CN112903788A - Polymer membrane electrode for detecting phenol pollutants and preparation method thereof - Google Patents
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Abstract
The scheme relates to a polymer membrane electrode for detecting phenolic pollutants and a preparation method thereof. The preparation method is simple and low in cost; the selective monomer is more, can be used for carrying out quantitative analysis on a plurality of phenolic compounds, and has wide application range; in the film forming process, a polymer film with a porous structure is formed, so that more enzyme activity centers can be exposed to be contacted with a target object to be detected; the method has the advantages of high reaction speed, low detection lower limit and wide detection range; the prepared electrochemical biosensor has high sensitivity and good selectivity and stability, and can be used for detecting phenolic substances in a water body environment.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a polymer membrane electrode for detecting phenolic pollutants and a preparation method thereof.
Background
In the industrial production process of oil refining, paper making, plastics, ceramics, textiles and the like, the produced industrial wastewater often contains phenolic substances, and if the organic phenolic substances are discharged into the surrounding environment, even trace phenolic organic substances can cause toxic action on the growth and reproduction of surrounding aquatic organisms, and can pollute drinking water sources and harm human health. Therefore, it is necessary to control the content of phenols in the surrounding water environment, and the detection of phenols is particularly important, so that the safety condition of the water environment can be monitored through the detection. At present, the traditional detection method for phenolic substances is established based on chromatography and spectrophotometry, but the two methods both need large-scale analytical instruments, have poor continuity, complicated pretreatment and higher cost. A rapid and simple phenolic substance detection method is established, and the method has great significance for environment monitoring work.
With the development of electrochemical sensor technology, researchers began to explore the application of electrochemical sensors in environmental monitoring and their application in the detection of target substances. At present, more and more researches are being carried out on applying an enzyme electrochemical sensor to the detection of phenolic substances in natural water. Patent CN102928488B discloses a method for detecting phenolic compounds in a water body environment by an enzyme electrochemical biosensor, wherein the sensor adopted in the method is prepared by immobilizing a neuraminidase on a novel ionic liquid modified mesoporous carbon composite material. The ordered mesoporous carbon material is required to be used and can play a role in fixing enzyme molecules, but the preparation steps of the ordered mesoporous carbon material are complex. Patent CN102680547B discloses an electrode for detecting phenolic substances in water and a preparation method thereof, wherein the related electrochemical sensor is prepared by using a boron-doped diamond film as an electrode substrate and modifying the surface of the electrode substrate by using nano diamond particles and a neuraminidase together. Patent CN109628545A discloses a bacterial laccase sensor for detecting phenolic substances in high concentration. In the method for preparing the bacterial laccase sensor, the used modified electrode mixed solution is a multi-walled carbon nanotube-chitosan-ABTS solution, and the expression acquisition steps of the related proprietary bacterial laccase CotA are complex.
From the foregoing, the problems existing in the current process of preparing an enzyme electrochemical sensor are that the preparation steps are complex, and a plurality of reagents and materials are used in the preparation process to achieve the purpose of enzyme immobilization, which causes great environmental pollution.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to construct the enzyme electrochemical sensor for detecting the phenolic substances in the water environment, which has the advantages of simple preparation steps, easy operation, high sensitivity, high selectivity and good stability.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of a polymer membrane electrode for detecting phenolic pollutants comprises the following steps:
the method comprises the following steps: polishing pretreatment is carried out on the surface of the glassy carbon electrode;
step two: dissolving polyphenol oxidase in a phosphate buffer solution to obtain a polyphenol oxidase solution with the concentration of 1mg/mL, and refrigerating the polyphenol oxidase solution at the temperature of 0-4 ℃ for later use;
step three: dissolving the hyperbranched amphiphilic block copolymer in chloroform to obtain a high molecular polymer solution, and refrigerating the high molecular polymer solution at the temperature of 0-4 ℃ for later use;
step four: dropwise adding the polyphenol oxidase solution obtained in the step two to the surface of the glassy carbon electrode obtained in the step one, and drying at room temperature until a layer of polyphenol oxidase solution film is formed on the surface of the electrode;
step five: and (4) dropwise adding the high molecular polymer solution obtained in the step three onto the surface of the polyphenol oxidase solution membrane formed by the electrode obtained in the step four, quickly transferring the solution to a constant temperature and humidity box, standing the solution until the surface of the electrode forms a uniform high molecular polymer membrane containing polyphenol oxidase, and finally preparing the high molecular membrane electrode for detecting the phenolic pollutants.
