CN116297696A - Preparation method of COFs iodine vapor electrochemical sensor based on redox activity - Google Patents
Preparation method of COFs iodine vapor electrochemical sensor based on redox activity Download PDFInfo
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 54
- 239000011630 iodine Substances 0.000 title claims abstract description 54
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 29
- 230000000694 effects Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000010931 gold Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- WQOWBWVMZPPPGX-UHFFFAOYSA-N 2,6-diaminoanthracene-9,10-dione Chemical compound NC1=CC=C2C(=O)C3=CC(N)=CC=C3C(=O)C2=C1 WQOWBWVMZPPPGX-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 4
- 230000010802 Oxidation-Reduction Activity Effects 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000010257 thawing Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 238000006479 redox reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 21
- 230000004044 response Effects 0.000 description 13
- 239000003570 air Substances 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 238000002847 impedance measurement Methods 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 239000005338 frosted glass Substances 0.000 description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 239000003758 nuclear fuel Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 208000016560 COFS syndrome Diseases 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013499 data model Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000001917 fluorescence detection Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000013316 polymer of intrinsic microporosity Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000002901 radioactive waste Substances 0.000 description 1
- 239000002915 spent fuel radioactive waste Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
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- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
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Abstract
The invention relates to a preparation method of a COFs iodine vapor electrochemical sensor based on redox activity, which comprises the steps of adding COFs with redox activity into methanol to obtain a mixture, transferring the mixture into an active area of an interdigital electrode, and heating to evaporate a solvent to obtain the iodine vapor electrochemical sensor. The iodine vapor electrochemical sensor has the characteristics of high stability, high selectivity, high sensitivity, capability of sensitively and rapidly detecting iodine vapor due to rapid decrease of impedance of the electrochemical sensor based on oxidation-reduction reaction when air mixed with iodine vapor passes through the electrochemical sensor, simple preparation, low cost, simple process, easy production, high adsorption capacity and the like, and has good application prospect in the fields of iodine vapor sensing technology and the like.
Description
Technical Field
The invention relates to a preparation method of a COFs iodine vapor electrochemical sensor based on redox activity, and belongs to the technical field of gas sensors.
Background
Global energy demand has continued to rise for the 21 st century due to population growth and industry growth, creating significant pressure on existing fossil fuel supplies. The nuclear energy density is high, zero emission is widely regarded as a cleaner alternative energy source for sustainable energy power generation. However, the most serious problem faced by the nuclear industryIs the treatment of radioactive waste produced throughout the nuclear fuel cycle phase. Most of the radionuclide emissions occur during post-treatment of spent fuel, including radioactive iodine, a highly liquid gas with the main volatile components 129 I and 131 I。 131 i is of great interest because of its high activity and the combination of biotoxicity with human metabolic processes, but does not constitute a long-term risk because its half-life is only 8.02 days. While 129 I half-life is long (t) 1/2 ＝1.6×10 7 y), the fluidity is strong in geological environment, and the biological accumulation can be continuously carried out in the atmosphere or carried out through a food chain, so that the human metabolic process is directly influenced, and the human health and the environment are more threatened. Therefore, in nuclear accidents and industrial nuclear fuel post-treatment processes, development of a gas sensor with high response speed and high detection speed is important to public and environmental safety.
In recent years, metal Organic Frameworks (MOFs) and self-contained microporous Polymers (PIMs) have the advantages of high specific surface area and storage capacity, adjustable pore size, uniformly dispersed active sites, post-modification functionalization and the like, and have excellent effects on the adsorption of iodine molecules. Covalent organic framework materials (COFs) are novel covalent organic crystal form porous materials, are connected through covalent bonds, have good chemical stability and thermal stability, are composed of light elements, have low density, are regular in structure, uniform in pore channels, large in specific surface area and good in stability, and contain abundant surface functional groups as crystal form materials, and become ideal adsorption materials for iodine vapor. However, these porous materials are generally used for capturing or adsorbing iodine, and iodine vapor detection is rarely performed.
