CN111912883B - PEDOT for detecting gaseous hydrogen peroxide: PSS visual sensor - Google Patents
PEDOT for detecting gaseous hydrogen peroxide: PSS visual sensor Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
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- 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
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Abstract
The invention discloses a PEDOT for detecting gas-phase hydrogen peroxide, which comprises the following steps: PSS visual sensor relates to gas detection technique and organic photoelectron material technique field. The sensor of the present invention prepares PEDOT on a substrate by spin coating: PSS-organic acid titanyl salt film, and then the chronoamperometry method is adopted in PEDOT: and preparing the PEDOT film by electrochemical polymerization on the PSS-organic acid titanium oxide film. The sensor prepared by the invention not only can realize the gas phase H 2 O 2 The dual effective detection of the electrical signal and the visualization has practical application value of industrial and biological monitoring, provides a new method for detecting the chemical active gas, realizes self-repairing of the electrode material by a moisture driving mode, and has 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 PEDOT for detecting gas-phase hydrogen peroxide, which comprises the following steps: PSS visualizes the sensor.
Background
Hydrogen peroxide (H) 2 O 2 ) The aqueous solution of (2) is commonly called hydrogen peroxide, has strong oxidizing property, is a common disinfectant, bactericide, bleaching agent and oxidizing agent, and is widely applied to the fields of industrial bleaching, surgical disinfection and the like. As an important active oxygen in living body, H is generally the case 2 O 2 Is necessary and beneficial for the organism, but when H 2 O 2 When excessive amounts are produced, various diseases may be caused. Relative to the liquid phase, gas phase H 2 O 2 Detection techniques (co-existence with moisture, oxidizing) are lacking and present a significant challenge. In addition, peroxomonosporants such as triacetoneperoxide (TATP) contain unstable peroxo groups (-O-), and are prone toPhotolysis of the produced H 2 O 2 Are considered as marker compounds for the detection of such explosives. The explosive materials are easy to obtain, the manufacturing process is simple, the explosive materials are extremely sensitive to heat, collision and friction, more than two grams of TATP can explode, and the explosion of smaller mass can even be carried out under a slightly airtight condition, which is called an 'entropy explosive', so that the rapid and low-cost detection of the explosive materials is urgently needed. Only a few literature reports fluorescence methods on H 2 O 2 But has the problems of long detection reaction time, troublesome material selection and synthesis, difficult sampling and signal conversion, complex instrument calibration, large environmental interference and the like. H 2 O 2 The accurate detection of (C) has important significance in aspects of food analysis, biology, industry, clinical control, environmental monitoring and the like.
In the search for sensing sensitive materials, conductive polymers with reversible electrical properties that can change resistance, current or electrochemical potential through reaction with chemicals are considered good candidates for chemical gas sensors. Wherein, poly (3, 4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT: PSS) has 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, PEDOT: PSS is often combined with other materials for electrochemical detection of certain components in liquid phase systems, and no related art has been reported for sensitization and visual detection of chemically active gases. PEDOT: PSS is converted from original deep blue to semitransparent light blue to complete transparent during oxidation doping, and meanwhile, H 2 O 2 Can also be in the form of Fenton reagent (Fe 2+/3+ /H 2 O 2 ) Or under the optimized conditions of pH and peroxidase auxiliary catalysis, realizing the PEDOT: the preparation of conductive polymers such as PSS is not common due to their relatively weak oxidizing properties. The maximum concentration of commercial hydrogen peroxide is 50% (9.17 mmHg,25 ℃), 3% is the concentration of a common disinfectant, is not higher than the level when the commercial hydrogen peroxide is used as an oxidant, the influence on polymer degradation is controllable, and the saturated vapor pressure generated by the commercial hydrogen peroxide is between trace ppb and trace ppm and the peroxide explosive is generatedDecomposition released H 2 O 2 Is generally at the ppt-ppb level. Considering low concentration of H 2 O 2 To PEDOT: the PSS film has no obvious color effect, organic titanyl salt is selected as a color developing additive, the visual response of the color is enhanced, and the titanyl salt and H are mixed 2 O 2 Complexation forms Ti (IV) -peroxide bonds, with a maximum absorption wavelength of about 400nm, exhibiting a pronounced color change, which is induced by this complexation only for H 2 O 2 Is selective 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 effect of moisture is not negligible, so there is now a need for a PEDOT for detecting gas phase hydrogen peroxide: PSS visual sensor not only can detect H 2 O 2 Can also realize the concentration of H 2 O 2 Visual response of the gas; self-repair is enabled when the sensor is destroyed.