Further, in the above scheme, in the step one, the glassy carbon electrode pretreatment step is: respectively adopting alumina powder with the particle size of 0.2-0.5 mu m and alumina powder with the particle size of 0.02-0.05 mu m to polish the glassy carbon sheet, respectively ultrasonically cleaning the glassy carbon sheet for 2-3min by using ethanol and distilled water, and airing the glassy carbon sheet for later use.
Further, in the above scheme, in the second step, the concentration of the phosphoric acid buffer solution is 1mmol/L, and the pH value is 5.5-7.0.
Further, in the above scheme, in step three, the mass concentration of the high molecular polymer solution is 0.02 wt% to 0.1 wt%, and the preparation process of the hyperbranched amphiphilic block copolymer is as follows:
s1: preparation of RAFT Agents
Adding 1g of sodium hydride into a reaction bottle, introducing argon, then adding anhydrous ether, placing the reaction bottle into an ice-water bath, dropwise adding 10 equivalents of dodecyl mercaptan, moving the reaction bottle to room temperature after dropwise adding, stirring for reaction for 10min, transferring the reaction bottle into the ice-water bath again, dropwise adding 11 equivalents of carbon disulfide, and stirring for reaction for 2h at room temperature after dropwise adding is completed to obtain yellow liquid 1 for later use;
adding 0.04 equivalent of palladium acetate, 65 equivalent of bromoacetic acid and 10 equivalent of vinyl acetate into a single-neck bottle, stirring at 90 ℃ for reaction for 24 hours, filtering, and performing column chromatography separation on the liquid to obtain yellow liquid 2 for later use;
slowly dropwise adding the yellow liquid 1 into the yellow viscous liquid 2, stirring at room temperature for 1-2h, and after the reaction is finished, washing with water, drying, and performing column chromatography separation to obtain an RAFT reagent;
s2: polymerisation reaction
Weighing 1 equivalent of RAFT reagent and 0.02 equivalent of free radical initiator in a Schlenk bottle, adding 100-500 equivalent of hydrophobic monomer, introducing argon to replace air in the bottle, filling argon in the bottle, sealing, stirring and polymerizing at 60-90 ℃, diluting the polymer with tetrahydrofuran, precipitating in n-hexane, filtering and drying to obtain a prepolymer;
and adding 1 equivalent of the obtained prepolymer into another schlenk bottle, adding 0.05 equivalent of the initiator and 100-500 equivalent of the hydrophilic monomer, and repeating the steps to obtain the hyperbranched amphiphilic block copolymer.
Further, in the above scheme, the hydrophobic monomer is selected from one of styrene, methyl methacrylate, butyl acrylate, vinyl acetate, glycidyl methacrylate, fluorine-containing acrylate or vinyl trimethylsilane.
Further, in the above scheme, the hydrophilic monomer is selected from one of 4-vinylpyridine, dimethylaminoethyl methacrylate, N-vinylpyrrolidone or N-isopropylacrylamide.
Further, in the above scheme, in the fourth step, the polyphenol oxidase solution is measured in an amount of 2-12 μ L, and the drying time at room temperature is 10-30 min.
Further, in the above scheme, in the fifth step, the amount of the high molecular polymer solution is measured to be 4-14 μ L, the temperature of the constant temperature and humidity chamber is 20-40 ℃, the humidity is 60% RH-90% RH, and the standing time is 0.5-5 h.
