CN111912883A - PEDOT for the detection of gaseous hydrogen peroxide: PSS visual chemosensitive sensor - Google Patents
PEDOT for the detection of gaseous hydrogen peroxide: PSS visual chemosensitive sensor Download PDFInfo
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Abstract
The invention discloses a method for detecting PEDOT of gas-phase hydrogen peroxide: a PSS visual chemosensor relates to the technical field of gas detection technology and organic optoelectronic materials. The sensor of the present invention was fabricated by spin coating PEDOT: PSS-titanyl organo-ate films, then amperometric at the ratio PEDOT: the PSS-titanyl organic acid salt film is electrochemically polymerized to prepare the PEDOT film. The sensor prepared by the invention can realize the gas phase H2O2The dual effective detection of electrical signals and visualization has the practical application value of industrial and biological monitoring, a new method is provided for the detection of chemical active gas, and the electrode material can realize self-repair in a moisture-driven manner, thereby having great significance for prolonging the service life and improving the performance stability of the device.
Description
Technical Field
The invention relates to the technical field of gas detection technology and organic optoelectronic materials, in particular to a method for detecting PEDOT of gas-phase hydrogen peroxide: PSS visualization chemosensitive sensor.
Background
Hydrogen peroxide (H)2O2) The aqueous solution of (a) is usually called hydrogen peroxide, has strong oxidizing property, is a common disinfectant, bactericide, bleaching agent and oxidant, and is widely applied to the fields of industrial bleaching, surgical disinfection and the like. As an important active oxygen in vivo, H is usually used2O2Is necessary and beneficial to the organism, but when H2O2When excessive, various diseases may be caused. Gas phase H relative to liquid phase2O2Detection techniques (in the presence of moisture, with oxidizing properties) are lacking and present significant challenges. Furthermore, peroxidized explosives such as triacetoneperoxide (TATP) contain unstable peroxide groups (-O-O-), and are easily photolyzed to generate H2O2Are considered to be marker compounds for the detection of such explosives. The explosive is easy to obtain raw materials, simple in manufacturing process and extremely sensitive to heat, collision and friction, more than two grams of TATP can explode, the smaller mass of TATP can explode even under a slightly closed condition, and the smaller mass of TATP is called as entropy explosive, so that the explosive is urgently required to be detected quickly and cheaply. Only a few documents report the fluorescence method on H2O2The gas phase detection method has the problems of long detection reaction time, troublesome material selection and synthesis, difficult sampling and signal conversion, complicated instrument calibration, large environmental interference and the like. H2O2The accurate detection of the method has important significance in the aspects of food analysis, biology, industry, clinical control, environmental monitoring and the like.
In the search for sensing materials, conductive polymers have reversible electrical properties, and can change resistance, current or electrochemical potential through reaction with chemical substances, and are considered to be good candidates for chemical gas sensors. Wherein, the poly (3, 4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS) has good chemical and thermal stability and excellent film forming and processability, and is currently Commercialized (CLEVIOS)TM) The most successfulOne of the conductive polymers, PEDOT: PSS is often used in combination with other materials for detecting certain components in a liquid phase system by an electrochemical method, and no relevant technical report on chemosensitivity and visual detection of chemically active gases exists. PEDOT: PSS can be converted from original deep blue to semitransparent light blue to complete transparency in oxidation doping, and simultaneously, H2O2It can also be in the form of Fenton's reagent (Fe)2+/3+/H2O2) Or realizing the conditions of PEDOT: PSS and other conductive polymers are prepared, but are not commonly used due to their relatively weak oxidizing properties. The maximum concentration of commercial hydrogen peroxide is 50% (9.17mmHg, 25 ℃), 3% is the concentration of general disinfectant, the level is not higher than the level when the disinfectant is used as an oxidant, the influence on the degradation of polymers is controllable, the saturated vapor pressure generated by the disinfectant is from trace ppb to trace ppm, and H released by decomposition of peroxide explosives is2O2Commonly at the ppt-ppb level. Taking into account the low concentration of H2O2Weak oxidation to PEDOT: the PSS film has no obvious influence on the color, organic titanium oxysalt is selected as a color developing additive to enhance the visual response of the color, and the titanium oxysalt and H are mixed2O2The complex forms Ti (IV) -peroxide bond, the maximum absorption wavelength is about 400nm, and the obvious color change is shown, and the color change induced by the complex is only for H2O2Has selectivity and is not interfered by water, oxygen or common organic reagents (such as alcohol, hexane, acetone and the like). For most gas phase sensing, the effects of moisture are not negligible, so there is a need for a PEDOT: PSS visual chemosensor capable of detecting H2O2Can also realize the concentration of H2O2A visual response of the gas; the sensor is capable of self-repairing when damaged.
