CN110470710B - Preparation and test method of electromagnetic composite material - Google Patents

Preparation and test method of electromagnetic composite material Download PDF

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CN110470710B
CN110470710B CN201910599572.9A CN201910599572A CN110470710B CN 110470710 B CN110470710 B CN 110470710B CN 201910599572 A CN201910599572 A CN 201910599572A CN 110470710 B CN110470710 B CN 110470710B
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CN110470710A (en
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马明明
杜茹
张�杰
王邦泽
王继伟
郭诗园
郭添帅
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Xian Polytechnic University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
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Abstract

The preparation method of the electromagnetic composite material comprises the following steps: preparing MWCNT-PEC by using pencil core and carbon nanotube powder and preparing MWCNT-PEC electrode; preparing a 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode on the surface of the MWCNT-PEC electrode; then polymerizing PANI/NIHCF on the electrode to obtain the 2,4-DMA-MIP/PANI/NIHCF electromagnetic composite material. The invention also discloses a method for testing the electrochemical performance of the electromagnetic composite material. The electrochemical method is adopted, the multi-walled carbon nanotube modified pencil lead electrode is subjected to primary electropolymerization on the surface of the electrode to form the 2, 4-dimethylaniline imprinted polymer membrane electrode, and then secondary electropolymerization is performed to form the polyaniline and nickel ferricyanide doped composite membrane layer, so that the conductive composite membrane has the advantages of large specific surface area, controllable membrane layer thickness, light weight, good chemical stability and excellent conductivity.

Description

Preparation and test method of electromagnetic composite material
Technical Field
The invention belongs to the technical field of electromagnetic materials, and particularly relates to a preparation method of an electromagnetic composite material, and a method for testing the electrochemical performance of the electromagnetic composite material.
Background
Polyaniline (PANI) is a common conductive polymer with simple synthesis, high conductivity, large dielectric constant, good volt-ampere performance, light weight, good chemical stability, strong capacity of storing electric quantity and excellent doping property. Nickel ferricyanide (NIHCF) has a cubic framework structure similar to a molecular sieve, is an inorganic coordination compound formed by connecting electrochemically reversible iron (II/III) as a center through a cyano bond-CN-and nickel ions, is often applied to the fields of electrochemical sensors, electrocatalysis, supercapacitors and the like because of good redox reversibility, simple preparation and easy loading on the surface of an electrode, but at present, there is no literature report on research on electromagnetic materials at home and abroad. 2, 4-dimethylaniline (2,4-DMA) is often used as a fine chemical intermediate for synthesizing medicines, pigments, dyes, pesticides and organic matters, and the organic matters synthesized by the material have the characteristics of high stability, wide application range and the like.
The Molecularly Imprinted Polymer (MIP) is a solid state high molecular polymer which is formed around a specific template molecule by taking a target molecule as the template molecule and combining a functional polymer monomer with a complementary structure with the template molecule in a covalent or non-covalent mode, and after the template molecule is extracted after the reaction is finished, an imprinted cavity which is matched with the spatial structure of the template molecule and has multiple action points can be formed on the surface of the polymer. The molecular imprinting technology is often applied to the fields of drug analysis, solid phase extraction, membrane separation technology, food detection, chromatographic separation and the like due to the predetermination, specific identification, high selectivity and practicability. However, there are no reports on electromagnetic materials so far, and thus the search for this gap is very essential.
Disclosure of Invention
The invention aims to provide a preparation method of an electromagnetic composite material, which combines the structure controllable conductivity of a polyaniline conductive polymer, a unique cubic framework structure similar to a molecular sieve of nickel ferricyanide and a 2,4-DMA-MIP circularly renewable molecular imprinting hole structure, and improves the overall electrochemical performance of the electromagnetic composite material by changing the material structure.
The invention also aims to provide a method for testing the electrochemical characteristics of the electromagnetic composite material.