The invention provides a polymer membrane electrode for detecting phenolic pollutants, which is prepared by the preparation method.
The synthesized RAFT reagent can be used as a chain transfer agent and a branched monomer for copolymerization, so that the polymer has a hyperbranched structure and has active tail ends, and therefore, a section of hydrophobic monomer is prepolymerized firstly during polymerization, and the hydrophilic monomer is grafted by using the active tail ends, so that the amphiphilic block copolymer with the hyperbranched structure is obtained; the research of the scheme discovers that the use effect of the polymer prepared by using dimethylaminoethyl methacrylate (DMAEMA) as a hydrophilic monomer and vinyl trimethylsilane as a hydrophobic monomer is optimal, because the hydrophobic monomer contains silane groups, the surface of a formed film is smoother, and the subsequent pore-forming is facilitated to be carried out smoothly; DMAEMA molecules contain tertiary amino, ester group and unsaturated double bond, and have strong alkalinity, the tertiary amino has positive charge on the surface of oil water, and can be combined with polyphenol oxidase with negative charge more firmly, the ester group increases molecular flexibility, and molecular chain stretching is facilitated, so that the tertiary amino and the ester group are orderly arranged on the surface of the polyphenol oxidase.
According to the invention, a respiratory map method is adopted, a polyphenol oxidase solution is taken as a substrate, the pouring of a polymer solution is carried out in a low-temperature high-humidity environment, chloroform is volatile, the temperature of the substrate is obviously reduced, water vapor in the high-humidity environment is condensed to the surface of the polymer solution to form micron-sized water drops, the temperature of the substrate is recovered to the environmental temperature after the solvent is completely volatilized, and the water drops are volatilized into the air again, so that a porous structure can be left on the surface of the membrane. Meanwhile, the polymer chains with the hyperbranched structure reduce the chain entanglement among molecular chains, reduce the contractility, and form an ordered network structure by self-assembly on the surface of oil and water through amphiphilic induction; the polyphenol oxidase with positive charges and the polymer with the ordered network structure with negative charges enable biomolecules and polymer molecules to be ordered through charge action, the prepared porous membrane is more regular, and ordered directional immobilization of the polyphenol oxidase can be realized. Meanwhile, the macromolecular polymer forms a macromolecular membrane with a porous structure under the drive of the hydrophilicity and hydrophobicity of the macromolecular polymer, so that more enzyme activity centers can be exposed to be contacted with a target object to be detected.
The invention has the beneficial effects that: the preparation method of the polymer membrane electrode for detecting the phenolic pollutants is simple and low in cost; the selective monomer is more, can be used for carrying out quantitative analysis on a plurality of phenolic compounds, and has wide application range; in the film forming process, a polymer film with a porous structure is formed, so that more enzyme activity centers can be exposed to be contacted with a target object to be detected; the method has the advantages of high reaction speed, low detection lower limit and wide detection range; the prepared electrochemical biosensor has high sensitivity and good selectivity and stability, and can be used for detecting phenolic substances in a water body environment.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a graph showing a calibration curve of the response current of catechols according to the present invention with respect to time in examples 1 to 5 and comparative examples 1 to 3.