Disclosure of Invention
In order to solve the problems, the invention provides a PEDOT for detecting gas-phase hydrogen peroxide: PSS visualizes the sensor. By H 2 O 2 Is combined with the oxidizing ability of the pair H 2 O 2 Organic titanyl salt with selectivity; considering moisture vs PEDOT: the electrochemical polymerization of a layer of PEDOT is selected to weaken the surface hydrophilicity and enhance the film conductivity and stability, and meanwhile, the surface nano structure of the electropolymerized PEDOT layer can strengthen the effect on H 2 O 2 Adsorption of gas, and final realization of gas phase H by the film electrode material 2 O 2 Is provided.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a PEDOT for detecting gaseous hydrogen peroxide: PSS visual sensor, which is prepared by the following method:
(1) Sequentially ultrasonically cleaning a substrate by using dichloromethane, acetone, ethanol and ultrapure water, drying by nitrogen, and then cleaning by ultraviolet ozone to obtain a pretreated substrate;
(2) Poly (3, 4-ethylenedioxythiophene): the polystyrene sulfonate (PEDOT: PSS) solution was filtered, and the filtered PEDOT: adding dimethyl sulfoxide (DMSO), isopropyl alcohol (IPA) and 1-15% of organic acid titanium oxide salt into the PSS solution, and stirring for 24h at 25 ℃ after ultrasonic treatment to obtain PEDOT: PSS-organic acid titanyl salt solution;
(3) And (3) obtaining the PEDOT in the step (2): spin-coating PSS-organic acid titanyl salt solution on the pretreated substrate obtained in the step (1), and drying to obtain uniform coverage PEDOT: a substrate of the PSS-organic acid titanyl salt film;
(4) Adding 3, 4-Ethylenedioxythiophene (EDOT) monomer into the electrolyte, taking a platinum sheet electrode as an auxiliary electrode, silver/silver chloride as a reference electrode, and uniformly covering the PEDOT obtained in the step (3): the substrate of the PSS-organic acid titanium oxide film is used as a working electrode, and electrochemical polymerization is carried out at room temperature by using a time-current method to obtain the uniform coverage PEDOT: and (3) eluting the substrate of the PSS-organic acid titanyl salt/PEDOT film with acetonitrile, and drying with nitrogen to obtain the substrate loaded with PEDOT: PSS-organic acid titanyl salt/PEDOT film sensor.
Preferably, in step (1), the substrate is a rigid glass substrate or a flexible plastic substrate.
Preferably, in step (2), PEDOT: the PSS solution is filtered through a polytetrafluoroethylene filter membrane with the pore diameter of 0.45 mu m; the organic acid titanyl salt is titanyl ammonium oxalate (ATO) or Potassium Titanyl Oxalate (PTO).
Preferably, in step (3), the spin coating is: the rotating speed at the beginning of the spin coating is 1500rpm, the rotating speed is increased to 2500-4000 rpm after the spin coating is performed for 20-40 s, and the spin coating is continued for 10-20 s.
Preferably, in step (3), 100 to 160. Mu.L of PEDOT is spin-coated on each 1X 2em pre-treated substrate: PSS-organic acid titanyl salt solution.
Preferably, in step (3), the drying temperature is 50℃and the drying time is 2 hours.
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 electrochemical polymerization by the chronoamperometric method is 1.2-1.4V, and the polymerization time is 10-30 s.
In a second aspect of the invention, there is provided the use of the above sensor for detecting hydrogen peroxide in the gas phase.