The invention adopts a technical scheme that: a preparation method of an electromagnetic composite material comprises the following steps:
step 1, preparing MWCNT-PEC by using pencil core and carbon nanotube powder, and winding a conductive wire on the MWCNT-PEC after pretreatment to prepare an MWCNT-PEC electrode;
step 2, preparing a 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode on the surface of the MWCNT-PEC electrode;
and 3, polymerizing PANI/NIHCF on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode to obtain the electromagnetic composite material.
Further, the step 1 specifically comprises:
step 1.1, cleaning pencil leads;
step 1.2, adding carbon nanotube powder into sodium dodecyl benzene sulfonate-ethanol solution according to the proportion of respectively adding 0-100 mg of multi-walled carbon nanotube powder into each 10ml of sodium dodecyl benzene sulfonate-ethanol solution for ultrasonic dispersion treatment to obtain uniform carbon nanotube water dispersion; adding carbon nanotube powder into molten paraffin according to the proportion of respectively adding 0-100 mg of multi-walled carbon nanotube powder into each 10ml of molten paraffin for ultrasonic dispersion treatment to obtain uniform carbon nanotube paraffin dispersion liquid; soaking the pencil lead cleaned in the step 1.1 in the carbon nano tube water dispersion liquid for a period of time, taking out and drying the pencil lead, then soaking the pencil lead in the carbon nano tube paraffin dispersion liquid for a period of time, taking out and drying the pencil lead to obtain the MWCNT-PEC;
step 1.3, pretreating the MWCNT-PEC, specifically polishing the MWCNT-PEC, performing ultrasonic cleaning by using absolute ethyl alcohol and distilled water respectively, and finally drying in the air;
and step 1.4, winding a conductive wire on the MWCNT-PEC pretreated in the step 1.3 to prepare the MWCNT-PEC electrode.
Further, the step 2 specifically comprises:
step 2.1, adopting a three-electrode system, taking the MWCNT-PEC electrode as a working electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, putting the three-electrode system into a first electrolyte to carry out nitrogen introduction and oxygen removal, wherein the first electrolyte contains 2, 4-dimethylaniline, acrylic acid and PBS buffer solution, and the concentration of the 2, 4-dimethylaniline is 9 x 10-6～7.5×10-3mol/L, acrylic acid concentration 7.2X 10-5～3×10-2mol/L, and the 2, 4-bisThe concentration ratio of methylaniline to acrylic acid was 1: (1-8), wherein the pH value of the PBS buffer solution is 5.91-7.73;
step 2.2, conducting power-on circular scanning on the MWCNT-PEC electrode to obtain a semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode;
and 2.3, carrying out elution treatment on the semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode to obtain the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode.
Furthermore, in the step 2.2, when the MWCNT-PEC electrode is subjected to power-on cyclic scanning, the scanning potential is-0.2V-1.0V, the scanning speed is 0.04V/s-0.2V/s, and the cyclic scanning is performed for 10-30 circles;
and in the step 2.3, when the semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode is subjected to elution treatment, the elution time is 2-6 min.
Further, the step 3 specifically includes:
step 3.1, adopting a three-electrode system, taking the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode as a working electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, putting the three-electrode system into a second electrolyte to carry out nitrogen introduction and oxygen removal, wherein the second electrolyte contains aniline and H2SO4、Na2SO4、NiSO4And K3Fe(CN)6Wherein the concentration of the aniline is 0.05-0.3 mol/L, H2SO4Na with a concentration of 0.2-0.8 mol/L2SO4A concentration of 0.15-0.35 mol/L, NiSO4The concentration is 0.001 to 0.003mol/L, K3Fe(CN)6The concentration is 0.001-0.003 mol/L;
and 3.2, performing power-on circular scanning on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode, forming a 2,4-DMA-MIP/PANI/NIHCF composite material film on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode, and washing and drying after power is off to obtain the electromagnetic composite material.
Furthermore, in the step 3.2, when the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode is subjected to circular power-on scanning, the scanning potential is-0.2V-1.05V, the scanning speed is 0.04V/s-0.2V/s, and the circular scanning is performed for 10-30 circles.