Disclosure of Invention
In order to solve the problems, the invention provides a method for detecting PEDOT in gas-phase hydrogen peroxide: PSS visualization chemosensitive sensor. By means of H2O2Oxidizing power of, binding pair H2O2Selective organic titanium oxideSalt; considering moisture versus PEDOT: PSS electric property and structure stability, the electrochemical polymerization PEDOT layer is selected to weaken the surface hydrophilicity and enhance the film conductivity and stability, and meanwhile, the surface nano structure of the electropolymerization PEDOT layer can also strengthen the H pair2O2The adsorption of gas finally realizes that the film electrode material is used for adsorbing gas phase H2O2The dual signal response of (2).
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, a method for detecting PEDOT: PSS visualizes chemosensitive sensors, which are prepared by the following method:
(1) ultrasonically cleaning a substrate by using dichloromethane, acetone, ethanol and ultrapure water in sequence, drying the substrate by using nitrogen, and then cleaning the substrate by using ultraviolet ozone to obtain a pretreated substrate;
(2) reacting poly (3, 4-ethylenedioxythiophene): the solution of polystyrene sulfonate (PEDOT: PSS) was filtered, and the ratio of PEDOT: adding dimethyl sulfoxide (DMSO), Isopropanol (IPA) and organic acid titanyl salt with the mass fraction of 1% -15% into the PSS solution, carrying out ultrasonic treatment, and stirring for 24h at 25 ℃ to obtain PEDOT: PSS-titanyl organic acid salt solution;
(3) and (3) preparing PEDOT obtained in the step (2): and (3) spin-coating a PSS-organic acid titanyl salt solution on the pretreated substrate obtained in the step (1), and drying to obtain a uniform coverage PEDOT: PSS-substrate of titanyl salt of organic acid thin film;
(4) adding a 3, 4-Ethylenedioxythiophene (EDOT) monomer into the electrolyte, taking a platinum sheet electrode as an auxiliary electrode and silver/silver chloride as a reference electrode, and uniformly covering the PEDOT obtained in the step (3): and (3) taking the substrate of the PSS-organic acid titanyl salt film as a working electrode, and electrochemically polymerizing at room temperature by a time current method to obtain a film with uniform coverage of PEDOT: PSS-a substrate of organic acid titanyl oxide/PEDOT film, washing acetonitrile, and drying with nitrogen to obtain a substrate loaded with PEDOT: PSS-sensor of titanyl salt of organic acid/PEDOT film.
Preferably, in step (1), the substrate is a rigid glass substrate or a flexible plastic substrate.
Preferably, in the step (2), PEDOT: filtering the PSS solution through a polytetrafluoroethylene filter membrane with the aperture of 0.45 mu m; the organic acid titanium oxysalt is Ammonium Titanyl Oxalate (ATO) or Potassium Titanyl Oxalate (PTO).
Preferably, in the step (3), the spin coating is: the rotating speed is 1500rpm when the spin coating is started, the rotating speed is increased to 2500-4000 rpm after the spin coating is carried out for 20-40 s, and the spin coating is continued for 10-20 s.
Preferably, in the step (3), 100 to 160 μ L of PEDOT is spin-coated on each 1 × 2em of pretreated substrate: PSS-titanyl organic acid salt solution.
Preferably, in the step (3), the drying temperature is 50 ℃ and the drying time is 2 h.
Preferably, in the step (4), the electrolyte is obtained by uniformly mixing 0.1M tetrabutylammonium hexafluorophosphate serving as a supporting electrolyte and acetonitrile serving as an electrolytic solvent.
Preferably, in the step (4), the controlled polymerization potential of the chronoamperometric electrochemical polymerization is 1.2 to 1.4V, and the polymerization time is 10 to 30 s.
In a second aspect of the invention, there is provided the use of the sensor described above for detecting gaseous hydrogen peroxide.
