Molecularly imprinted polymer electrocatalytic electrode plate, and preparation method and application thereof

Abstract

The application discloses a molecular imprinting polymer electrocatalytic polar plate and a preparation method and application thereof, and the preparation method comprises the following steps: cleaning an electrode plate; stirring a benzene[1,2-B:4,5-B']dithiophene-4,8-dione, 3-boronic acid thiophene, azithromycin, 3,3'-bithiophene and tetrabutylammonium perchlorate acetonitrile solution to obtain a polymerization solution; taking a graphite plate as a working electrode and a counter electrode, and taking a non-aqueous Ag + The electrode is a reference electrode, the electro-polymerization is completed in the polymerization solution, and a MIP (PBth-BQ) molecular imprinting catalytic electrode is obtained; the MIP (PBth-BQ) molecular imprinting catalytic electrode is taken as a working electrode, the graphite sheet is taken as a counter electrode, saturated mercury is taken as a reference electrode, constant-temperature water bath stirring is carried out, the template is removed, and cleaning is carried out. The electrocatalytic polar plate has holes on the surface, the azithromycin is wrapped first and then removed, the adsorption effect is better, the selectivity is high, the adsorption and electrocatalysis are synergistically combined, and the removal effect is good.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of electrocatalytic degradation of organic matter, and particularly relates to a molecular imprinting polymer electrocatalytic plate and a preparation method and application thereof. BACKGROUND

[0002] New pollutants in sewage represented by antibiotics pose a great threat to the ecological environment and human health, and targeted removal technologies need to be developed to reduce water quality risks. Electro-catalysis is an important technology for upgrading the next generation of sewage treatment plants, which mainly uses input electrical energy to catalyze direct oxidation of pollutants or catalyze advanced oxidation reactions to indirectly break down pollutants, and has the advantages of being clean, high degradation degree, and simple operation. There are currently studies on the removal of antibiotics in sewage by electro-catalysis, which are mostly based on electro-catalytic advanced oxidation reactions, such as electro-Fenton, electro-activated persulfate, etc., and the obvious disadvantage is the need to add exogenous reagents (such as Fe 2+ , H2O2, SO4 2- , etc.), which not only increases the cost but also introduces new pollution sources. Electro-catalytic direct oxidation of pollutants is more suitable for the advanced treatment of new pollutants in sewage plants, but existing technologies are still limited by the diffusion mass transfer of low-concentration new pollutants, making it difficult to achieve efficient and energy-saving removal. Considering the complexity of sewage composition and the numerous interferents, the electro-catalytic plate is required to have selective enrichment ability. Molecular imprinting polymers can selectively recognize and bind target substances based on covalent or non-covalent interactions, which is expected to solve the diffusion mass transfer limitation, especially the thienyl polymer skeleton has strong electrochemical stability, and the design of molecular imprinting electro-catalytic plate based thereon is expected to solve the efficient and directional removal of specific new pollutants in sewage.

[0003] Existing catalysts lack the ability of selective enrichment, and are limited by diffusion mass transfer in the removal of low-concentration new pollutants, resulting in high cost and long power-on time of electro-catalytic method. Moreover, other high-concentration interferents (such as dissolved organic matter) in complex water bodies significantly affect the selectivity and efficiency of electro-catalytic reaction. In addition, although the existing molecular imprinting technology can achieve selective enrichment of a certain pollutant, it relies on the organic acid solution removal method, which consumes a large amount of organic reagents and is not environmentally friendly, and the removed pollutant molecules still need further treatment. SUMMARY

[0004] The present application aims to overcome the deficiencies in the prior art, and provides a molecular imprinting polymer electro-catalytic plate which can selectively enrich azithromycin, resist interference, and has fast adsorption speed; another object of the present application is to provide a preparation method of a molecular imprinting polymer electro-catalytic plate which has low cost and short power-on time; and still another object of the present application is to provide an application of the molecular imprinting polymer electro-catalytic plate in electro-catalytic degradation of the pollutant azithromycin.