The other technical scheme adopted by the invention is as follows: a test method of an electromagnetic composite material is used for calculating the charge value and the electrochemical impedance of the electromagnetic composite material, and specifically comprises the following steps:
adopting a three-electrode system, taking an electromagnetic composite material electrode as a working electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, and placing the three-electrode system in an acidic solution;
electrifying and scanning to obtain a cyclic voltammetry curve of the electromagnetic composite material, and calculating the charge value of the electromagnetic composite material according to the area of the cyclic voltammetry curve; and in the range of 0.1 to 105And testing the electrochemical impedance spectrum of the electromagnetic composite material at the Hz working frequency, obtaining an equivalent circuit diagram of the electromagnetic composite material through fitting, and calculating an impedance value.
Further, the pH value of the acidic solution is 0-0.3.
Preferably, the acidic solution is H2SO4And KNO3Wherein the H is2SO4The concentration is 0.5mol/L, the H2SO4And KNO3The concentration ratio of (1): (0.5 to 4).
Further, when the charge value of the electromagnetic composite material is calculated, the scanning potential is-0.2V-1.0V, the scanning rate is 0.05V/s, and the number of scanning turns is 2 turns.
The invention adopts an electrochemical method to perform primary electropolymerization on the surface of a pencil lead electrode (MWCNT-PEC) modified by a multi-wall carbon nano tube to form a 2, 4-dimethylaniline imprinted polymer membrane electrode (2,4-DMA-MIP-MWCNT-PEC), and then performs secondary electropolymerization on the imprinted polymer membrane electrode to finally form a composite membrane layer doped with polyaniline and nickel hexacyanoferrate, namely the 2,4-DMA-MIP/PANI/NIHCF electromagnetic composite material; as a novel nano material, the nano material has the advantages of large specific surface area, controllable film thickness, light weight, low cost, good chemical stability, small resistivity, excellent conductivity and the like.
Drawings
FIG. 1 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different electrolyte pH;
FIG. 2 is a graph comparing the charge of the electromagnetic composite of the present invention at different electrolyte pH's in FIG. 1;
FIG. 3 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different multiwall carbon nanotube contents;
FIG. 4 is a graph comparing the charge of the electromagnetic composite of the present invention at different multi-walled carbon nanotube contents of FIG. 3;
FIG. 5 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different concentration ratios;
FIG. 6 is a graph comparing the charge levels of the electromagnetic composite of the present invention at different concentration ratios in FIG. 5;
FIG. 7 is a plot of cyclic voltammetry for an electromagnetic composite of the present invention at different scan cycles;
FIG. 8 is a graph comparing the charge of the electromagnetic composite of the present invention at different scan cycles of FIG. 7;
FIG. 9 is a plot of cyclic voltammetry for an electromagnetic composite of the invention at different scan potential ranges;
FIG. 10 is a graph comparing the charge levels of the electromagnetic composite of the present invention at different scanning potentials of FIG. 9;
FIG. 11 is a plot of cyclic voltammetry for an electromagnetic composite of the invention at different scan rates;
FIG. 12 is a graph comparing the charge of the electromagnetic composite of the present invention at different scan rates of FIG. 11;
FIG. 13 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different elution times;
FIG. 14 is a graph comparing the charge levels of the electromagnetic composite of the invention at different elution times of FIG. 13;
FIG. 15 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different aniline concentrations;
FIG. 16 is a graph comparing the charge of the electromagnetic composite of the invention at different aniline concentrations in FIG. 15;
FIG. 17 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different sulfuric acid concentrations;
FIG. 18 is a graph comparing the charge of the electromagnetic composite of the invention at different sulfuric acid concentrations of FIG. 17;
FIG. 19 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different sodium sulfate concentrations;
FIG. 20 is a graph comparing the charge of the electromagnetic composite of the invention at different sodium sulfate concentrations of FIG. 19;
FIG. 21 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different nickel sulfate concentrations;
FIG. 22 is a graph comparing the charge of the electromagnetic composite of the invention at different nickel sulfate concentrations in FIG. 21;