In a third aspect of the present invention, there is provided a method for detecting gaseous hydrogen peroxide by the sensor, comprising: h is to be2O2Putting the solution into a glass pool, sealing until the solution reaches saturated vapor pressure, and detecting the content of PEDOT: the visual quick sensor that passes of PSS hangs in H behind connecting test circuit2O2At the very center above the solution, PEDOT: PSS-titanium oxysalt of organic acid/PEDOT film resistance value according to H at saturated vapor pressure2O2Constructing a detection standard curve according to the change relation of the gas concentration and the resistance value, and calculating H in the solution to be detected according to the standard curve2O2The gas concentration.
Preferably, the method can also be used for detecting the concentration of the hydrogen peroxide in the gas phase by using the PEDOT: PEDOT of PSS visualization chemosensitive sensor: color change judgment H for PSS-titanyl organic acid salt/PEDOT film2O2The gas concentration is such that the film color is from deep blue to transparent yellow, the lighter the color isDescription of the invention H2O2The higher the gas concentration. The color visualization effect is good.
PEDOT: PSS-titanyl organic acid/PEDOT film pitch H2O2The height of the liquid level of the solution has little influence on the detection effect, and the PEDOT can be set according to the size of the glass pool or the actual situation: PSS-titanyl organic acid/PEDOT film pitch H2O2Height of solution level, PEDOT: PSS-titanyl organic acid/PEDOT film and H2O2The solution is not contacted.
Preferably, said H2O2The detection standard curve of the change relation of the concentration and the resistance value is as follows: y-1397.76758 +4284.03812 x.
Preferably, the linear range is: 5ppb to 214 ppm; the lower detection limit is: 0.08 ppb. If the system is further tested, the thin film is thinned, the area is smaller, the conductivity is higher, and a better sensing signal can be obtained.
The invention has the beneficial effects that:
1. the invention is based on PEDOT: the film prepared by PSS and organic acid titanyl salt can realize H pair2O2Dual signal detection of gases, i.e. change of electrical signal and macroscopic color transition. The electropolymerized PEDOT layer not only improves the conductivity, the sensing sensitivity and the testing reliability, but also weakens the influence of moisture and improves the sensing reliability, and the surface nano structure of the PEDOT layer can also enhance the H pair2O2And (4) adsorbing the gas. The conductivity is improved by adding the DMSO and other conductive promoters, and if the thin film is thinner and has a smaller area, a better sensing signal can be obtained, so that the lower limit of detection is lower.
2. The preparation method has the advantages of simple preparation process and low cost, and can realize H pair2O2The gas detection is effective, and the visual response is realized, so that a new solution is provided for the detection of the chemically active gas.
3. The sensor of the invention has the self-repairing capability driven by moisture, and the ratio of PEDOT: the PSS-organic acid titanyl salt/PEDOT film can be self-repaired after being damaged, is suitable for detection under various severe conditions, and enlarges the detection range.
Drawings
FIG. 1 is a schematic diagram of a dual-mode sensing architecture according to the present invention;
fig. 2 is PEDOT prepared in example 2: microscopic images of the PSS/PEDOT film at the crack wounds before and after repair;
FIG. 3 shows the exposure of the thin films prepared in examples 2 to 4 to H2O2Pictures before and after 30min of gas;
in the figure, (a) (c) (e) shows the original condition of the film, and (b) (d) (f) shows the film exposed to H2O2Color status after 30min of gas, (a) and (b) are pictures of example 2, (c) and (d) are pictures of example 3, (e) and (f) are pictures of example 4, in example 2, the color of the film visible to the naked eye is changed from original dark blue to transparent light blue until nearly completely colorless and transparent, in examples 3 and 4, the color of the film visible to the naked eye is changed from original dark blue to gray green and then changed to transparent yellow;
FIG. 4 shows the exposure of the thin films prepared in examples 1 to 4 to H2O2Resistance change chart before and after 30min of gas;
fig. 5 is based on PEDOT: PSS colorimetric and chemosensitive dual-mode sensor pair H2O2Response-concentration curve of gas.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As described in the background section, poly (3, 4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS) has higher conductivity, good chemical and thermal stability and excellent film forming property and processability, and is currently Commercialized (CLEVIOS)TM) One of the most successful conductive polymers has been widely used in the electrochemical detection of hydrogen peroxide and the gas-phase sensing of ammonia, CO, NOx, etc. in the environment, food or organism. PEDOT: PSS can be converted from original deep blue to semitransparent light blue to complete transparency in oxidation doping, and simultaneously, H2O2It can also be in the form of Fenton's reagent (Fe)2+/3+/H2O2) Or realizing the conditions of PEDOT: PSS and other conductive polymers are prepared, but are not commonly used due to their relatively weak oxidizing properties.
