1.
Comparative example 4
This comparative example, which prepared an acetic acid gas-sensitive film, was different from example 1 in the time for the electropolymerization in step (2), and the polymerization time of this comparative example was 300s, and otherwise referred to example 1.
Comparative example 5
This comparative example, which prepared an acetic acid gas-sensitive film, was different from example 1 in the time of electropolymerization in step (2), and the polymerization time of this comparative example was 400s, and otherwise referred to example 1.
Test examples
1. The films prepared in example 1 and comparative examples 1-2 were tested for resistance change with 200ppm acetic acid gas, and the specific steps were:
the performance of the prepared gas sensor is tested on a WS-30A gas sensor testing system. The test voltage is fixed at 5V, a 10M omega load resistance card is adopted, the heating voltage is adjusted to 0V, and the detection is kept at room temperature. In the testing process, an internal circulating fan is required to be started all the time, the film is clamped on a base and installed in a testing system, a sealing cover is covered to open a heating evaporation chamber, the testing is started, the system runs for 50S to obtain a stable base line of the film, the liquid to be tested is injected quantitatively from an injection hole, heating is closed after the liquid is volatilized, after response is stable, the cover is uncovered, air is introduced to recover the base line, the sensitivity S (S = Rgas/Rair) and the response and recovery time are calculated, and in addition, a high-temperature thermometer is required to be used for directly testing the corresponding working temperature of the ceramic tube under different heating voltages.
The test container is a sealed space with a volume of 18L, a small electric fan for assisting the dispersion of gas molecules is arranged in the test container, a test board connected with a gas-sensitive 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 represented 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 is acquired, because the sensor is in a stable state to be tested at the moment, and therefore the system error of the test is avoided. Then according to the required test concentration inject a certain amount of gas to be tested into the container, at this moment the gas sensor will absorb the gas molecule to be tested and generate the resistance change, this change will be recorded and displayed on the computer collection system software, after the resistance value stabilizes, the resistance value under the atmosphere of the gas to be tested can be obtained, the ratio of this resistance value to the resistance value when not injecting gas is defined as the sensitivity of the gas sensor to the gas to be tested of this concentration, and the time required for this resistance change is the response time, finally the gas to be tested is extracted, the resistance of the sensor restores to the original resistance value again, and the time required for this change is the restoration time, so the data collected by the computer can obtain the three most important data of this gas test, which are: 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 the resistance signal of the sensor changes significantly in a very short time by adding acetic acid gas, and shows a trend of first weak increase and then instant decrease, i.e. shows response to acetic acid vapor, and the resistance change can be applied to the detection of acetic acid vapor.
Fig. 4 is a graph comparing the response of the films prepared in example 1 and comparative examples 1 to 2 to 200ppm of acetic acid gas (Ra/Rg is a ratio of resistance/response resistance in an initial state). As can be seen from fig. 4, after the acetic acid gas is added, the response ratio of the PTCTA film of comparative example 1 and the ZnO film of comparative example 2 is still maintained near the baseline 1 and has no significant change, while the PTCTA & ZnO films of examples have significant changes and can be substantially restored to the initial state, which shows that only the PTCTA and ZnO are compounded to realize the oxidation reaction of the acetic acid vapor on the interface through the special structure of the heterojunction, thereby causing the change of the overall conductivity of the material, i.e. realizing the detection of the acetic acid vapor.
2. The film prepared in example 1 was tested for response to acetic acid gas of different concentrations, and the specific steps were:
the film is clamped on a base, the film is installed in a testing system, the testing is started after a sealing cover is covered, an initial baseline of the film is obtained after the system runs for 50s, 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 testing system by a micro sampler to be heated and volatilized, the resistance of the film in acetic acid vapor in a sealed environment is changed and then converted into a resistance signal to be displayed on a computer of the testing system, and the signal is basically recovered to the initial state after the cover is opened and ventilated.