FIG. 2 is a graph showing the results of a long-term stability test of the polymer membrane electrode obtained in example 5.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of a polymer membrane electrode for detecting phenolic pollutants, which comprises the following steps:
the method comprises the following steps: polishing pretreatment is carried out on the surface of the glassy carbon electrode: respectively adopting alumina powder with the particle size of 0.2-0.5 mu m and alumina powder with the particle size of 0.02-0.05 mu m to polish the glassy carbon sheet, then respectively ultrasonically cleaning the glassy carbon sheet for 2-3min by using ethanol and distilled water, and airing the glassy carbon sheet for later use;
step two: dissolving polyphenol oxidase in 1mmol/L phosphate buffer solution (pH value of 5.5-7.0) to obtain polyphenol oxidase solution with concentration of 1mg/mL, and refrigerating at 0-4 deg.C;
step three: dissolving the hyperbranched amphiphilic block copolymer into chloroform to obtain 0.02 wt% -0.1 wt% of high molecular polymer solution, and refrigerating the high molecular polymer solution at the temperature of 0-4 ℃ for later use;
step four: dripping 2-12 mu L of polyphenol oxidase solution obtained in the step II on the surface of the glassy carbon electrode obtained in the step I, and drying at room temperature for 10-30min until a layer of polyphenol oxidase solution film is formed on the surface of the electrode;
step five: and (3) dropwise adding 4-14 mu L of the high molecular polymer solution obtained in the third step onto the surface of the polyphenol oxidase solution membrane formed by the electrode obtained in the fourth step, quickly transferring the solution to a constant-temperature and constant-humidity box with the temperature of 20-40 ℃ and the humidity of 60-90% RH, and standing for 0.5-5h until the surface of the electrode forms a uniform high molecular polymer membrane containing polyphenol oxidase, thus finally preparing the high molecular membrane electrode for detecting the phenol pollutants.
In the above embodiment, the preparation process of the hyperbranched amphiphilic block copolymer in step three is as follows:
s1: preparation of RAFT Agents
Adding 1g of sodium hydride into a reaction bottle, introducing argon, then adding anhydrous ether, placing the reaction bottle into an ice-water bath, dropwise adding 10 equivalents of dodecyl mercaptan, moving the reaction bottle to room temperature after dropwise adding, stirring for reaction for 10min, transferring the reaction bottle into the ice-water bath again, dropwise adding 11 equivalents of carbon disulfide, and stirring for reaction for 2h at room temperature after dropwise adding is completed to obtain yellow liquid 1 for later use;
adding 0.04 equivalent of palladium acetate, 65 equivalent of bromoacetic acid and 10 equivalent of vinyl acetate into a single-neck bottle, stirring at 90 ℃ for reaction for 24 hours, filtering, and performing column chromatography separation on the liquid to obtain yellow liquid 2 for later use;
slowly dropwise adding the yellow liquid 1 into the yellow viscous liquid 2, stirring at room temperature for 1-2h, and after the reaction is finished, washing with water, drying, and performing column chromatography separation to obtain an RAFT reagent;
s2: polymerisation reaction
Weighing 1 equivalent of RAFT reagent and 0.02 equivalent of free radical initiator in a Schlenk bottle, adding 100 equivalents of hydrophobic monomer, introducing argon to replace air in the bottle, filling the bottle with argon, sealing, stirring and polymerizing at 60-90 ℃, diluting the polymer with tetrahydrofuran, precipitating in n-hexane, filtering and drying to obtain a prepolymer;
and adding 1 equivalent of the obtained prepolymer into another schlenk bottle, adding 0.05 equivalent of the initiator and 200 equivalents of the hydrophilic monomer, and repeating the steps to obtain the hyperbranched amphiphilic block copolymer.
The following specific examples are given in conjunction with the above schemes, and it is apparent that the described examples are some, but not all, of the examples of the present invention.
Example 1: the mass fraction of the high molecular polymer solution is 0.05 percent, the polyphenol oxidase solution is 6 mul, and the high molecular polymer solution is 7 mul; the hydrophobic monomer is styrene, and the hydrophilic monomer is 4-vinylpyridine.
Example 2: the mass fraction of the high molecular polymer solution is 0.05 percent, the polyphenol oxidase solution is 6 mul, and the high molecular polymer solution is 7 mul; the hydrophobic monomer is vinyl trimethylsilane, and the hydrophilic monomer is dimethylaminoethyl methacrylate.
Example 3: the mass fraction of the high molecular polymer solution is 0.05 percent, the polyphenol oxidase solution is 6 mul, and the high molecular polymer solution is 7 mul; the hydrophobic monomer is perfluorooctyl ethyl acrylate, and the hydrophilic monomer is N-vinyl pyrrolidone.