FIG. 23 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different potassium ferricyanide concentrations;
FIG. 24 is a graph comparing the charge levels of the electromagnetic composite material of the present invention at different concentrations of potassium ferricyanide in FIG. 23;
FIG. 25 is a plot of cyclic voltammetry for an electromagnetic composite of the invention at different scanning potentials;
FIG. 26 is a graph comparing the charge levels of the electromagnetic composite of the invention at different scanning potentials of FIG. 25;
FIG. 27 is a plot of cyclic voltammetry for an electromagnetic composite of the invention at different scan cycles;
FIG. 28 is a graph comparing the charge of the electromagnetic composite of the present invention at different scan cycles of FIG. 27;
FIG. 29 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different scan rates;
FIG. 30 is a graph of the charge versus scan rate of the electromagnetic composite of the invention of FIG. 29;
FIG. 31 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different effective MWCNT-PEC conductive lengths;
FIG. 32 is a graph comparing the charge capacity of the electromagnetic composite of the invention at different effective conductive lengths of MWCNT-PEC in FIG. 31;
FIG. 33 is a plot of cyclic voltammetry for electromagnetic composites of the invention with different types of potassium salts;
FIG. 34 is a graph comparing the charge levels of the electromagnetic composite of the invention for different types of potassium salts of FIG. 33;
FIG. 35 is a plot of cyclic voltammetry for electromagnetic composites of the invention under different acidic conditions;
FIG. 36 is a graph comparing the charge levels of the electromagnetic composite of the invention under different acidic conditions of FIG. 35;
FIG. 37 is a plot of cyclic voltammetry for electromagnetic composites of the invention at different concentration ratios of potassium nitrate to sulfuric acid;
FIG. 38 is a graph comparing the charge levels of the electromagnetic composite of the present invention with different concentration ratios of potassium nitrate to sulfuric acid of FIG. 37;
FIG. 39 is a plot of cyclic voltammetry for electromagnetic composites of the invention for different types of composites;
FIG. 40 is a graph comparing the charge of the electromagnetic composite of the present invention for different types of composites of FIG. 39;
FIG. 41 is H at 0.5mol/L for MWCNT, MWCNT-2,4-DMA-MIP, 2,4-DMA-MIP/PANI, and 2,4-DMA-MIP/PANI/NIHCF four materials2SO4And 1.0mol/L of KNO3An equivalent circuit diagram of impedance spectra in the mixed solution; in which, FIG. 41(a) is an equivalent circuit diagram of MWCNT, FIG. 41(b) is an equivalent circuit diagram of MWCNT-2,4-DMA-MIP, and FIG. 41(c) is an equivalent circuit diagram of 2,4-DMA-MIP/PANI and 2, 4-DMA-MIP/PANI/NIHCF.
Detailed Description
The preparation method of the electromagnetic composite material provided by the invention comprises the following steps:
step 1, preparing MWCNT-PEC by using pencil core and carbon nanotube powder, and winding a conductive metal wire on the MWCNT-PEC after pretreatment to prepare an MWCNT-PEC electrode; the method specifically comprises the following steps:
step 1.1, cleaning the pencil core, removing impurities attached to colloid and the like on the pencil core, soaking the pencil core in an acid solution for a period of time, then soaking in absolute ethyl alcohol for a period of time, and finally cleaning and drying with distilled water;
step 1.2, adding carbon nanotube powder into sodium dodecyl benzene sulfonate-ethanol solution for ultrasonic dispersion treatment according to the proportion of respectively adding 0-100 mg of multi-walled carbon nanotube powder into 10ml of sodium dodecyl benzene sulfonate-ethanol solution to obtain uniform carbon nanotube water dispersion; adding carbon nanotube powder into molten paraffin according to the proportion of respectively adding 0-100 mg of multi-walled carbon nanotube powder into each 10ml of molten paraffin for ultrasonic dispersion treatment to obtain uniform carbon nanotube paraffin dispersion liquid; soaking the pencil lead cleaned in the step 1.1 in the carbon nano tube water dispersion liquid for a period of time, taking out and drying the pencil lead, then soaking the pencil lead in the carbon nano tube paraffin dispersion liquid for a period of time, taking out and drying the pencil lead to obtain MWCNT-PEC;
step 1.3, pretreating the MWCNT-PEC, specifically polishing the MWCNT-PEC, performing ultrasonic cleaning by using absolute ethyl alcohol and distilled water respectively, and finally drying in the air;
and step 1.4, winding a conductive metal wire on the MWCNT-PEC pretreated in the step 1.3 to prepare the MWCNT-PEC electrode.