In recent years, there have been reports on the preparation of fluorescence sensors for the detection of iodine vapor based on stable porous materials, and although fluorescence detection has a clear response, such a reaction is either irreversible in nature or takes a long time to react. And the detection equipment is expensive, large in size and inconvenient to carry.
Electrochemical Impedance Spectroscopy (EIS) is a valuable tool for determining the electrical response of multiphase material systems. In EIS, it is a small amplitude sinusoidal voltage signal applied across the electrodes that defines the impedance, resulting in a measurable current response. Since the frequency of the sine wave is varied, the measurement can be repeated over a wide frequency range, e.g., 100kHz to 10mHz, to facilitate a better understanding of the different components of the system, and to observe the process that is characteristic of a particular frequency range. EIS is widely used in many fields such as ion selective electrodes, biosensors and electrochemical sensors. In summary, electrochemical methods are an ideal choice due to their ease of use, low cost and miniaturized equipment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a COFS iodine vapor electrochemical sensor based on redox activity.
The iodine vapor electrochemical sensor has high stability, high selectivity and high sensitivity, when air mixed with iodine vapor passes through the electrochemical sensor, iodine is captured by the polymer film, the impedance of the electrochemical sensor is rapidly reduced based on oxidation-reduction reaction, the iodine vapor can be sensitively and rapidly detected, and the problems of low efficiency, expensive material, low response speed and the like in the existing detection of the iodine vapor are solved.
The invention is realized by the following technical scheme:
a preparation method of a COFs iodine vapor electrochemical sensor based on redox activity comprises the following steps:
1) Adding COFs with oxidation-reduction activity into methanol, ultrasonically crushing for 5-20min to obtain a mixture a,
2) Soaking the interdigital electrode in methanol, drying under nitrogen, heating in air, cooling to obtain pretreated interdigital electrode,
3) Transferring the mixture a in the step 1) into the active area of the interdigital electrode, heating and evaporating the solvent, and forming a layer of closely adhered film in the active area of the interdigital electrode to obtain the iodine vapor electrochemical sensor.
According to the present invention, in step 1), the COFs having a redox activity are prepared as follows:
adding 2,4, 6-trihydroxy-1, 3, 5-trityl aldehyde and 2, 6-diaminoanthraquinone into a mixed solution of mesitylene and 1, 4-dioxane, performing ultrasonic treatment to form a uniform solution to obtain a mixture b, dropwise adding acetic acid into the mixture b at room temperature, and performing degassing in a freezing-pumping-thawing cycle under a liquid nitrogen bath; sealing, heating for reaction, cooling to room temperature, filtering to obtain red precipitate, washing with acetone, dichloromethane and ethanol respectively, soxhlet extracting with ethanol as extractant, and vacuum drying the product.
According to the present invention, the molar ratio of 2,4, 6-trihydroxy-1, 3, 5-trityl aldehyde to 2, 6-diaminoanthraquinone is preferably (0.6-1): (1-3), the volume ratio of the molar amount of the 2,4, 6-trihydroxy-1, 3, 5-trityl aldehyde to the mixed solution is (0.6-1) mmol: (15-20) mL.
According to the invention, preferably mesitylene: 1, 4-dioxane: the volume ratio of acetic acid is 6:6:1.
According to the invention, the sealed heating reaction is preferably a sealed reaction tube, heated at 120℃for 72 hours.
The reaction formula of COFs with redox activity is shown in the following formula I:
according to the invention, in step 1), the mass-to-volume ratio of COFs with redox activity to methanol is preferably 5-15:1, unit: mg/mL.
Most preferably, in step 1), the mass to volume ratio of COFs with redox activity to methanol is 10:1, unit: mg/mL.
According to the preferred embodiment of the present invention, in the step 2), the interdigital electrode comprises 10 pairs of gold wires, the line width is 80-120 μm, the line distance is 80-120 μm, and the thickness is 0.3-0.5mm.