The results are shown in fig. 5, wherein a is a response curve of the PTCTA & ZnO film prepared in example 1 under room temperature environment continuously to acetic acid vapor with different concentrations, the response time and recovery time of the composite film under 1500ppm acetic acid vapor are respectively 500s and 600s, and for 50ppm acetic acid vapor are respectively 54s and 72s, the data show that the detection limit of the material to the acetic acid vapor is 50ppm, as can be clearly seen in b, the sensitivity of the PTCTA & ZnO film has obvious dependence on the acetic acid vapor concentration and shows strong linear relation, and the specific acetic acid vapor concentration can be obtained by theoretically fitting the curve and inputting the sensitivity value.
3. The film prepared in example 1 was subjected to a 200ppm acetic acid performance test for 3 consecutive cycles, specifically, after the response in acetic acid vapor reached a maximum, the cover was opened and the vent was vented, and the signal was substantially restored to the original state, which was regarded as one cycle, and the results are shown in fig. 6. It can be seen from fig. 6 that the film still maintained 90% of the detection performance after the continuous 3-cycle test, which indicates that the acetic acid vapor can be smoothly adsorbed and desorbed from the film even under the room temperature environment, and the sensitivity is maintained at a high level, i.e., the cycle performance of the film is good.
4. The stability of the 200ppm acetic acid vapor response over 30 days was tested for the film prepared in example 1 and the results are shown in fig. 7. From FIG. 7, the film can still maintain 75% of 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 film prepared in example 1 was subjected to resistance change responses of 1000ppm vapors of different organic solutions, and the results are shown in FIG. 8. From fig. 8, it can be seen that the membrane responds to VOCs other than acetic acid to a very low degree, with the highest response to acetic acid, indicating that the membrane can achieve selective sensing of acetic acid vapor at room temperature.
6. The response graphs and initial resistance values of PTCTA & ZnO composite films (examples 1-3, comparative examples 3-5) with different polymerization times to 200ppm acetic acid are respectively shown in FIG. 9 and FIG. 10, and the response time and recovery time are shown in FIG. 11, it can be seen from FIG. 9 that when the electropolymerization time of TCTA is 600s, the obtained film has the highest sensing performance, which corresponds to the maximum initial resistance under the condition in FIG. 10, and it can be seen from FIG. 11 that when the electropolymerization time is more than 700s, the response time and recovery time of the film are greatly increased, and in combination, the sensors prepared by electropolymerization for 500 s-700 s have better performance and recovery time of the response time.
7. The composite film prepared in example 1 was subjected to X-ray diffraction, and the result is shown in FIG. 12. As can be seen from fig. 12, znO prepared by electrodeposition is a typical ZnO hexagonal wurtzite structure.
The IR chart before and after the electrochemical polymerization of the TCTA molecule is shown in FIG. 13 (a), the detail comparison charts are shown in FIGS. 13 (b) and 13 (c), and the comparison of the TCTA energy spectrum before the polymerization shows that 876cm appears after the polymerization -1 、811cm -1 Is a C-H out-of-plane bending vibration peak of 1,2, 4-trisubstituted benzene due to a structure formed by mutual crosslinking of carbazole groups after electrochemical polymerization. Benzene type structure characteristic peak 1478cm of N-Ph-N in TCTA -1 Disappear and replace with 1572cm -1 The peak of quinoid structure is appeared, which shows that after TCTA molecule is electropolymerized, the conjugation degree between polymers is increased, and the monomers are connected by quinoid structure.
The IR chart before and after adding acetic acid gas to PTCTA formed after electrochemical polymerization of TCTA molecules is shown in FIG. 14 (a), the detailed comparison chart is shown in FIGS. 14 (b) and 14 (c), and the comparison shows that 3446cm of PTCTA appears after adding acetic acid -1 Is the absorption peak of the typical imino-NH-structure, and 1572cm -1 The characteristic peak of the quinoid structure at the position is greatly weakened and at the same time 1390cm -1 The absorption peak of 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, and the fluidity of electrons is reduced, and the resistance is macroscopically increased.