Example 4: the mass fraction of the high molecular polymer solution is 0.07 percent, the polyphenol oxidase solution is 6 mul, and the high molecular polymer solution is 7 mul; the hydrophobic monomer is vinyl trimethylsilane, and the hydrophilic monomer is dimethylaminoethyl methacrylate.
Example 5: the mass fraction of the high molecular polymer solution is 0.1 percent, the polyphenol oxidase solution is 6 mul, and the high molecular polymer solution is 7 mul; the hydrophobic monomer is vinyl trimethylsilane, and the hydrophilic monomer is dimethylaminoethyl methacrylate.
Comparative example 1: substitution of hyperbranched amphiphilic Block copolymers for homomonomeric Linear amphiphilic Block copolymers, RAFT reagentsReference J.Polym.Sci.part A: Polym.Chem.2010, 48,3573-3580, the rest of the procedure being as in example 5.
Comparative example 2: the polymer membrane electrode is prepared by a traditional embedding method, and the method can be specifically carried out by the following steps.
The method comprises the following steps: polishing pretreatment is carried out on the surface of the glassy carbon electrode: respectively adopting alumina powder with the particle size of 0.2-0.5 mu m and alumina powder with the particle size of 0.02-0.05 mu m to polish the glassy carbon sheet, then respectively ultrasonically cleaning the glassy carbon sheet for 2-3min by using ethanol and distilled water, and airing the glassy carbon sheet for later use;
step two: dissolving polyphenol oxidase in 1mmol/L phosphate buffer solution (pH value of 5.5-7.0) to obtain polyphenol oxidase solution with concentration of 1mg/mL, and refrigerating at 0-4 deg.C;
step three: dissolving hyperbranched amphiphilic block copolymer (hydrophobic monomer is vinyl trimethylsilane, hydrophilic monomer is dimethylaminoethyl methacrylate) in chloroform to obtain 0.1 wt% of high molecular polymer solution, and refrigerating the high molecular polymer solution at the temperature of 0-4 ℃ for later use;
step four: dropwise adding 2-12 mu L of polyphenol oxidase solution obtained in the step II and 4-14 mu L of high molecular polymer solution obtained in the step III into a centrifuge tube, fully shaking and uniformly mixing, transferring 13 mu L of polyphenol oxidase solution to be dropwise added onto the surface of the glassy carbon electrode obtained in the step I, and placing the glassy carbon electrode in an air environment until the surface of the electrode is completely dried; finally, the polymer membrane electrode for detecting the phenol pollutants is prepared.
Comparative example 3: the polymer membrane electrode is prepared by adopting a traditional self-crosslinking method, and the method can be carried out by the following steps.
The method comprises the following steps: polishing pretreatment is carried out on the surface of the glassy carbon electrode: respectively adopting alumina powder with the particle size of 0.2-0.5 mu m and alumina powder with the particle size of 0.02-0.05 mu m to polish the glassy carbon sheet, then respectively ultrasonically cleaning the glassy carbon sheet for 2-3min by using ethanol and distilled water, and airing the glassy carbon sheet for later use;
step two: dissolving polyphenol oxidase in 1mmol/L phosphate buffer solution (pH value of 5.5-7.0) to obtain polyphenol oxidase solution with concentration of 1mg/mL, and refrigerating at 0-4 deg.C;
step three: and (3) measuring 6 mu L of polyphenol oxidase solution obtained in the second step by using a micropipette, dropwise adding the polyphenol oxidase solution obtained in the first step onto the surface of the glassy carbon electrode until a layer of polyphenol oxidase semi-dry film is formed on the surface of the electrode, suspending the glassy carbon electrode above a closed container filled with 25 wt% of glutaraldehyde solution, standing, and crosslinking volatilized glutaraldehyde and polyphenol oxidase molecules until the surface of the electrode is completely dried to finally obtain the polymer membrane electrode for detecting phenolic pollutants.