Step 2, preparing a 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode on the surface of the MWCNT-PEC electrode; the method specifically comprises the following steps:
step 2.1, adopting a three-electrode system, taking the MWCNT-PEC electrode as a working electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, putting the three-electrode system into a first electrolyte to carry out nitrogen introduction and oxygen removal, wherein the first electrolyte contains 2, 4-dimethylaniline, acrylic acid and PBS buffer solution, and the concentration of the 2, 4-dimethylaniline is 9 x 10-6～7.5×10-3mol/L, acrylic acid concentration 7.2X 10-5～3×10-2mol/L, and the concentration ratio of the 2, 4-dimethylaniline and acrylic acid is 1: (1-8), wherein the pH value of the PBS buffer solution is 5.91-7.73;
step 2.2, conducting power-on circular scanning on the MWCNT-PEC electrode to obtain a semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode; specifically, when the MWCNT-PEC electrode is subjected to power-on cyclic scanning, the scanning potential is-0.2V-1.0V, the scanning speed is 0.04V/s-0.2V/s, and the cyclic scanning is carried out for 10-30 circles;
and 2.3, carrying out elution treatment on the semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode for 2-6 min to obtain the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode.
Step 3, polymerizing PANI/NIHCF on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode to obtain a 2,4-DMA-MIP/PANI/NIHCF composite film, namely the electromagnetic composite material; the method specifically comprises the following steps:
step 3.1, adopting a three-electrode system, taking a 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode as a working electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, putting the three-electrode system into a second electrolyte for nitrogen introduction and oxygen removal, wherein the second electrolyte contains aniline and H2SO4、Na2SO4、NiSO4And K3Fe(CN)6Wherein the concentration of the aniline is 0.05-0.3 mol/L, H2SO4Na with a concentration of 0.2-0.8 mol/L2SO4A concentration of 0.15-0.35 mol/L, NiSO4The concentration is 0.001 to 0.003mol/L, K3Fe(CN)6The concentration is 0.001-0.003 mol/L;
and 3.2, performing power-on circular scanning on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode, forming a 2,4-DMA-MIP/PANI/NIHCF composite film on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode, after the power is cut off, washing and drying to obtain the 2,4-DMA-MIP/PANI/NIHCF, namely the electromagnetic composite material, specifically, when the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode is subjected to power-on circular scanning, the scanning potential is-0.2V-1.05V, the scanning speed is 0.04V/s-0.2V/s, and the circular scanning lasts for 10-30 circles.
The invention also provides a test method of the electromagnetic composite material (namely the 2,4-DMA-MIP/PANI/NIHCF prepared by the method), which is used for calculating the charge value and the electrochemical impedance of the electromagnetic composite material, and specifically comprises the following steps:
adopting a three-electrode system, taking an electromagnetic composite material electrode as a working electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, and placing the three-electrode system in an acidic solution; specifically, the pH value of the acidic solution is 0-0.3. Illustratively, the acidic solution is H2SO4And KNO3In the mixed solution of (1), wherein H2SO4Concentration of 0.5mol/L, H2SO4And KNO3The concentration ratio of (1): (0.5 to 4).
Electrifying and scanning to obtain a cyclic voltammetry curve of the electromagnetic composite material, and calculating the charge value of the electromagnetic composite material according to the area of the cyclic voltammetry curve, wherein when the charge value of the electromagnetic composite material is specifically calculated, the scanning potential is-0.2V-1.0V, the scanning rate is 0.05V/s, and the number of scanning cycles is 2 cycles; and in the range of 0.1 to 105And testing the electrochemical impedance spectrum of the electromagnetic composite material at the working frequency of Hz, obtaining an equivalent circuit diagram of the electromagnetic composite material through fitting, and calculating an impedance value.