[0005] Technical solution: The molecular formula of the molecularly imprinted polymer electrocatalytic plate is P(TBA2-Bth-BQ1-3,3'-Bth1)@GC, and the structural formula is:

[0006]

[0007] The preparation method of the molecularly imprinted polymer electrocatalytic plate comprises the following steps:

[0008] Step one, cleaning: clean the electrode plate;

[0009] Step two, preparation of polymerization solution: prepare an acetonitrile solution of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, 3-thiophene boronic acid, azithromycin, 3,3'-bithiophene and tetrabutylammonium perchlorate, stir to obtain a polymerization solution;

[0010] Step three, electro-polymerization: use the cleaned electrode plate as the working electrode and the counter electrode, use the non-aqueous Ag + electrode as the reference electrode, complete the electro-polymerization in the polymerization solution by cyclic voltammetry, clean after polymerization to obtain the MIP(PBth-BQ) molecularly imprinted catalytic electrode;

[0011] Step four, template removal: use the MIP(PBth-BQ) molecularly imprinted catalytic electrode as the working electrode, the electrode plate as the counter electrode, and saturated mercury as the reference electrode, constant temperature water bath and stirring, remove the template azithromycin by applying pulse potential or cyclic voltammetry scanning method, clean to obtain the molecularly imprinted polymer electrocatalytic plate, and the molecularly imprinted polymer electrocatalytic plate is stored in pure water for use.

[0012] Further, in step one, the cleaning is sequentially performed using acid, base and acetonitrile solution. Preferably, the acid is 0.01-0.1M sulfuric acid, and the base is 0.01-0.1M sodium hydroxide. The electrode plate is a graphite plate or a glassy carbon electrode.

[0013] Further, in step two, the molar ratio of the acetonitrile solution of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, 3-thiophene boronic acid, azithromycin, 3,3'-bithiophene (3,3'-Bth) and tetrabutylammonium perchlorate is 1-10:1-10:1-10:0.5-5:100. Preferably, the molar ratio of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, 3-thiophene boronic acid, azithromycin and 3,3'-bithiophene is 1:1:1:0.5, which is conducive to structural stability and makes the molecularly imprinted plate have the largest adsorption capacity. The stirring speed is 100-500 rpm, and the stirring time is 8-12 h.

[0014] Further, in step three, the potential of the cyclic voltammetry is -0.5-2.3V, the scanning rate is 10-100mV / s, and the scanning number is 2-10. Preferably, the lower limit of the potential of the cyclic voltammetry is -0.5-0.5V, and the upper limit is 2.3V.

[0015] Further, in step four, the high voltage of the pulse voltage is 0.7-1.2V, the low voltage is -1.0--0.7V, the time is 5-60s, and the cycle number is 10-30. Preferably, the time is 30s. The temperature of the constant temperature water bath is 25-35℃, and the stirring speed is 300-1000rpm. Preferably, the temperature of the constant temperature water bath is 30℃, and the stirring speed is 500rpm.

[0016] Further, in step four, the scanning range of the cyclic voltammetry scanning method is -1.0-1.2V, the scanning rate is 20-100mV / s, and the scanning number is 10-50. The effect of the pulse potential is better than that of the cyclic voltammetry scanning method.

[0017] The application of the molecularly imprinted polymer electro-catalytic plate in the electro-catalytic degradation of pollutants azithromycin.

[0018] Preparation principle: the electro-polymerization preparation method of the electro-catalytic plate is based on the oxidative electro-polymerization of a thiophene-based monomer. The obtained molecularly imprinted polymer realizes the selective enrichment of azithromycin on the surface of the electrode, and removes azithromycin efficiently through electrochemical oxidation. In the molecularly imprinted polymer, the covalent interaction between the boronic acid bond of the functional monomer and the ortho-hydroxyl group of azithromycin, and the space-matching hole site reserved in the electro-polymerization process realize the selective enrichment of azithromycin. After a period of enrichment, the concentration of azithromycin on the surface of the electro-catalytic plate is much higher than that in the sewage, and then the electro-catalytic degradation is carried out by electrifying. The addition of the catalytic center PBth-BQ in the MIP skeleton reduces the oxidation potential of azithromycin and enhances the electron transfer, and realizes more efficient electro-catalytic removal.