In a third aspect of the present invention, a method for detecting gaseous hydrogen peroxide by using the above sensor is provided: will H 2 O 2 Filling the solution into a glass tank, sealing until reaching saturated vapor pressure, and detecting PEDOT of gas-phase hydrogen peroxide: PSS visual sensor is suspended in H after being connected with test circuit 2 O 2 Right above the solution, PEDOT was tested by multimeter: resistance value of PSS-organic acid titanyl salt/PEDOT film according to H under saturated vapor pressure 2 O 2 Constructing a detection standard curve according to the relation between the gas concentration and the resistance value change, and calculating H in the solution to be detected according to the standard curve 2 O 2 Gas concentration.
Preferably, the method may further be performed by PEDOT for detecting hydrogen peroxide in the gas phase: PSS visualizes PEDOT of the sensor: color change judgment H of PSS-organic acid titanyl salt/PEDOT film 2 O 2 The gas concentration, i.e. the film color changes from dark blue to transparent yellow, the lighter the color is, the more H is indicated 2 O 2 The higher the gas concentration. The color visualization effect is good.
PEDOT: PSS-organic acid titanyl salt/PEDOT film distance H 2 O 2 The 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 a glass pool or the actual situation: PSS-organic acid titanyl salt/PEDOT film distance H 2 O 2 Height of solution level, PEDOT: PSS-organic acid titanyl salt/PEDOT film and H 2 O 2 The solution is not contacted.
Preferably, the H 2 O 2 The detection standard curve of the relation between the concentration and the resistance value is as follows: y= -1397.76758+4284.03812x.
Preferably, the linear range is: 5ppb to 214ppm; the lower detection limit is as follows: 0.08ppb. If the test system is further optimized, the thin film is thinned, the area is smaller, the conductivity is higher, and better sensing signals 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 titanium oxide salt can realize H-phase reaction 2 O 2 Dual signal detection of gas, i.e. a change in electrical signal and a macroscopic color transition. The electropolymerized PEDOT layer not only improves conductivity, sensing sensitivity and test reliability, but also reduces the influence of moisture and improves sensing reliability, and the surface nano structure can also enhance the sensitivity to H 2 O 2 Adsorption of the gas. By adding a conductive accelerator such as DMSO to improve the conductivity, if the thin film is thinner and the area is smaller, a better sensing signal can be obtained, and the detection lower limit is lower.
2. The preparation process is simple, the cost is low, and H can be realized 2 O 2 The method has the advantages of effective detection of the gas and visual response, and provides a new solution for the detection of the chemically active gas.
3. The sensor of the present invention has a moisture driven self-healing capability, PEDOT: the PSS-organic acid titanium oxide/PEDOT film can be self-repaired after being damaged, is suitable for detection under various severe conditions, and expands the detection range.
Drawings
FIG. 1 is a schematic diagram of a dual mode sensor structure according to the present invention;
fig. 2 is PEDOT prepared in example 2: microscopic image of the PSS/PEDOT film at the crack wound before and after repair;
FIG. 3 shows the films prepared in examples 2-4 after exposure to H 2 O 2 Pictures before and after 30min of gas;
in the figure, (a) (c) (e) is the original condition of the film, and (b) (d) (f) is the exposure of the film to H 2 O 2 Color 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 macroscopic film color changes from original deep blue to transparent pale blue until almost completely colorless transparent, in examples 3 and 4 the macroscopic film color changes from original deep blue to pale green and then becomes transparentYellow;
FIG. 4 shows the films prepared in examples 1-4 after exposure to H 2 O 2 Resistance change diagrams before and after 30min of gas;
fig. 5 is based on PEDOT: colorimetric sensitive dual-mode sensor pair H of PSS 2 O 2 Response-concentration curve of gas.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present application. 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 high 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 electrochemical detection of hydrogen peroxide in the environment, food or organism and gas phase sensing of ammonia, CO, NOx, etc. PEDOT: PSS is converted from original deep blue to semitransparent light blue to complete transparent during oxidation doping, and meanwhile, H 2 O 2 Can also be in the form of Fenton reagent (Fe 2+/3+ /H 2 O 2 ) Or under the optimized conditions of pH and peroxidase auxiliary catalysis, realizing the PEDOT: the preparation of conductive polymers such as PSS is not common due to their relatively weak oxidizing properties.