When the electromagnetic composite material is prepared, the thickness and uniformity of a polymer film can be adjusted and controlled by changing electrochemical parameters through an electrochemical synthesis technology; the operation is simple and convenient; the polyaniline/nickel hexacyanoferrate composite material is prepared by doping the polyaniline and copolymerizing the polyaniline in one step; and the technological process meets the synthesis requirements of environmental protection and no pollution, so the invention utilizes the electrochemical method to prepare the 2,4-DMA-MIP/PANI/NIHCF, which is a necessary and optimal scheme.
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
The embodiment discloses a preparation method of an electromagnetic composite material (2,4-DMA-MIP/PANI/NIHCF), which is implemented according to the following steps:
step 1, preparing MWCNT-PEC, pretreating, winding conductive copper wire on the MWCNT-PEC to prepare MWCNT-PEC electrode:
step 1.1, cutting the 2B pencil lead into small sections of 1.5cm, and soaking in nitric acid water (HNO)3And H2The volume ratio of O is 1: 1) soaking in the solution for 20min to remove impurities, wood dust and colloid on the surface of the pencil lead, and air drying; soaking in anhydrous ethanol for 20min to remove nitric acid and other impurities on the surface of the pencil lead, and air drying; finally, soaking the pencil lead in distilled water for 20min, removing ethanol and impurities on the surface of the pencil lead, and drying the pencil lead in the air;
step 1.2, adding 50mg of carbon nano tube powder into 10ml of sodium dodecyl benzene sulfonate-ethanol solution, and carrying out ultrasonic dispersion treatment until uniform carbon nano tube water dispersion is obtained; 50mg of carbon nanotube powder was added to 10ml of molten paraffin and ultrasonically dispersed until a uniform carbon nanotube paraffin dispersion was obtained. Placing the pencil lead electrode manufactured in the step 1.1 in a carbon nano tube water dispersion liquid for soaking for 10min, drying, then placing in a carbon nano tube paraffin wax dispersion liquid for soaking for 10min, and drying to obtain pretreated MWCNT-PEC for later use;
step 1.3, pretreating the MWCNT-PEC, polishing the MWCNT-PEC prepared in the step 1.2 by using weighing paper, then ultrasonically washing the MWCNT-PEC for 6min by using absolute ethyl alcohol and secondary distilled water respectively to remove impurities on the surface of the electrode, and airing;
step 1.4, shearing a 6cm copper wire, winding the copper wire at one end of the MWCNT-PEC, and fixing the copper wire and the pencil lead together by using AB glue to prepare the MWCNT-PEC electrode;
step 2, preparing a 2, 4-dimethylaniline molecularly imprinted polymer membrane on the surface of the MWCNT-PEC electrode:
step 2.1, adopting a three-electrode system, taking an MWCNT-PEC electrode as a working electrode, a Saturated Calomel Electrode (SCE) as a reference electrode and a platinum electrode as an auxiliary electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, placing the three electrodes in a first electrolyte, introducing nitrogen to remove oxygen for 15min, wherein the first electrolyte contains 2, 4-dimethylaniline, acrylic acid and a PBS buffer solution, the concentration of the 2, 4-dimethylaniline is 0.00005mol/L, the concentration of the acrylic acid is 0.0002mol/L, the concentration ratio of the 2, 4-dimethylaniline to the acrylic acid is 1:4, and the pH value of the PBS buffer solution is 6.81;
step 2.2, electrifying the electrode after the oxygen removal in the step 2.1, circularly scanning for 20 circles at a scanning speed of 0.1V/s within a scanning potential range of-0.8V, wherein the effective conductive length of the MWCNT-PEC electrode is 1.0cm, and preparing a semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode;
and 2.3, eluting the semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode prepared in the step 2.2, taking the semi-finished product electrode out of the first electrolyte, and then putting the semi-finished product electrode into an ethanol-ammonia water (the volume ratio of ethanol to ammonia water is 19:1) solution for ultrasonic elution for 5min to obtain the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode.