[0019] Advantages: compared with the prior art, the present application has the following obvious characteristics:

[0020] 1. The surface of the electro-catalytic plate has holes, which are wrapped with azithromycin first and then removed. The azithromycin in the sewage is selectively enriched before electro-catalysis, the adsorption effect is better, the selectivity is high, the adsorption and electro-catalysis synergistically act, and the removal effect is good.

[0021] 2. The electrochemical method removes the azithromycin molecular template in situ without using organic solvents.

[0022] 3. The preparation is convenient, no special equipment and high temperature and high pressure operation conditions are needed, the cost is low, and the electrification time is short.

[0023] 4. No additional reagent is needed in the catalytic process, and the final electron acceptor for the oxidation of pollutants is H2O or O2. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 is a preparation schematic of the present application;

[0025] Figure 2 is a surface water contact angle photo, A is a bare glassy carbon electrode, and B is a catalytic electrode loaded with MIP (PBth-BQ) ;

[0026] Figure 3 is an infrared reflection spectrum of the MIP (PBth-BQ) molecular imprinting catalytic electrode of the present application before removal of the AZN template, after removal of the AZN template, after recapturing of the AZN, and pure AZN;

[0027] Figure 4 is a kinetic curve of adsorption and removal of AZN by the MIP (PBth-BQ) @GC molecular imprinting catalytic electrode and the PBth-BQ @GC catalytic electrode of the present application;

[0028] Figure 5 is a kinetic curve of adsorption and electrocatalytic removal of AZN at -0.7 V and 1.2 V after adsorption by the MIP (PBth-BQ) @GC molecular imprinting catalytic electrode and the PBth-BQ @GC catalytic electrode of the present application. DETAILED DESCRIPTION

[0029] In the following examples, the materials, reagents, etc. used, unless otherwise specified, can be obtained from commercial channels. The experimental methods not specified in the examples are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturer.

[0030] Example 1

[0031] As Figure 1 A preparation method of a molecular imprinting polymer electrocatalytic plate includes the following steps:

[0032] (1) Cleaning: The graphite plate (4 cm x 2 cm x 0.1 cm) is sequentially cleaned with 0.1 M sulfuric acid, 0.1 M sulfuric acid and acetonitrile solution.

[0033] (2) Preparation of polymerization solution: 1 mM of benzene [1,2-B:4,5-B'] dithiophene-4,8-dione, 1 mM of 3-thiophene boronic acid, 1 mM of azithromycin, 0.5 mM of 3,3'-bithiophene and 0.1 M of tetrabutylammonium perchlorate acetonitrile solution are stirred at 500 rpm for 8 h to obtain the polymerization solution.

[0034] (3) Electro-polymerization: The cleaned graphite plate is used as the working electrode and the counter electrode, and the non-aqueous Ag +The electrode is a reference electrode, and 10 cycles of cyclic voltammetry are performed in the polymerization solution at a potential window of 0-2.3 V and a scan rate of 10 mV / s to complete the electro polymerization. After polymerization, acetonitrile and ultrapure water are used for cleaning to obtain the MIP (PBth-BQ) molecularly imprinted catalytic electrode.

[0035] (4) Template removal: The MIP (PBth-BQ) molecularly imprinted catalytic electrode is used as the working electrode, the graphite plate is used as the counter electrode, and the saturated calomel electrode is used as the reference electrode. The template azithromycin is removed by applying a pulse potential. The pulse is set to 0.7 V for 60 s, -0.7 V for 60 s, and the cycle is repeated for 30 times. During the template removal process, the constant temperature water bath is 25°C, and the stirring speed is 1000 rpm. The electrode after removing the AZN template is cleaned with ultrapure water, and then stored in pure water for use.

[0036] Example 2

[0037] A preparation method of a molecularly imprinted polymer electrocatalytic electrode plate, comprising the following steps:

[0038] (1) Cleaning: The graphite plate (4 cm x 2 cm x 0.1 cm) is cleaned with 0.1 M sulfuric acid, 0.1 M sulfuric acid, and acetonitrile solution.

[0039] (2) Preparation of polymerization solution: 10 mM of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, 10 mM of 3-thiophene boronic acid, 10 mM of azithromycin, 5 mM of 3,3'-bithiophene, and 0.1 M of tetrabutylammonium perchlorate acetonitrile solution are stirred at 100 rpm for 12 h to obtain the polymerization solution.