Based on this, a PEDOT for detecting gaseous hydrogen peroxide is provided: the invention discloses a PSS visual sensor, and aims to explore a detection method of chemically active gas hydrogen peroxide. For most gas phase sensing, the effect of moisture is not negligible, in the present invention, for H containing moisture 2 O 2 Gas, its oxidizing ability makes PEDOT: the electrical signal of PSS changes, PEDOT: the PSS undergoes color change during oxidation doping, the polymerized PEDOT layer reduces the influence of moisture while improving conductivity, sensing sensitivity and test reliability, improves sensing reliability, and in addition, H 2 O 2 The color change resulting from the complexation reaction with the additive titanyl organic acid salt also helps to achieve a macroscopic sensing response.
In order to enable those skilled in the art to more clearly understand the technical solutions of the present application, 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 are commercially available.
PEDOT in the example: PSS solution was purchased from Heraeus, germany, model PH1000, ITO conductive glass from ZhuhaiKai, photoelectric technology Co., ltd., ATO from Alfa Esa (China) chemical Co., ltd., 30% H 2 O 2 Solutions were purchased from fomes chemical reagent limited, other concentrations of H 2 O 2 The solution was passed through 30% H 2 O 2 The solution was diluted and the multimeter model KEITHLEY DMM6500.
Embodiment case 1: PEDOT: preparation of PSS film and H-pair 2 O 2 Detection of gases
(1) PEDOT: preparation of PSS film
1.1 Placing an ITO glass substrate of 1 multiplied by 2em in a beaker, sequentially ultrasonically cleaning the ITO glass substrate with dichloromethane, acetone, ethanol and ultrapure water for 20min, placing the ITO glass substrate in a bottle filled with sufficient ethanol for storage for standby after ultrasonic cleaning is completed, taking out the ITO glass substrate, drying the ITO glass substrate by high-purity nitrogen, placing the glass substrate in a glass culture dish, placing the glass culture dish in an ultraviolet ozone cleaner, and taking out the glass culture dish after 15min of treatment;
1.2 Disposable needle tube aspirates an appropriate amount of PEDOT: the PSS solution was filtered through a polytetrafluoroethylene filter membrane filter head having a pore size of 0.45 μm, and the filtered PEDOT: putting the PSS solution into a clean glass bottle for temporary storage;
1.3 Placing the ITO glass substrate treated in step 1.1) at the center of rotation of a spin coater, covering about 120 μLPEDOT: the PSS solution starts to rotate, the primary rotating speed is 1500rpm, the time is 40s, the secondary rotating speed is 4000rpm, the time is 20s, the spin coating process is repeated for 3 times, and the uniform coverage PEDOT is obtained: ITO glass of the PSS film is dried at 50 ℃ for 2 hours;
(2) Film pair H 2 O 2 Detection of gases
Taking H with mass fraction of 3% 2 O 2 5mL of the solution was placed in a glass cell and sealed for 12 hours to reach saturated vapor pressure, with PEDOT prepared in example 1: after the PSS film is used as an electrode to be connected with a test circuit, the PSS film is suspended in a glass pool and is placed in H 2 O 2 2em above the center of the solution level; the resistance change of the film was measured and recorded by a multimeter (see fig. 4) at a test temperature of 25 ℃.
Embodiment case 2: PEDOT: preparation of PSS/PEDOT film and preparation of P/PEDOT film for H 2 O 2 Detection of gases
(1) PEDOT: preparation of PSS/PEDOT film
1.1 Placing an ITO glass substrate of 1 multiplied by 2em in a beaker, sequentially ultrasonically cleaning the ITO glass substrate with dichloromethane, acetone, ethanol and ultrapure water for 20min, placing the ITO glass substrate in a bottle filled with sufficient ethanol for storage for standby after ultrasonic cleaning is completed, taking out the ITO glass substrate, drying the ITO glass substrate by high-purity nitrogen, placing the glass substrate in a glass culture dish, placing the glass culture dish in an ultraviolet ozone cleaner, and taking out the glass culture dish after 15min of treatment;
1.2 Disposable needle tube aspirates an appropriate amount of PEDOT: the PSS solution was filtered through a polytetrafluoroethylene filter membrane filter head having a pore size of 0.45 μm, and the filtered PEDOT: putting the PSS solution into a clean glass bottle for temporary storage;
1.3 Placing the ITO glass substrate treated in step 1.1) at the center of rotation of the spin coater, covering about 120 μl of PEDOT: the PSS solution starts to rotate, the primary rotating speed is 1500rpm, the time is 40s, the secondary rotating speed is 4000rpm, the time is 20s, the spin coating process is repeated for 3 times, and the uniform coverage PEDOT is obtained: ITO glass of the PSS film is dried at 50 ℃ for 2 hours;
1.4 Tetrabutylammonium hexafluorophosphate (0.1M) was added to acetonitrile (5 mL) as a supporting electrolyte, monomer EDOT (5 mM) was added, and after mixing uniformly, it was used as an electrolyte, a platinum sheet electrode was used as an auxiliary electrode, silver/silver chloride was used as a reference electrode, and the uniform coverage PEDOT obtained in 1.3) was used: the ITO glass of the PSS film is used as a working electrode, and electrochemical polymerization is carried out for 30s at room temperature by adopting a chronoamperometric method, so that the PEDOT is uniformly covered: the substrate of PSS/PEDOT film.