According to a preferred embodiment of the present invention, in step 2), the interdigital electrode is an Au metal interdigital electrode of an alumina substrate.
According to a preferred embodiment of the invention, in step 2), the soaking time in methanol is 5-15min and the heating in air is to 70 ℃ in air for 30 min.
A COFs iodine vapor electrochemical sensor based on redox activity is prepared by the method.
The invention has the technical characteristics and advantages that:
1. the iodine vapor electrochemical sensor has the characteristics of high stability, high selectivity and high sensitivity, when air mixed with iodine vapor passes through the electrochemical sensor, iodine is captured by a polymer film, the impedance of the electrochemical sensor is rapidly reduced based on oxidation-reduction reaction, the iodine vapor can be sensitively and rapidly detected, the iodine vapor is directly detected by means of an electrochemical impedance spectroscopy method and combining with a covalent organic framework polymer, the preparation is simple, the cost is low, the process is simple and easy to produce, the adsorption capacity is high, and the like, and the iodine vapor electrochemical sensor has good application prospects in the fields of iodine vapor sensing technology and the like.
2. The iodine vapor electrochemical sensor has rapid response, high sensitivity, signal response can occur within 5 minutes after saturated iodine vapor is introduced at room temperature, and the resistance change is about 200×.
3. The iodine vapor electrochemical sensor has high environmental stability and long service life, and meanwhile, the device has smaller volume and is easy to prepare in large batch.
4. The iodine vapor electrochemical sensor has high gaseous iodine selectivity, has negligible response to air, water vapor, methanol, ethanol vapor and the like at room temperature, and can be suitable for detection in complex environments.
5. The main consumable part of the iodine vapor electrochemical sensor comprises: the Au metal interdigital electrode is simple to prepare and convenient to replace, and can be produced in a large scale.
Drawings
FIG. 1 shows the redox active COFs of example 1 13 C nuclear magnetic resonance spectrum.
FIG. 2 is a graph showing the nitrogen adsorption-desorption isotherms of the redox active COFs in example 1.
FIG. 3 is a schematic diagram showing the function of the iodine vapor electrochemical sensor prepared in Experimental example 1.
Fig. 4 is a schematic diagram of an equivalent circuit for creating an impedance data model in experimental example 1 overlaid on an iodine vapor electrochemical sensor.
Fig. 5 is a baud chart of the different treatments in experimental example 1.
Fig. 6 is a baud diagram of the electrochemical sensor of example 2 in experimental example 1 at different temperatures.
Fig. 7 is a graph showing the gas response of the electrochemical sensors of experimental example 1 at different times.
Fig. 8 is a graph showing a selective gas response test of the electrochemical sensor of example 2 in experimental example 1.
FIG. 9 is a graph showing the redox performance of the redox active COFs in example 1.
Detailed description of the preferred embodiments
The present invention is further illustrated by the following examples, which are intended to be illustrative, not limiting, and not intended to limit the scope of the invention.
In the examples, the aluminum oxide substrate Au metal interdigital electrode (IDEs) comprises 10 pairs of gold wires, the line width and the line distance are 100 μm, and the thickness is 0.38mm, which is the prior art.
Example 1:
preparation of redox active COFs:
0.9mmol (189 mg) of 2,4, 6-trihydroxy-1, 3, 5-trityl aldehyde and 1.35mmol (321.3 mg) of 2, 6-diaminoanthraquinone were added to a mixed solution of 9mL of mesitylene and 1, 4-dioxane (1:1, v/v), the mixture was sonicated for 10 minutes to form a homogeneous solution, and then 1.5mL of 6M acetic acid was added dropwise to the mixture at room temperature. The degassing was carried out 3 times in a freeze-pump-thaw cycle under a liquid nitrogen bath. The reaction tube was sealed and heated at 120℃for 72 hours. Cooling to room temperature, filtering to obtain red precipitate, washing with acetone, dichloromethane and ethanol for 4-5 times, respectively, soxhlet extracting with ethanol for 24 hr, and vacuum drying at 70deg.C for 24 hr to obtain red powder.