[0040] (3) Electro polymerization: The cleaned graphite plate is used as the working electrode and the counter electrode, and the non-aqueous Ag + The electrode is a reference electrode, and 10 cycles of cyclic voltammetry are performed in the polymerization solution at a potential window of 0-2.3 V and a scan rate of 10 mV / s to complete the electro polymerization. After polymerization, acetonitrile and ultrapure water are used for cleaning to obtain the MIP (PBth-BQ) molecularly imprinted catalytic electrode.

[0041] (4) Template removal: The MIP (PBth-BQ) molecularly imprinted catalytic electrode is used as the working electrode, the graphite plate is used as the counter electrode, and the saturated calomel electrode is used as the reference electrode. The template azithromycin is removed by applying a pulse potential. The pulse is set to 1.2 V for 30 s, -1.0 V for 30 s, and the cycle is repeated for 10 times. During the template removal process, the constant temperature water bath is 35°C, and the stirring speed is 300 rpm. The electrode after removing the AZN template is cleaned with ultrapure water, and then stored in pure water for use.

[0042] Example 3

[0043] A preparation method of a molecularly imprinted polymer electrocatalytic electrode plate, comprising the following steps:

[0044] (1) Cleaning: Clean the graphite plate (4 cm x 2 cm x 0.1 cm) with 0.1M sulfuric acid, 0.1M sulfuric acid and acetonitrile solution in turn.

[0045] (2) Preparation of polymerization solution: 4mM of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, 4mM of 3-thiophene boronic acid, 4mM of azithromycin, 2mM of 3,3'-bithiophene and 0.1M of tetrabutylammonium perchlorate acetonitrile solution, 500rpm stirring for 10h, to obtain the polymerization solution.

[0046] (3) Electro-polymerization: The cleaned graphite plate is used as the working electrode and the counter electrode, and the non-aqueous Ag + electrode is used as the reference electrode. The cyclic voltammetry is performed in the polymerization solution at a potential window of -0.5-2.3V with a scan rate of 20mV / s for 3 cycles to complete the electro-polymerization. After the polymerization is completed, the MIP(PBth-BQ) molecular imprinting catalytic electrode is obtained by cleaning with acetonitrile and ultrapure water in turn.

[0047] (4) Template removal: The MIP(PBth-BQ) molecular imprinting catalytic electrode is used as the working electrode, the graphite plate is used as the counter electrode, and the saturated calomel electrode is used as the reference electrode. The template azithromycin is removed by applying a pulse potential. The pulse is set to 1.2V for 30s, -1.0V for 30s, and the cycle is repeated for 10 times. During the template removal process, the constant temperature water bath is 30℃, and the stirring speed is 500rpm. The electrode after the AZN template is removed is cleaned with ultrapure water, and then stored in pure water for use.

[0048] Example 4

[0049] A preparation method of a molecular imprinting polymer electro-catalytic electrode plate, comprising the following steps:

[0050] (1) Cleaning: Clean the glassy carbon electrode (4 cm x 2 cm x 0.1 cm) with 0.1M sulfuric acid, 0.1M sulfuric acid and acetonitrile solution in turn.

[0051] (2) Preparation of polymerization solution: 4mM of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, 4mM of 3-thiophene boronic acid, 4mM of azithromycin, 2mM of 3,3'-bithiophene and 0.1M of tetrabutylammonium perchlorate acetonitrile solution, 500rpm stirring for 12h, to obtain the polymerization solution.

[0052] (3) Electro-polymerization: The cleaned glassy carbon electrode is used as the working electrode and the counter electrode, and the non-aqueous Ag +The electrode is a reference electrode, and cyclic voltammetry is performed 5 times at a scanning speed of 50 mV / s in a potential window of 0.5-2.3 V in the polymerization solution to complete the electro-polymerization. After the polymerization is completed, the MIP (PBth-BQ) molecular imprinting catalytic electrode is washed with acetonitrile and ultrapure water in sequence to obtain the MIP (PBth-BQ) molecular imprinting catalytic electrode.