Based on the above, the method provides the PEDOT: the invention discloses a PSS visual chemosensor, and aims to search a detection method of chemical active gas hydrogen peroxide. For most gas phase sensing, the effect of moisture is not negligible, and in the present invention, H containing moisture is addressed2O2Gas, the oxidizing power of which is such that PEDOT: change in electrical signal of PSS, PEDOT: PSS undergoes color change during oxidation doping, and the polymerized PEDOT layer reduces the influence of moisture and improves the sensing reliability while improving the conductivity, the sensing sensitivity and the testing reliability, and in addition, H2O2The color change produced by the complexation reaction with the additive organic acid titanyl salt also contributes to the sensory response visible to the naked eye.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments.
The test materials used in the examples of the present invention are all conventional in the art and commercially available.
PEDOT in the examples: the PSS solution was purchased from Heraeus, Germany, with a PH of 1000, the ITO conductive glass was purchased from Kyork, Kyoho, Afaha, chemical Co., Ltd., 30% H2O2Solutions were purchased from Fonshen (Tianjin) Chemicals, Inc., other concentrations of H2O2The solution was passed through 30% H2O2The solution was diluted and tested for multimeter model KEITHLEY DMM 6500.
Example 1: PEDOT: preparation of PSS film and p-H2O2Detection of gases
(1) PEDOT: preparation of PSS film
1.1) placing an ITO glass substrate of 1 multiplied by 2em in a beaker, carrying out ultrasonic cleaning for 20min by using dichloromethane, acetone, ethanol and ultrapure water in sequence, wherein all solvents submerge the ITO glass substrate, placing the ITO glass substrate in a bottle filled with sufficient ethanol for storage after the ultrasonic cleaning is finished, taking out the ITO glass substrate, drying the ITO glass substrate by using high-purity nitrogen, placing the ITO glass substrate in a glass culture dish, placing the glass culture dish in an ultraviolet ozone cleaning machine, and taking out the ITO glass substrate after the treatment for 15 min;
1.2) sucking a proper amount of PEDOT from a disposable syringe: and (3) filtering the PSS solution through a polytetrafluoroethylene filter membrane filter head with the pore diameter of 0.45 mu m, wherein the content of the filtered PEDOT: placing the PSS solution in a clean glass bottle for temporary storage;
1.3) placing the ITO glass substrate treated in step 1.1) at the rotation center of a spin coater, covering about 120 μ L PODOT: and (3) starting the PSS solution to rotate, wherein the primary rotation speed is 1500rpm, the time is 40s, the secondary rotation speed is 4000rpm, and the time is 20s, repeating the spin coating process for 3 times to obtain a solution with uniform coverage of PEDOT: drying the ITO glass of the PSS film for 2h at 50 ℃;
(2) film pair H2O2Detection of gases
Taking H with the mass fraction of 3%2O25mL of the solution was charged into a glass cell, sealed for 12h to reach the saturated vapor pressure, and the amount of PEDOT prepared in example 1: the PSS film is suspended in a glass cell and placed in H after being connected with a test circuit by an electrode2O22cm above the center of the solution liquid level; the resistance change of the film was measured and recorded by a multimeter (see fig. 4) at a test temperature of 25 ℃.