(2) Film pair H 2 O 2 Detection of gases
Taking H with mass fraction of 3% 2 O 2 5mL of the solution was placed in a glass cell and sealed for 12 hours to reach saturated vapor pressure, with PEDOT prepared in example 2: after the PSS/PEDOT film is used as an electrode to connect a test circuit, the test circuit is suspended in a glass pool and placed in H 2 O 2 2em above the center of the solution level; the resistance change of the film was measured and recorded by a multimeter at a test temperature of 25 ℃.
PEDOT prepared in example 2: the PSS/PEDOT film was scratched with a blade having a width of about 5.725 μm, and was exposed to 3% H under a metallographic microscope 2 O 2 H produced by solution 2 O 2 After the gas, the cracks become smaller, giving rise to obvious signs of repair, as shown in fig. 2 (a) and (b). The combination of the color change of FIG. 2 and the resistance data change of FIG. 4 shows that the film prepared by the invention is not only suitable for H 2 O 2 The gas has dual response and self-repairing capability.
Embodiment 3: PEDOT: preparation of PSS-ATO/PEDOT film and H-pair 2 O 2 Detection of gases
(1) PEDOT: preparation of PSS-ATO/PEDOT film
1.1 Placing an ITO glass substrate of 1 multiplied by 2em in a beaker, sequentially ultrasonically cleaning the ITO glass substrate with dichloromethane, acetone, ethanol and ultrapure water for 20min, placing the ITO glass substrate in a bottle filled with sufficient ethanol for storage for standby after ultrasonic cleaning is completed, taking out the ITO glass substrate, drying the ITO glass substrate by high-purity nitrogen, placing the glass substrate in a glass culture dish, placing the glass culture dish in an ultraviolet ozone cleaner, and taking out the glass culture dish after 15min of treatment;
1.2 Disposable needle tube aspirates an appropriate amount of PEDOT: the PSS solution was filtered through a polytetrafluoroethylene filter membrane filter head having a pore size of 0.45 μm, and the filtered PEDOT: the PSS solution is put into a clean glass bottle for temporary storage, and PEDOT: adding ATO into the PSS solution, and stirring for 24 hours at the rotating speed of 400rpm after ultrasonic treatment for 15min, wherein the stirring temperature is 25 ℃, and the mass fraction of the ATO is 1%;
1.3 Placing the ITO glass substrate treated in step 1.1) at the center of rotation of the spin coater, covering about 100uL of PEDOT: the PSS-ATO solution starts to rotate, the primary rotating speed is 1500rpm, the time is 20s, the secondary rotating speed is 2500rpm, the time is 10s, the spin coating process is repeated for 3 times, and the uniform coverage PEDOT is obtained: ITO glass of the PSS-ATO film is dried at 50 ℃ for 2 hours;
1.4 Tetrabutylammonium hexafluorophosphate (0.1M) was added to acetonitrile (5 mL) as a supporting electrolyte, monomer EDOT (5 mM) was added, and after mixing uniformly, it was used as an electrolyte, a platinum sheet electrode was used as an auxiliary electrode, silver/silver chloride was used as a reference electrode, and the uniform coverage PEDOT obtained in 1.3) was used: the ITO glass of the PSS-ATO film is used as a working electrode, and the electrochemical polymerization is carried out for 30s at room temperature by adopting a chronoamperometric method, so that the PEDOT is uniformly covered: the substrate of PSS-ATO/PEDOT film.