[0053] (4) Template removal: The MIP (PBth-BQ) molecular imprinting catalytic electrode is used as the working electrode, the glassy carbon electrode is used as the counter electrode, and the saturated calomel electrode is used as the reference electrode. The template azithromycin is removed by applying a pulse potential. The pulse is set to 1.0 V for 30 s, -1.0 V for 30 s, and the cycle is repeated for 30 times. During the template removal process, the water bath is kept at 30°C and stirred at 500 rpm. The electrode after the AZN template is removed is washed with ultrapure water and then stored in pure water for use.

[0054] The contact angles of the MIP (PBth-BQ) molecular imprinting catalytic electrode before and after preparation in this example with water are shown in Figure 2 . After in-situ electro-polymerization of the MIP (PBth-BQ), the hydrophilicity of the electrode surface increases, and the water contact angle decreases from 89° to 43°, indicating that the molecular imprinting catalyst is successfully synthesized.

[0055] During the preparation of the MIP (PBth-BQ) on the surface of the glassy carbon electrode, the infrared reflection spectrum of the electrode surface at different stages is tested, and the results are shown in Figure 3 . On the electrode surface after electro-polymerization of the MIP (PBth-BQ) and without removal of the azithromycin template, there is a strong response at 1680 cm -1 from the stretching vibration of -C=O (from the ester bond of the azithromycin macrocycle). After the azithromycin template is removed by electric pulse, the response significantly decreases, and after the azithromycin is recaptured, the response becomes strong again, indicating that the molecular imprinting polymer catalytic electrode is successfully synthesized and can reversibly capture and remove azithromycin molecules.

[0056] Example 5

[0057] A method for preparing a molecular imprinting polymer electro-catalytic electrode plate, comprising the following steps:

[0058] (1) Cleaning: The graphite plate (4 cm x 2 cm x 0.1 cm) is sequentially cleaned with 0.1 M sulfuric acid, 0.1 M sulfuric acid, and acetonitrile solution.

[0059] (2) Preparation of polymerization solution: 4 mM of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, 4 mM of 3-thiophene boronic acid, 4 mM of azithromycin, 2 mM of 3,3'-bithiophene, and 0.1 M of tetrabutylammonium perchlorate acetonitrile solution are stirred at 500 rpm for 12 h to obtain the polymerization solution.

[0060] (3) Electro-polymerization: The cleaned graphite plate was used as the working electrode and the counter electrode, and the non-aqueous Ag+ electrode was used as the reference electrode. Electro-polymerization was completed by cyclic voltammetry for 5 cycles at a scan rate of 50 mV / s in the potential window of 0-2.3 V in the polymerization solution. After polymerization, the MIP (PBth-BQ) molecularly imprinted catalytic electrode was obtained by cleaning with acetonitrile and ultrapure water in sequence. + Electro-polymerization: The cleaned graphite plate was used as the working electrode and the counter electrode, and the non-aqueous Ag+ electrode was used as the reference electrode. Electro-polymerization was completed by cyclic voltammetry for 5 cycles at a scan rate of 50 mV / s in the potential window of 0-2.3 V in the polymerization solution. After polymerization, the MIP (PBth-BQ) molecularly imprinted catalytic electrode was obtained by cleaning with acetonitrile and ultrapure water in sequence.

[0061] (4) Template removal: The MIP (PBth-BQ) molecularly imprinted catalytic electrode was used as the working electrode, the graphite plate was used as the counter electrode, and the saturated calomel electrode was used as the reference electrode. The template azithromycin was removed by applying a pulse potential. The pulse was set to 1.0 V for 30 s, -1.0 V for 30 s, and the cycle was repeated for 30 times. The template removal process was carried out in a constant temperature water bath at 30°C with 500 rpm stirring. The electrode after removing the AZN template was cleaned with ultrapure water and then stored in pure water for use.

[0062] Example 6

[0063] A method for preparing a molecularly imprinted polymer catalytic electrode plate, comprising the following steps:

[0064] (1) Cleaning: The graphite plate (4 cm x 2 cm x 0.1 cm) was cleaned with 0.1M sulfuric acid, 0.1M sulfuric acid and acetonitrile solution in sequence.