The prepared COFs with redox activity 13 C nuclear magnetic resonance spectrum is shown in figure 1, and nitrogen adsorption-desorption isotherm curve is shown in figure 2; oxidation of redox active COFsThe reduction activity is shown in FIG. 9.
Example 2:
the preparation method of the COFs iodine vapor electrochemical sensor based on the oxidation-reduction activity comprises the following steps:
1) In a 5mL glass liquid flash bottle, placing the 10mg polymer powder into 1mL methanol, sealing the mixture, ultrasonically crushing for 10min to obtain a mixture a,
2) The Au metal interdigital electrode of the alumina substrate is placed in methanol to be soaked for 10 minutes, dried under nitrogen, heated to 70 ℃ in air for 30 minutes, finally cooled to room temperature for standby,
3) Transferring 10 mu L of the mixture a in the step 1) into an active area of an Au metal interdigital electrode of an alumina substrate, drying on a heating plate, and then heating in air at 70 ℃ for 30 minutes to form a layer of tightly adhered film in the active area of the interdigital electrode to obtain the iodine vapor electrochemical sensor.
Experimental example 1:
1. to equilibrate the iodine vapor, iodine was placed in a 250mL glass bottle with a frosted glass plug and placed in a constant temperature for 2 hours. The sensor of example 2 was then placed in a glass bottle and closed to give IDE+AQ-COF+I 2 An electrochemical sensor; and making different control groups respectively of IDE (Au metal interdigital electrode of blank alumina substrate), IDE+I 2 (glass bottle closure with Au metal interdigitated electrodes of the blank alumina substrate placed in iodine vapor), ide+aq-COF (iodine vapor electrochemical sensor placed in glass bottle closure without iodine vapor), each process Electrochemical Impedance Spectroscopy (EIS) measurement was performed on an electrochemical workstation (Corrtest CS 310M). The high input impedance of the system allows impedance measurements up to 10 12 Omega. Electrochemical Impedance Spectroscopy (EIS) was then performed at a frequency range of 10 -2 -10 5 Hz (70 points total, oscillation amplitude 50mV, offset voltage 0V). The different process electrochemical sensors were placed on 5mm thick alumina plates in a faraday cage and tested at room temperature. Equivalent circuit fitting was performed on the electrochemical impedance data by Zview software.
The baud diagram of the different treatments is shown in fig. 5.
2. Iodine was placed in a 250mL glass bottle with a frosted glass plug and placed in a constant temperature for 2h. The sensor of example 2 was then placed in a glass bottle and closed, and left at 70℃for 0.5 min, 1 min and 5min, respectively, with an iodine vapor pressure of 1.18kPa at 70℃and different controls were made; individual process Electrochemical Impedance Spectroscopy (EIS) measurements were performed on an electrochemical workstation (Corrtest CS 310M). The high input impedance of the system allows impedance measurements up to 10 12 Omega. Electrochemical Impedance Spectroscopy (EIS) was then performed at a frequency range of 10 -2 -10 5 Hz (70 points total, oscillation amplitude 50mV, offset voltage 0V).
The gas response diagrams of different electrochemical sensors at different times are shown in fig. 7.
3. Iodine was placed in a 250mL glass bottle with a frosted glass plug and placed in a constant temperature for 2h. The sensor of example 2 was then placed in a glass jar and closed and left at 25, 30 and 70 ℃ for 5 minutes, respectively, with iodine vapor pressures of 0.041, 0.062kPa, 1.18kPa, respectively, and each processed Electrochemical Impedance Spectroscopy (EIS) measurement performed on an electrochemical workstation (Corrtest CS 310M). The high input impedance of the system allows impedance measurements up to 10 12 Omega. Electrochemical Impedance Spectroscopy (EIS) was then performed at a frequency range of 10 -2 -10 5 Hz (70 points total, oscillation amplitude 50mV, offset voltage 0V).