10.PTCTA&The ZnO thin film sensing acetic acid vapor mechanism is shown in FIG. 15. As can be seen from fig. 15, oxygen in the air is adsorbed on the surface of ZnO, and electrons are captured from the conduction band of ZnO and ionized into active oxygen species O - (ads), leading to the formation of a surface depletion layer, which reacts to release electrons when acetic acid gas comes into contact with the reactive oxygen species, producing carbon dioxide and water, which is weakened and macroscopically manifested as a decrease in the resistance of the sensor.
11. The response value of example 1 to 200ppm acetic acid vapor is tested under different relative air humidities, and the result is shown in fig. 16, and it can be seen from fig. 16 that room temperature sensing of acetic acid vapor can be realized in the range of 40% -80% of air humidity, wherein the detection effect is the best at 70%, which indicates that the film can maintain high detection effect in a higher humidity environment.
12. The response Rg/Ra of example 1 to 200ppm under 90% humidity is shown in FIG. 17, and it can be seen from FIG. 16 that when the air humidity reaches 90%, the resistance of the film in acetic acid vapor is no longer reduced, and only the resistance is increased, which indicates that under the environment of ultra-high air humidity, the acetic acid can only react with PTCTA to reduce the conjugation degree, but can not react with active oxygen substances to release electrons, and the signal shows that the resistance is increased, and the response mode is opposite to that 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, in fig. 18, (a) 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, the content of N atom in the quaternary amine state increases after PTCTA is composited with ZnO, which is advantageous for the active oxygen species O - Adsorption of (ads) to increase material surface O - (ads) content, thereby promoting the generation of an electron depletion layer.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. An acetic acid gas sensitive film, which is characterized by comprising 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.
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. The method for preparing an acetic acid gas-sensitive film according to any one of claims 1 to 3, comprising the steps of:
s1: mixing the electrolyte with a 4,4' -tris (carbazole-9-yl) triphenylamine monomer to obtain an electropolymerization electrolyte;
s2: placing a three-electrode system which is formed by taking ITO as a working electrode, a counter electrode and a reference electrode in the electropolymerization electrolyte S1, and performing constant potential electropolymerization to obtain ITO with a conductive polymer film layer deposited on the surface;
s3: and (3) taking the ITO with the conductive polymer film layer deposited on the surface of the S2 as a working electrode, placing a three-electrode system consisting of the ITO with a counter electrode and a reference electrode into an aqueous solution containing metal salt, and depositing a metal oxide film layer on the surface of the conductive polymer film layer at a constant potential to obtain the acetic acid gas sensitive film.
5. The method according to claim 4, wherein the electrolyte solution of S1 comprises a co-electrolyte, dichloromethane, tetrahydrofuran and acetonitrile; the concentration of the auxiliary electrolyte in the electrolyte is 0.01 mol/L-0.5 mol/L.
6. The method according to claim 4, wherein the concentration of 4,4',4 "-tris (carbazol-9-yl) triphenylamine monomer in the electropolymerization electrolyte in S1 is 0.2mg/mL to 2mg/mL.
7. The method according to claim 4, wherein the constant potential in S2 is 1.6V to 2V; the time of the constant potential electropolymerization is 5-15 min.
8. The method according to claim 4, wherein the constant potential in S3 is-1.1V to-1.4V; the constant potential deposition time is 10-15 min.
9. An acetic acid gas detection sensor comprising the acetic acid gas-sensitive film according to any one of claims 1 to 3.
10. Use of the acetic acid gas-sensitive film according to any one of claims 1 to 3 for detection of acetic acid gas.
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| CN109254076A (en) * | 2018-09-11 | 2019-01-22 | 南京理工大学 | The preparation method of volatile organic acids gas sensor |
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