[0065] (2) Preparation of polymerization solution: 4mM of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, 4mM of 3-thiophene boronic acid, 4mM of azithromycin, 2mM of 3,3'-bithiophene and 0.1M of tetrabutylammonium perchlorate acetonitrile solution were stirred at 500 rpm for 12h to obtain the polymerization solution.

[0066] (3) Electro-polymerization: The cleaned graphite plate was used as the working electrode and the counter electrode, and the non-aqueous Ag+ electrode was used as the reference electrode. Electro-polymerization was completed by cyclic voltammetry for 5 cycles at a scan rate of 50 mV / s in the potential window of 0-2.3 V in the polymerization solution. After polymerization, the MIP (PBth-BQ) molecularly imprinted catalytic electrode was obtained by cleaning with acetonitrile and ultrapure water in sequence.

[0067] (4) Template removal: The MIP (PBth-BQ) molecularly imprinted catalytic electrode was used as the working electrode, the graphite plate was used as the counter electrode, and the saturated calomel electrode was used as the reference electrode. The template azithromycin was removed by applying a pulse potential. The pulse was set to 1.0 V for 30 s, -1.0 V for 30 s, and the cycle was repeated for 30 times. The template removal process was carried out in a constant temperature water bath at 30°C with 500 rpm stirring. The electrode after removing the AZN template was cleaned with ultrapure water and then stored in pure water for use.

[0068] Example 7

[0069] A preparation method of a molecularly imprinted polymer electrocatalytic electrode plate, comprising the following steps:

[0070] (1) Cleaning: using 0.1M sulfuric acid, 0.1M sulfuric acid and acetonitrile solution to clean the graphite plate (4cmx2cmx0.1cm) in turn.

[0071] (2) Preparation of polymerization solution: 4mM of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, 4mM of 3-thiophene boronic acid, 4mM of azithromycin, 2mM of 3,3'-bithiophene and 0.1M of tetrabutylammonium perchlorate acetonitrile solution, 500rpm stirring for 12h, to obtain the polymerization solution.

[0072] (3) Electro-polymerization: using the cleaned graphite plate as the working electrode and the counter electrode, and using the non-aqueous Ag+ electrode as the reference electrode, the electro-polymerization is completed by cyclic voltammetry for 5 cycles in the polymerization solution within the potential window of 0-2.3V at a scan rate of 50mV / s. After the polymerization is completed, the MIP(PBth-BQ) molecularly imprinted catalytic electrode is obtained by cleaning with acetonitrile and ultrapure water in turn.

[0073] (4) Template removal: using the MIP(PBth-BQ) molecularly imprinted catalytic electrode as the working electrode, the graphite plate as the counter electrode, and the saturated calomel electrode as the reference electrode, the template azithromycin is removed by cyclic voltammetry scanning. The cyclic voltammetry scanning range is set to-0.7-0.7V, the scanning rate is 50mV / s, and the scanning number is 20. During the template removal process, the constant temperature water bath is 30℃, and the stirring speed is 500rpm. The electrode after removing the AZN template is cleaned with ultrapure water, and then stored in pure water for use.

[0074] Example 8

[0075] A preparation method of a molecularly imprinted polymer electrocatalytic electrode plate, comprising the following steps:

[0076] (1) Cleaning: using 0.1M sulfuric acid, 0.1M sulfuric acid and acetonitrile solution to clean the graphite plate (4cmx2cmx0.1cm) in turn.

[0077] (2) Preparation of polymerization solution: 4mM of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, 4mM of 3-thiophene boronic acid, 4mM of azithromycin, 2mM of 3,3'-bithiophene and 0.1M of tetrabutylammonium perchlorate acetonitrile solution, 500rpm stirring for 12h, to obtain the polymerization solution.

[0078] (3) Electro-polymerization: The cleaned graphite plate was used as the working electrode and the counter electrode, and the non-aqueous Ag+ electrode was used as the reference electrode. The electro-polymerization was completed by cyclic voltammetry for 5 cycles at a scan rate of 50 mV / s in a potential window of 0-2.3 V in the polymerization solution. After the polymerization was completed, the MIP (PBth-BQ) molecularly imprinted catalytic electrode was cleaned with acetonitrile and ultrapure water to obtain the MIP (PBth-BQ) molecularly imprinted catalytic electrode.