The steps of applying the polymer membrane electrode of the embodiments 1 to 5 and the comparative examples 1 to 3 to detecting catechol in a water environment are as follows: the catechol in the sample to be detected was detected by an electrochemical detection device consisting of a chemical workstation (Shanghai Hua Model CHI660A), a three-electrode system (the polymer membrane glassy carbon electrode prepared by the above method was used as a working electrode, a 5mm x 6mm platinum sheet electrode was used as a counter electrode, and a saturated calomel electrode was used as a reference electrode), and an electrolytic cell.
Before the concentration of the catechol in the sample to be detected is detected, a standard curve needs to be drawn by using a catechol standard solution. Adding 10mL of 0.1mol/L phosphoric acid buffer solution (pH is 6.0) into an electrolytic cell of the electrochemical detection equipment by adopting an amperometric method, ensuring that the front ends of three electrodes are immersed below the liquid level of a sample to be detected, setting an electrochemical workstation to be in a constant potential timing current mode, setting a working potential to be-200 mV (vs. saturated calomel electrode), measuring the response current of the electrodes under stable electromagnetic stirring, detecting to obtain a step curve of the response current along with the change of time, obtaining a corresponding relation between the concentration of the catechol and the response current according to the step curve, and performing linear fitting on data points in the graph to obtain a standard curve of the catechol (figure 1).
When the concentration of the catechol in the sample to be detected is detected, 10mL of the sample to be detected diluted by 0.1mol/L phosphoric acid buffer solution (with the pH value being 6.0) (the dilution ratio of the 0.1mol/L phosphoric acid buffer solution to the sample to be detected is 99) to 1, the response current corresponding to the concentration of the catechol in the diluted sample to be detected is detected by adopting the detection method and the steps, the response current value is substituted into the fitted equation, the concentration of the catechol in the diluted sample to be detected can be calculated, and the concentration value of the catechol in the sample is recorded in table 1.
TABLE 1
As can be seen from table 1, the polymer film sensors prepared in examples 1 to 5 all have higher sensitivity, wherein the sensitivity of examples 3 to 5 is relatively higher in the present application, and the detected concentrations of catechol in the samples to be detected are relatively close. In addition, the detection limit of the sensor is low as seen from example 5, the linear detection range is 0.10-30 μ M, and the detection limit is 0.068 μ M. Fig. 2 shows the long-term stability test results of the sensor fabricated from the polymer membrane electrode fabricated in example 1, and it can be seen from the figure that the response current of the electrode to catechol can still maintain 88.7% of the initial current after the functional polymer membrane sensor fabricated in the present invention is stored for 30 days, which shows better stability.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (9)
1. A preparation method of a polymer membrane electrode for detecting phenolic pollutants is characterized by comprising the following steps:
the method comprises the following steps: polishing pretreatment is carried out on the surface of the glassy carbon electrode;
step two: dissolving polyphenol oxidase in a phosphate buffer solution to obtain a polyphenol oxidase solution with the concentration of 1mg/mL, and refrigerating the polyphenol oxidase solution at the temperature of 0-4 ℃ for later use;
step three: dissolving the hyperbranched amphiphilic block copolymer in chloroform to obtain a high molecular polymer solution, and refrigerating the high molecular polymer solution at the temperature of 0-4 ℃ for later use;
step four: dropwise adding the polyphenol oxidase solution obtained in the step two to the surface of the glassy carbon electrode obtained in the step one, and drying at room temperature until a layer of polyphenol oxidase solution film is formed on the surface of the electrode;
step five: and (4) dropwise adding the high molecular polymer solution obtained in the step three onto the surface of the polyphenol oxidase solution membrane formed by the electrode obtained in the step four, quickly transferring the solution to a constant temperature and humidity box, and standing until the surface of the electrode forms a uniform high molecular polymer membrane containing polyphenol oxidase, thus finally preparing the high molecular membrane electrode for detecting the phenolic pollutants.