(2) Film pair H 2 O 2 Detection of gases
Taking H with mass fraction of 3% 2 O 2 5mL of the solution was placed in a glass cell and sealed for 12 hours to reach saturated vapor pressure, with PEDOT prepared in example 3: the PSS-ATO/PEDOT film is suspended in a glass pool after being connected with a test circuit by an electrode and is placed in H 2 O 2 2em above the center of the solution level; the resistance change of the film was measured and recorded by a multimeter at a test temperature of 25 ℃.
PEDOT prepared in example 2 above: PSS/PEDOT film, exposed to H 2 O 2 After the gas, the color of the film was observed to change from dark blue to translucent light blue as shown in (a) and (b) of fig. 3, but the macroscopic change was not obvious at 30min, and the PEDOT prepared in example 3: as shown in (c) and (d) of FIG. 3, the PSS-ATO/PEDOT film was tested under the same conditions with the aid of ATO, and the color change was more pronounced, from dark blue to dark green and then to transparent yellow.
Embodiment 4: PEDOT: preparation of PSS-ATO/PEDOT film and H-pair 2 O 2 Detection of gases
(1) PEDOT was prepared as in example 3: method of PSS-ATO/PEDOT film PEDOT was prepared again: PSS-ATO/PEDOT film.
(2) Film pair H 2 O 2 Detection of gases
Taking H with mass fraction of 30% 2 O 2 5mL of the solution was placed in a glass cell and sealed for 12 hours to reach saturated vapor pressure, with PEDOT prepared in example 4: the PSS-ATO/PEDOT film is suspended in a glass pool after being connected with a test circuit by an electrode and is placed in H 2 O 2 2cm above the center of the solution level; 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 films prepared in examples 1 to 3 were used as electrode test H 2 O 2 The resistance value in example 1 changed the most at the concentration, because the test of example 1 was run with PEDOT: PSS film as electrode, 3% H 2 O 2 When the solution is gaseous, moisture is the predominant part, for PEDOT: PSS, moisture has a great influence on its resistance change and even allows the film to be detached from the substrate. To avoid this problem, the present invention is described in PEDOT: the PEDOT is polymerized on the PSS-ATO film to weaken the influence of moisture and improve the detection stability. As can be seen from fig. 3 and 4, only in PEDOT: detection of H by polymerizing PEDOT as electrode on PSS film 2 O 2 At the concentration, the visual response was not apparent while the resistance value was varied. In addition, in the embodiment 2, a long time is required for changing the color of the film from deep blue to light blue, and finally, the film becomes almost colorless and transparent, so that in a complex environment of practical application, the colorless and transparent film is easy to be fused with the surrounding environment and is easy to be ignored, and the practical application is influenced. The invention is therefore achieved by the following steps in PEDOT: adding ATO into the PSS solution to prepare PEDOT: the PSS-ATO film is polymerized on the PEDOT film, the time for changing the color from dark blue to gray green is short, the visual response is enhanced, meanwhile, the problem that moisture causes the film to fall off from the substrate is avoided, and the practical application is facilitated.
Embodiment case 5: film pair H 2 O 2 Response-concentration curve of gas
By using pure water to 30wt.% of H 2 O 2 Diluting to generate various satietysAnd (equilibration) of the solution to obtain different H' s 2 O 2 Vapor pressures of 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 placed in a glass cell, and sealed for 12 hours to reach saturated vapor pressure, and PEDOT was prepared as in example 3: method for PSS-ATO/PEDOT film, repeated preparation of PEDOT: PSS-ATO/PEDOT films are used for H with various concentrations 2 O 2 Detection is carried out, and PEDOT: PSS-ATO/PEDOT film distance H 2 O 2 The height of the liquid level is 2em; recording film exposure to H by multimeter 2 O 2 The resistance after 30min of gas was changed and the test temperature was 25 ℃. H under saturated steam pressure 2 O 2 The gas concentration (ppm) is taken as an abscissa, a resistance value change value (omega) measured by a universal meter is taken as an ordinate, a standard curve is established, and the standard curve is obtained by: y= -1397.76758+4284.03812x, pedot: PSS-ATO/PEDOT film pair H 2 O 2 The response-concentration linear fit curve of the gas is shown in figure 5.