[0079] (4) Template removal: The MIP (PBth-BQ) molecularly imprinted catalytic electrode was used as the working electrode, and the graphite plate was used as the counter electrode. The saturated calomel electrode was used as the reference electrode. The template azithromycin was removed by cyclic voltammetry scanning. The cyclic voltammetry scanning range was set to -1.0-1.2 V, the scanning rate was 100 mV / s, and the scanning number was 50 cycles. During the template removal process, the water bath was kept at 30°C and stirred at 500 rpm. The electrode after the AZN template was removed was cleaned with ultrapure water and then stored in pure water for use.

[0080] Comparative Example 1

[0081] A preparation method of a PBth-BQ catalytic electrode, comprising the following steps:

[0082] (1) The graphite plate (4 cm x 2 cm x 0.1 cm) was sequentially cleaned with acid, base and organic solution.

[0083] (2) Then, the PBth-BQ catalytic electrode was electro-polymerized: The cleaned graphite plate was used as the working electrode and the counter electrode, and the non-aqueous Ag+ electrode was used as the reference electrode. The polymerization solution was 4 mM benzo[1,2-B:4,5-B']dithiophene-4,8-dione and 0.1 M tetrabutylammonium perchlorate acetonitrile solution. The electro-polymerization was completed by cyclic voltammetry for 5 cycles at a scan rate of 50 mV / s in a potential window of 0-2.3 V. After the polymerization was completed, the PBth-BQ catalytic electrode was cleaned with acetonitrile and ultrapure water.

[0084] Performance test:

[0085] I. Adsorption capacity test of azithromycin:

[0086] The MIP (PBth-BQ) molecularly imprinted polymer catalytic electrode prepared in Example 5 and the PBth-BQ catalytic electrode prepared in Comparative Example 1 were respectively placed in 100 mL of an aqueous solution containing 5 mg / L of azithromycin, and stirred at a speed of 500 rpm at 30°C to test the adsorption capacity of azithromycin. The adsorption kinetics curve is shown in Figure 4 The MIP (PBth-BQ) molecularly imprinted polymer catalytic electrode has greater adsorption capacity and faster selective adsorption rate than the PBth-BQ catalytic electrode.

[0087] II. Low-voltage electrocatalysis experiment:

[0088] The MIP (PBth-BQ) molecularly imprinted polymer catalytic electrode prepared in Example 5 was taken as the working electrode, ruthenium oxide as the counter electrode, and silver / silver chloride as the reference electrode, and electrocatalysis experiment was carried out in 0.1M Na2SO4 solution containing 5mM azithromycin. The water temperature was controlled at 30 degrees Celsius, and the stirring rate was 500 rpm. The electrocatalysis started after 2 hours of adsorption, and the oxygen exposure rate was 50 mL / min, and the working electrode was applied with a voltage of -0.7V.

[0089] The PBth-BQ catalytic electrode prepared in Comparative Example 1 was taken as the working electrode, ruthenium oxide as the counter electrode, and silver / silver chloride as the reference electrode, and electrocatalysis experiment was carried out in 0.1M Na2SO4 solution containing 5mM azithromycin. The water temperature was controlled at 30 degrees Celsius, and the stirring rate was 500 rpm, and the oxygen exposure rate was 50 mL / min, and the working electrode was applied with a voltage of -0.7V.

[0090] As shown in Figure 5 , the total removal rate of the pollutant azithromycin was 61.3% one hour after the start of electrocatalysis, which was increased by 26.7% compared with the non-molecularly imprinted polymer catalytic electrode PBth-BQ.

[0091] Three, high-voltage electrocatalysis experiment:

[0092] The MIP (PBth-BQ) molecularly imprinted polymer catalytic electrode prepared in Example 5 was taken as the working electrode, ruthenium oxide as the counter electrode, and silver / silver chloride as the reference electrode, and electrocatalysis experiment was carried out in 0.1M Na2SO4 solution containing 5mM azithromycin. The water temperature was controlled at 30 degrees Celsius, and the stirring rate was 500 rpm. The electrocatalysis started after 2 hours of adsorption, and the working electrode was applied with a voltage of 1.2V.