Example 2: PEDOT: preparation of PSS/PEDOT film and p-H2O2Detection of gases
(1) PEDOT: preparation of PSS/PEDOT films
1.1) placing an ITO glass substrate of 1 multiplied by 2em in a beaker, carrying out ultrasonic cleaning for 20min by using dichloromethane, acetone, ethanol and ultrapure water in sequence, wherein all solvents submerge the ITO glass substrate, placing the ITO glass substrate in a bottle filled with sufficient ethanol for storage after the ultrasonic cleaning is finished, taking out the ITO glass substrate, drying the ITO glass substrate by using high-purity nitrogen, placing the ITO glass substrate in a glass culture dish, placing the glass culture dish in an ultraviolet ozone cleaning machine, and taking out the ITO glass substrate after the treatment for 15 min;
1.2) sucking a proper amount of PEDOT from a disposable syringe: and (3) filtering the PSS solution through a polytetrafluoroethylene filter membrane filter head with the pore diameter of 0.45 mu m, wherein the content of the filtered PEDOT: placing the PSS solution in a clean glass bottle for temporary storage;
1.3) placing the ITO glass substrate processed in the step 1.1) at the rotating center of a spin coater, covering about 120 μ L of PEDOT: and (3) starting the PSS solution to rotate, wherein the primary rotation speed is 1500rpm, the time is 40s, the secondary rotation speed is 4000rpm, and the time is 20s, repeating the spin coating process for 3 times to obtain a solution with uniform coverage of PEDOT: drying the ITO glass of the PSS film for 2h at 50 ℃;
1.4) adding tetrabutylammonium hexafluorophosphate (0.1M) as a supporting electrolyte into acetonitrile (5mL), adding a monomer EDOT (5mM), uniformly mixing to obtain an electrolyte, taking a platinum sheet electrode as an auxiliary electrode, taking silver/silver chloride as a reference electrode, and uniformly covering the PEDOT obtained in the step 1.3): and (3) taking the ITO glass of the PSS film as a working electrode, and electrochemically polymerizing for 30s at room temperature by adopting a chronoamperometry method to obtain a material which is uniformly covered with PEDOT: PSS/PEDOT film substrate.
(2) Film pair H2O2Detection of gases
Taking H with the mass fraction of 3%2O25mL of the solution was charged into a glass cell, sealed for 12h to reach the saturated vapor pressure, and the amount of PEDOT prepared in example 2: after the PSS/PEDOT film is used as an electrode to be connected with a test circuit, the test circuit is suspended in a glass tank and placed in H2O22cm above the center of the solution liquid level; the resistance change of the film was measured and recorded by a multimeter, the test temperature being 25 ℃.
PEDOT prepared in example 2: PSS/PEDOT films were scratched with a razor blade having a width of about 5.725 μm and were exposed to 3% H under metallographic microscope2O2Solution generated H2O2After gassing, the cracks become smaller, giving rise to clear signs of repair, as shown in fig. 2 (a) and (b). Combining the color change of FIG. 2 and the resistance data change of FIG. 4 shows that the film prepared by the present invention is not only for H2O2The gas has double response and self-repairing capability.
Example 3: PEDOT: PSS-ATO/PEDOT filmPreparation of (2) and p-H2O2Detection of gases
(1) PEDOT: preparation of PSS-ATO/PEDOT films
1.1) placing an ITO glass substrate of 1 multiplied by 2em in a beaker, carrying out ultrasonic cleaning for 20min by using dichloromethane, acetone, ethanol and ultrapure water in sequence, wherein all solvents submerge the ITO glass substrate, placing the ITO glass substrate in a bottle filled with sufficient ethanol for storage after the ultrasonic cleaning is finished, taking out the ITO glass substrate, drying the ITO glass substrate by using high-purity nitrogen, placing the ITO glass substrate in a glass culture dish, placing the glass culture dish in an ultraviolet ozone cleaning machine, and taking out the ITO glass substrate after the treatment for 15 min;
1.2) sucking a proper amount of PEDOT from a disposable syringe: and (3) filtering the PSS solution through a polytetrafluoroethylene filter membrane filter head with the pore diameter of 0.45 mu m, wherein the content of the filtered PEDOT: the PSS solution was stored in a clean glass bottle and the PEDOT: adding ATO into the PSS solution, carrying out ultrasonic treatment for 15min, and then stirring for 24h at the rotating speed of 400rpm, wherein the stirring temperature is 25 ℃, and the mass fraction of the ATO is 1%;
1.3) placing the ITO glass substrate processed in the step 1.1) at the rotating center of a spin coater, covering about 100uL PEDOT: and (3) starting to rotate the PSS-ATO solution, wherein the primary rotation speed is 1500rpm, the time is 20s, the secondary rotation speed is 2500rpm, and the time is 10s, repeating the spin coating process for 3 times to obtain the uniformly-covered PEDOT: drying the ITO glass of the PSS-ATO film for 2h at 50 ℃;
1.4) adding tetrabutylammonium hexafluorophosphate (0.1M) as a supporting electrolyte into acetonitrile (5mL), adding a monomer EDOT (5mM), uniformly mixing to obtain an electrolyte, taking a platinum sheet electrode as an auxiliary electrode, taking silver/silver chloride as a reference electrode, and uniformly covering the PEDOT obtained in the step 1.3): and (3) taking ITO glass of the PSS-ATO film as a working electrode, and electrochemically polymerizing for 30s at room temperature by adopting a chronoamperometry method to obtain a film with uniformly covered PEDOT: PSS-ATO/PEDOT film substrate.