As can be seen from FIG. 5, the resistance of the film varies and H is present in different concentrations 2 O 2 The gases are linearly related. The linear relation fitting degree R2 factor is 0.9907, which shows that the fitting degree of the regression line to the observed value is better, and 0.08ppb is H 2 O 2 The lower detection limit of the gas. In consideration of the uniformity of the film thickness and the test sensitivity of the resistance data, better sensing signals can be obtained if the test system is further optimized.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (10)
1. The PEDOT/PSS visual sensor for detecting the gas-phase hydrogen peroxide is characterized by being prepared by the following method:
(1) Sequentially ultrasonically cleaning a substrate by using dichloromethane, acetone, ethanol and ultrapure water, drying by nitrogen, and then cleaning by ultraviolet ozone to obtain a pretreated substrate;
(2) Filtering the PEDOT/PSS solution, adding dimethyl sulfoxide, isopropanol and 1-15% of organic acid titanyl salt into the filtered PEDOT/PSS solution, carrying out ultrasonic treatment, and stirring at 25 ℃ for 24 hours 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 EDOT monomer into electrolyte, using a platinum sheet electrode as an auxiliary electrode, using silver/silver chloride as a reference electrode, using a substrate uniformly covered with the PEDOT/PSS-organic acid titanium oxide film obtained in the step (3) as a working electrode, performing electrochemical polymerization at room temperature by using a time-consuming amperometric method to obtain a substrate uniformly covered with the PEDOT/PSS-organic acid titanium oxide/PEDOT film, eluting with acetonitrile, and drying with nitrogen to obtain the visual sensitive dual-mode sensor based on the PEDOT/PSS and capable of detecting gas-phase hydrogen peroxide.
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 of claim 1, wherein in step (2), the PEDOT: PSS solution is filtered through a polytetrafluoroethylene filter membrane having a pore size of 0.45 μm; the organic acid titanyl salt is titanyl ammonium oxalate or titanyl potassium oxalate.
4. The sensor of claim 1, wherein in step (3), the spin coating is: the rotating speed at the beginning of the spin coating is 1500rpm, the rotating speed is increased to 2500-4000 rpm after the spin coating is performed for 20-40 s, and the spin coating is continued for 10-20 s.
5. The sensor of claim 1, wherein in step (3), 100 to 160 μlpedot: PSS-titanyl organic acid salt solution is spin-coated on each 1 x 2cm of the pretreated substrate.
6. The sensor according to claim 1, wherein in the step (4), the electrolyte is obtained by uniformly mixing tetrabutylammonium hexafluorophosphate as a supporting electrolyte and acetonitrile as an electrolytic solvent.
7. The sensor of claim 1, wherein in step (4), the controlled polymerization potential of the chronoamperometric electrochemical polymerization is 1.2 to 1.4V and the polymerization time is 10 to 30s.
8. Use of the sensor according to any one of claims 1 to 7 for detecting hydrogen peroxide in the gas phase.
9. The method for detecting gaseous hydrogen peroxide by the sensor according to any one of claims 1 to 7, wherein the method comprises the steps of: will H 2 O 2 Loading the solution into a glass cell, sealing to reach saturated vapor pressure, connecting the sensor of any one of claims 1-7 to a test circuit, and then suspending the sensor in H 2 O 2 The resistance of the PEDOT: PSS-titanyl organic acid salt/PEDOT film was measured by a multimeter at the right center above the solution according to H under saturated vapor pressure 2 O 2 Constructing a detection standard curve according to the relation between the gas concentration and the resistance value change, and calculating H in the component to be detected according to the standard curve 2 O 2 Gas concentration.
10. The method according to claim 9, wherein the method further determines H by a color change of the PEDOT: PSS-organic titanyl titanate/PEDOT film on the sensor according to any one of claims 1 to 7 2 O 2 The magnitude of the gas concentration.
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