[0093] The PBth-BQ catalytic electrode prepared in Comparative Example 1 was taken as the working electrode, ruthenium oxide as the counter electrode, and silver / silver chloride as the reference electrode, and electrocatalysis experiment was carried out in 0.1M Na2SO4 solution containing 5mM azithromycin. The water temperature was controlled at 30 degrees Celsius, and the stirring rate was 500 rpm, and the working electrode was applied with a voltage of 1.2V.

[0094] As shown in Figure 5 , the total removal rate of the pollutant azithromycin was 82.14% one hour after the start of electrocatalysis, which was increased by 20.1% compared with the non-molecularly imprinted polymer catalytic electrode PBth-BQ. The P(TBA2-Bth-BQ1-3,3’-Bth1)@GC adsorption-electrocatalysis process can remove more than 80% of azithromycin within 1 hour at a voltage of 1.2V, while the pure electrocatalysis process of PBth-BQ@GC can only remove less than 60%.

[0095] In the above examples, Example 5 is the optimal example.

Claims

1. A molecularly imprinted polymer electrocatalytic electrode, characterized in that: The molecular formula is P(TBA2-Bth-BQ1-3, 3'-Bth1)@GC, and the structural formula is: 。 2. A method for preparing a molecularly imprinted polymer electrocatalytic electrode, characterized in that, Includes the following steps: Step 1: Clean the electrode plates; Step 2: Stir the acetonitrile solution of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, thiophene 3-boronate, azithromycin, 3,3'-bithiophene, and tetrabutylammonium perchlorate to obtain the polymerization solution; Step 3: Using the cleaned electrode plate as the working electrode and counter electrode, and using non-aqueous Ag... + The electrode is a reference electrode. Electropolymerization is completed in the polymerization solution by cyclic voltammetry. After polymerization, the electrode is washed to obtain the MIP (PBth-BQ) molecularly imprinted catalytic electrode. Step four: Using the MIP (PBth-BQ) molecularly imprinted catalytic electrode as the working electrode, the electrode plate as the counter electrode, and saturated calomel as the reference electrode, the template azithromycin is removed by applying pulse potential or cyclic voltammetry scanning method in a constant temperature water bath with stirring. After washing, the molecularly imprinted polymer electrocatalytic electrode plate is obtained.

3. The method for preparing a molecularly imprinted polymer electrocatalytic electrode according to claim 2, characterized in that: In step one, the cleaning process involves sequentially using acid, alkali, and acetonitrile solutions.

4. The method for preparing a molecularly imprinted polymer electrocatalytic electrode according to claim 2, characterized in that: In step two, the molar ratio of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, thiophene 3-boronic acid, azithromycin, 3,3'-bithiophene, and tetrabutylammonium perchlorate in acetonitrile solution is 1~10:1~10:1~10:0.5~5:

100.

5. The method for preparing a molecularly imprinted polymer electrocatalytic electrode according to claim 4, characterized in that: The molar ratio of benzo[1,2-B:4,5-B']dithiophene-4,8-dione, thiophene 3-boronic acid, azithromycin, and 3,3'-bithiophene is 1:1:1:0.

5.

6. The method for preparing a molecularly imprinted polymer electrocatalytic electrode according to claim 2, characterized in that: In step two, the stirring speed is 100~500 rpm and the stirring time is 8~12 h.

7. A method for preparing a molecularly imprinted polymer electrocatalytic electrode according to claim 2, characterized in that: In step three, the potential of the cyclic voltammetry is -0.5 to 2.3 V, the scan rate is 10 to 100 mV / s, and the number of scans is 2 to 10.

8. A method for preparing a molecularly imprinted polymer electrocatalytic electrode according to claim 2, characterized in that: In step four, the high voltage of the pulse voltage is 0.7~1.2 V, the low voltage is -1.0 ~ -0.7 V, the duration is 5~60 s, and the number of cycles is 10~30.

9. A method for preparing a molecularly imprinted polymer electrocatalytic electrode according to claim 2, characterized in that: In step four, the temperature of the constant temperature water bath is 25~35℃, and the stirring speed is 300~1000 rpm.

10. The application of the molecularly imprinted polymer electrocatalytic electrode according to claim 1 in the electrocatalytic degradation of the pollutant azithromycin.

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