(2) Film pair H2O2Detection of gases
Taking H with the mass fraction of 3%2O25mL of the solution was charged into a glass cell, sealed for 12h to reach the saturated vapor pressure, and the amount of PEDOT prepared in example 3: after the PSS-ATO/PEDOT film is used as an electrode to connect with a test circuit, the film is suspended in a glass tank and placed inH2O22cm above the center of the solution liquid level; the resistance change of the film was measured and recorded by a multimeter, the test temperature being 25 ℃.
PEDOT prepared in the above example 2: PSS/PEDOT films exposed to H2O2A color transition of the film from dark blue to translucent pale blue was observed after the gas as shown in (a), (b) of fig. 3, but the change visible to the naked eye was not significant at 30min, PEDOT prepared in example 3: the PSS-ATO/PEDOT film, as shown in (c) and (d) of FIG. 3, tested under the same conditions with the aid of ATO, changed color more significantly from dark blue to gray green and then changed to transparent yellow.
Example 4: PEDOT: preparation of PSS-ATO/PEDOT film and P-H2O2Detection of gases
(1) PEDOT was prepared as in example 3: method of PSS-ATO/PEDOT film PEDOT was again prepared: PSS-ATO/PEDOT films.
(2) Film pair H2O2Detection of gases
Taking H with the mass fraction of 30%2O25mL of the solution was charged into a glass cell, sealed for 12h to reach the saturated vapor pressure, and the amount of PEDOT prepared in example 4: after the PSS-ATO/PEDOT film is used as an electrode to be connected with a test circuit, the film is suspended in a glass tank and placed in H2O2The position 2cm above the center of the liquid level of the solution; the resistance change of the film was measured and recorded by a multimeter (see fig. 4) at a test temperature of 25 ℃.
As can be seen from FIG. 4, the thin films prepared in examples 1 to 3 were used as electrodes for test H2O2At concentration, the resistance value in example 1 varied most since the resistance value measured in PEDOT: PSS film as electrode, 3% H2O2As the solution evolves gas, moisture dominates, for PEDOT: PSS, the effect of moisture on its resistance change is significant and can even cause the film to peel off the substrate. To avoid this problem, the present invention provides a method for producing a polymer based on PEDOT: PEDOT is polymerized on the PSS-ATO film to reduce the influence of moisture and improve the detection stability. As can be seen from fig. 3 and 4, only in PEDOT: polymerization of PEDOT on PSS filmsFor electrode detection of H2O2At the time of concentration, the visual response is not obvious while the resistance value changes. In addition, in example 2, it takes a long time for the color of the film to change from deep blue to light blue, and finally the film becomes almost colorless transparent, so that in a complex environment of practical application, the colorless transparent is easily merged with the surrounding environment and is easily ignored, which all affect the practical application. The invention is therefore achieved by providing a PEDOT: adding ATO into the PSS solution to prepare PEDOT: and the PSS-ATO film is polymerized with PEDOT on the film, so that the time for changing the color from dark blue to gray green is short, the visual response is enhanced, the problem that the film is separated from the substrate by moisture is avoided, and the practical application is facilitated.
Example 5: film pair H2O2Response-concentration curve of gas
By using pure water to 30 wt.% of H2O2Dilution was performed to produce various saturated (equilibrium) solutions, yielding different H2O2The vapor pressure was 0.05, 0.1, 0.3, 0.5, 1.0, 1.3, 1.9, 2.7, 4.0, 5.7, 7.3, 9, 10.5ppm, respectively. 5mL of each diluted concentration solution was taken, and each diluted concentration solution was charged into a glass cell, sealed for 12 hours to reach a saturated vapor pressure, and PEDOT: method of PSS-ATO/PEDOT film, repeat preparation of PEDOT: PSS-ATO/PEDOT films for various concentrations of H2O2Detection was carried out, PEDOT: PSS-ATO/PEDOT film pitch H2O2The height of the liquid level is 2 cm; recording film exposure to H by multimeter2O2The resistance change after 30min of gas was 25 ℃. At saturated vapor pressure H2O2The gas concentration (ppm) is used as a horizontal coordinate, a standard curve is established by using the resistance value change value (omega) measured by a multimeter as a vertical coordinate, and the obtained standard curve is as follows: -1397.76758+4284.03812x, PEDOT: PSS-ATO/PEDOT film Pair H2O2The response-concentration linear fit curve for the gas is shown in fig. 5.