2. The method for preparing a polymer membrane electrode for detecting phenolic pollutants according to claim 1, wherein in the step one, the step of pretreating the glassy carbon electrode comprises the following steps: respectively adopting alumina powder with the particle size of 0.2-0.5 mu m and alumina powder with the particle size of 0.02-0.05 mu m to polish the glassy carbon sheet, then respectively ultrasonically cleaning the glassy carbon sheet for 2-3min by using ethanol and distilled water, and airing the glassy carbon sheet for later use.
3. The method for preparing a polymer film electrode for detecting phenolic pollutants as claimed in claim 1, wherein in the second step, the concentration of the phosphoric acid buffer solution is 1mmol/L, and the pH value is 5.5-7.0.
4. The method according to claim 1, wherein in step three, the mass concentration of the polymer solution is 0.02 wt% to 0.1 wt%, and the hyperbranched amphiphilic block copolymer is prepared by:
s1: preparation of RAFT Agents
Adding 1g of sodium hydride into a reaction bottle, introducing argon, then adding anhydrous ether, placing the reaction bottle into an ice-water bath, dropwise adding 10 equivalents of dodecyl mercaptan, moving the reaction bottle to room temperature after dropwise adding, stirring for reaction for 10min, transferring the reaction bottle into the ice-water bath again, dropwise adding 11 equivalents of carbon disulfide, and stirring for reaction for 2h at room temperature after dropwise adding is completed to obtain yellow liquid 1 for later use;
adding 0.04 equivalent of palladium acetate, 65 equivalent of bromoacetic acid and 10 equivalent of vinyl acetate into a single-neck bottle, stirring at 90 ℃ for reaction for 24 hours, filtering, and performing column chromatography separation on the liquid to obtain yellow liquid 2 for later use;
slowly dropwise adding the yellow liquid 1 into the yellow viscous liquid 2, stirring at room temperature for 1-2h, and after the reaction is finished, washing with water, drying, and performing column chromatography separation to obtain an RAFT reagent;
s2: polymerisation reaction
Weighing 1 equivalent of RAFT reagent and 0.02 equivalent of free radical initiator in a Schlenk bottle, adding 100-500 equivalent of hydrophobic monomer, introducing argon to replace air in the bottle, filling argon in the bottle, sealing, stirring and polymerizing at 60-90 ℃, diluting the polymer with tetrahydrofuran, precipitating in n-hexane, filtering and drying to obtain a prepolymer;
and adding 1 equivalent of the obtained prepolymer into another schlenk bottle, adding 0.05 equivalent of the initiator and 100-500 equivalent of the hydrophilic monomer, and repeating the steps to obtain the hyperbranched amphiphilic block copolymer.
5. The method of claim 4, wherein the hydrophobic monomer is selected from one of styrene, methyl methacrylate, butyl acrylate, vinyl acetate, glycidyl methacrylate, fluoroacrylate, and vinyltrimethylsilane.
6. The method according to claim 4, wherein the hydrophilic monomer is selected from one of 4-vinylpyridine, dimethylaminoethyl methacrylate, N-vinylpyrrolidone and N-isopropylacrylamide.
7. The method according to claim 1, wherein in the fourth step, the polyphenol oxidase solution is measured in an amount of 2 to 12 μ L, and the drying time at room temperature is 10 to 30 min.
8. The method for preparing a polymer film electrode for detecting phenolic pollutants as claimed in claim 1, wherein in the fifth step, the amount of the polymer solution is measured to be 4-14 μ L, the temperature of the constant temperature and humidity chamber is 20-40 ℃, the humidity is 60% RH-90% RH, and the standing time is 0.5-5 h.
9. A polymer membrane electrode for detecting phenolic contaminants prepared by the preparation method according to any one of claims 1 to 8.
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