The baud diagram of the electrochemical sensor of example 2 at different temperatures is shown in fig. 6.
4. The response to possible chemical interferents such as air, methanol, ethanol, and water at room temperature was studied. For air, the test method was the same as iodine vapor, using clean glass bottles without iodine; for methanol, ethanol, and water, 10mL of methanol, ethanol, or water was placed in a glass vial without iodine, again in accordance with the iodine vapor method. The vapor pressures of methanol, ethanol and water at room temperature were 16.8, 8.0 and 3.2kPa, respectively; individual process Electrochemical Impedance Spectroscopy (EIS) measurements were performed on an electrochemical workstation (Corrtest CS 310M). The high input impedance of the system allows impedance measurements up to 10 12 Omega. Electrochemical Impedance Spectroscopy (EIS) was then performed at a frequency range of 10 -2 -10 5 Hz (total 70 points, oscillation)Amplitude 50mV, offset voltage 0V).
The selective gas response of the electrochemical sensor of example 2 is shown in fig. 8, and it can be seen that the electrochemical sensor does not respond to air, methanol, ethanol and water, but only responds to iodine vapor, and has strong interference resistance.
Claims (10)
1. A preparation method of a COFs iodine vapor electrochemical sensor based on redox activity comprises the following steps:
1) Adding COFs with oxidation-reduction activity into methanol, ultrasonically crushing for 5-20min to obtain a mixture a,
2) Soaking the interdigital electrode in methanol, drying under nitrogen, heating in air, cooling to obtain pretreated interdigital electrode,
3) Transferring the mixture a in the step 1) into the active area of the interdigital electrode, heating and evaporating the solvent, and forming a layer of closely adhered film in the active area of the interdigital electrode to obtain the iodine vapor electrochemical sensor.
2. The method according to claim 1, wherein in step 1), the COFs having a redox activity are produced as follows:
adding 2,4, 6-trihydroxy-1, 3, 5-trityl aldehyde and 2, 6-diaminoanthraquinone into a mixed solution of mesitylene and 1, 4-dioxane, performing ultrasonic treatment to form a uniform solution to obtain a mixture b, dropwise adding acetic acid into the mixture b at room temperature, and performing degassing in a freezing-pumping-thawing cycle under a liquid nitrogen bath; sealing, heating for reaction, cooling to room temperature, filtering to obtain red precipitate, washing with acetone, dichloromethane and ethanol respectively, soxhlet extracting with ethanol as extractant, and vacuum drying the product.
3. The method according to claim 2, wherein the molar ratio of 2,4, 6-trihydroxy-1, 3, 5-trityl aldehyde to 2, 6-diaminoanthraquinone is (0.6-1): (1-3), the volume ratio of the molar amount of the 2,4, 6-trihydroxy-1, 3, 5-trityl aldehyde to the mixed solution is (0.6-1) mmol: (15-20) mL.
4. The method of claim 2, wherein mesitylene: 1, 4-dioxane: the volume ratio of acetic acid is 6:6:1.
5. The method according to claim 2, wherein the sealed heating reaction is a sealed reaction tube, and the reaction tube is heated at 120 ℃ for 72 hours.
6. The method according to claim 1, wherein in step 1), the mass-to-volume ratio of COFs having a redox activity to methanol is 5 to 15:1, unit: mg/mL, preferably, in step 1), the mass to volume ratio of COFs with redox activity to methanol is 10:1, units: mg/mL.
7. The method according to claim 1, wherein in the step 2), the interdigital electrode comprises 10 pairs of gold wires, the line width is 80-120 μm, the line spacing is 80-120 μm, and the thickness is 0.3-0.5mm.
8. The method of claim 1, wherein in step 2), the interdigital electrode is an Au metal interdigital electrode of an alumina substrate.
9. The method according to claim 1, wherein in step 2), the soaking time in methanol is 5-15min, and the heating in air is performed at 70 ℃ for 30 min.
10. A redox activity based COFs iodine vapor electrochemical sensor made by the method of claim 1.
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