As can be seen from FIG. 5, the resistance of the film changes and different concentrations of H2O2There is a linear correlation between the gases. The fitting degree R2 factor of the linear relation is 0.9907, which shows that the fitting degree of the regression line to the observed value is better,0.08ppb is H2O2Lower limit of gas detection. Considering the uniformity of the film thickness and the test sensitivity of the resistance data, if the test system is further optimized, a better sensing signal can be obtained.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A PEDOT/PSS visual chemosensor for detecting gas-phase hydrogen peroxide is characterized by being prepared by the following method:
(1) ultrasonically cleaning a substrate by using dichloromethane, acetone, ethanol and ultrapure water in sequence, drying the substrate by using nitrogen, and then cleaning the substrate by using ultraviolet ozone to obtain a pretreated substrate;
(2) filtering the PEDOT/PSS solution, adding dimethyl sulfoxide, isopropanol and organic acid titanyl salt with the mass fraction of 1% -15% into the filtered PEDOT/PSS solution, carrying out ultrasonic treatment, and stirring for 24h at 25 ℃ to obtain a PEDOT/PSS-organic acid titanyl salt solution;
(3) spin-coating the PEDOT, PSS-organic acid titanyl salt solution obtained in the step (2) on the pretreated substrate obtained in the step (1), and drying to obtain a substrate uniformly covered with the PEDOT, PSS-organic acid titanyl salt film;
(4) adding an EDOT monomer into the electrolyte, taking a platinum sheet electrode as an auxiliary electrode, taking silver/silver chloride as a reference electrode, taking the substrate uniformly covered with the PEDOT/PSS-organic acid titanyl salt film obtained in the step (3) as a working electrode, electrochemically polymerizing at room temperature by a time-current method to obtain the substrate uniformly covered with the PEDOT/PSS-organic acid titanyl salt/PEDOT film, spraying acetonitrile, and drying with nitrogen to obtain the visual and sensitive dual-mode sensor capable of detecting gas-phase hydrogen peroxide based on the PEDOT/PSS.
2. The sensor of claim 1, wherein in step (1), the substrate is a rigid glass substrate or a flexible plastic substrate.
3. The sensor according to claim 1, wherein in step (2), the PEDOT: PSS solution is filtered through a teflon filter with a pore size of 0.45 μm; the organic acid titanyl salt is ammonium titanyl oxalate or potassium titanyl oxalate.
4. The sensor according to claim 1, wherein in step (3), the spin coating is: the rotating speed is 1500rpm when the spin coating is started, the rotating speed is increased to 2500-4000 rpm after the spin coating is carried out for 20-40 s, and the spin coating is continued for 10-20 s.
5. The sensor according to claim 1, wherein in step (3), 100 to 160 μ L of PEDOT: PSS-titanyl organo-ate solution is spin coated on each 1X 2cm pretreated substrate.
6. The sensor according to claim 1, wherein in the step (4), the electrolyte is obtained by uniformly mixing tetrabutylammonium hexafluorophosphate serving as a supporting electrolyte and acetonitrile serving as an electrolytic solvent.
7. The sensor according to claim 1, wherein in the step (4), the controlled polymerization potential of the chronoamperometric electrochemical polymerization is 1.2 to 1.4V, and the polymerization time is 10 to 30 s.
8. Use of a sensor according to any one of claims 1 to 7 for detecting gaseous hydrogen peroxide.
9. The method for detecting gas-phase hydrogen peroxide by using the sensor as claimed in any one of claims 1 to 7, is characterized by comprising the following steps: h is to be2O2Filling the solution into a glass cell, sealing until a saturated vapor pressure is reached, connecting the sensor of any one of claims 1 to 7 to a test circuit, and suspending the sensor in H2O2The resistance of the PEDOT/PSS/organic acid titanyl oxide/PEDOT film was measured by a multimeter at the midpoint above the solution according to the saturated vapor pressure H2O2Constructing a detection standard curve according to the change relation of the gas concentration and the resistance value, and calculating H in the component to be detected according to the standard curve2O2The gas concentration.
10. The method according to claim 9, wherein the method further comprises determining H from the color change of PEDOT/PSS/titanyl organic acid/PEDOT thin film on the sensor according to any one of claims 1 to 72O2Magnitude of gas concentration.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114923961A (en) * | 2022-04-29 | 2022-08-19 | 安徽维纳物联科技有限公司 | SnO (stannic oxide) 2 Carbon monoxide gas sensor and preparation method thereof |
| CN115980162A (en) * | 2023-03-22 | 2023-04-18 | 北京大学 | Methane sensor |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102621206A (en) * | 2012-04-19 | 2012-08-01 | 江西科技师范学院 | Method for preparing poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) composite modified electrode |
| CN104977337A (en) * | 2014-04-09 | 2015-10-14 | 南京理工大学 | Biosensor for detecting hydrogen peroxide and polyphenol compounds at high sensitivity, and preparation and application thereof |
| US20160064672A1 (en) * | 2014-09-02 | 2016-03-03 | Gwangju Institute Of Science And Technology | Pedot:pss based electrode and method for manufacturing the same |
| CN106770588A (en) * | 2016-11-25 | 2017-05-31 | 深圳大学 | A kind of methyl amimoacetic acid detection means and preparation method thereof, application |
| US20170241025A1 (en) * | 2016-02-23 | 2017-08-24 | South Dakota Board Of Regents | Self-organized and electrically conducting pedot polymer matrix for applications in sensors and energy generation and storage |
| CN108777187A (en) * | 2018-05-29 | 2018-11-09 | 成都莫比斯科技有限公司 | A method of it improving PEDOT conductive films adhesive force and scratch resistance can |
| CN110372898A (en) * | 2019-07-05 | 2019-10-25 | 江西科技师范大学 | A kind of preparation method of transparent high conductive organic flexible PEDOT:PSS film |
-
2020
- 2020-07-06 CN CN202010643611.3A patent/CN111912883B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102621206A (en) * | 2012-04-19 | 2012-08-01 | 江西科技师范学院 | Method for preparing poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) composite modified electrode |
| CN104977337A (en) * | 2014-04-09 | 2015-10-14 | 南京理工大学 | Biosensor for detecting hydrogen peroxide and polyphenol compounds at high sensitivity, and preparation and application thereof |
| US20160064672A1 (en) * | 2014-09-02 | 2016-03-03 | Gwangju Institute Of Science And Technology | Pedot:pss based electrode and method for manufacturing the same |
| US20170241025A1 (en) * | 2016-02-23 | 2017-08-24 | South Dakota Board Of Regents | Self-organized and electrically conducting pedot polymer matrix for applications in sensors and energy generation and storage |
| CN106770588A (en) * | 2016-11-25 | 2017-05-31 | 深圳大学 | A kind of methyl amimoacetic acid detection means and preparation method thereof, application |
| CN108777187A (en) * | 2018-05-29 | 2018-11-09 | 成都莫比斯科技有限公司 | A method of it improving PEDOT conductive films adhesive force and scratch resistance can |
| CN110372898A (en) * | 2019-07-05 | 2019-10-25 | 江西科技师范大学 | A kind of preparation method of transparent high conductive organic flexible PEDOT:PSS film |
Non-Patent Citations (3)
| Title |
|---|
| XIAOFENG WANG 等: "Ti3C2Tx/PEDOT：PSS hybrid materisals for room-temperature methanol snesor", 《CHINESE CHEMICAL LETTERS》, pages 1018 - 1021 * |
| 朱雪乔 等: "氧化石墨烯掺杂含量对石墨烯／ＰＥＤＯＴ∶ＰＳＳ复合材料电化学性能的影响", 《化工新型材料》 * |
| 朱雪乔 等: "氧化石墨烯掺杂含量对石墨烯／ＰＥＤＯＴ∶ＰＳＳ复合材料电化学性能的影响", 《化工新型材料》, vol. 46, no. 12, 31 December 2018 (2018-12-31), pages 151 - 155 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114923961A (en) * | 2022-04-29 | 2022-08-19 | 安徽维纳物联科技有限公司 | SnO (stannic oxide) 2 Carbon monoxide gas sensor and preparation method thereof |
| CN115980162A (en) * | 2023-03-22 | 2023-04-18 | 北京大学 | Methane sensor |
| CN115980162B (en) * | 2023-03-22 | 2023-06-13 | 北京大学 | Methane sensor |
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