Step 3, preparing the 2,4-DMA-MIP/PANI/NIHCF composite material on the surface of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode:
step 3.1, adopting a three-electrode system, taking a 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as an auxiliary electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, placing the three electrodes in a second electrolyte solution, introducing nitrogen to remove oxygen for 15min, wherein the second electrolyte solution contains aniline and H2SO4、Na2SO4、NiSO4And K3Fe(CN)6Aniline concentration of 0.1mol/L, H2SO4The concentration is 0.5mol/L, Na2SO4Concentration of 0.25mol/L, NiSO4The concentration is 0.002mol/L, K3Fe(CN)6The concentration is 0.002 mol/L;
and 3.2, electrifying the electrode subjected to deoxidization in the step 3.1, circularly scanning for 20 circles at a scanning speed of 0.1V/s within a scanning potential range of-0.2-0.85V, forming a 2,4-DMA-MIP/PANI/NIHCF composite material film on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode, and washing and drying after power failure to obtain the electromagnetic composite material. Wherein the effective conductive length of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode is 1.0 cm.
The prepared 2,4-DMA-MIP/PANI/NIHCF composite material is also subjected to cyclic voltammetry and electrochemical impedance spectroscopy:
the method comprises the specific steps of adopting a three-electrode system, taking a 2,4-DMA-MIP/PANI/NIHCF electrode as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as an auxiliary electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, and putting the three-electrode system into 0.5mol/L H2SO4And 0.5mol/L of KNO3(pH is 0) in the mixed solution, carrying out an electrochemical performance test at a scanning rate of 0.05V/s under a voltage range of-0.2-1.0V, and calculating a charge-charge value through the area of a cyclic voltammetry curve; and in the range of 0.1 to 105Testing of 2,4-DMA-MIP at Hz operating frequencyAnd fitting the electrochemical impedance spectrum of the/PANI/NIHCF to obtain an equivalent circuit diagram of the electrochemical impedance spectrum, and finally calculating an impedance value.
Example 2
The embodiment discloses a preparation method of an electromagnetic composite material (2,4-DMA-MIP/PANI/NIHCF), which is implemented according to the following steps:
step 1, preparing MWCNT-PEC, pretreating, winding conductive copper wire on the MWCNT-PEC to prepare MWCNT-PEC electrode:
step 1.1, cutting the 2B pencil lead into small sections of 1.5cm, and soaking in nitric acid water (HNO)3And H2The volume ratio of O is 1: 1) soaking in the solution for 20min to remove impurities, wood dust and colloid on the surface of the pencil lead, and air drying; soaking in anhydrous ethanol for 20min to remove nitric acid and other impurities on the surface of the pencil lead, and air drying; finally, soaking the pencil lead in distilled water for 20min, removing ethanol and impurities on the surface of the pencil lead, and drying the pencil lead in the air;
step 1.2, adding 25mg of carbon nano tube powder into 10ml of sodium dodecyl benzene sulfonate-ethanol solution, and dispersing in ultrasonic until uniform carbon nano tube water dispersion is obtained; 25mg of carbon nanotube powder was added to 10ml of molten paraffin and ultrasonically dispersed until a uniform carbon nanotube paraffin dispersion was obtained. Placing the pencil lead electrode prepared in the step 1.1 in a carbon nano tube water dispersion liquid for soaking for 10min, drying, then placing in a carbon nano tube paraffin wax dispersion liquid for soaking for 10min, and drying to obtain pretreated MWCNT-PEC for later use;
step 1.3, pretreating the MWCNT-PEC, polishing the MWCNT-PEC prepared in the step 1.2 by using weighing paper, then ultrasonically washing the MWCNT-PEC for 6min by using absolute ethyl alcohol and secondary distilled water respectively to remove impurities on the surface of the electrode, and airing;
step 1.4, shearing a 6cm copper wire, winding the copper wire at one end of the MWCNT-PEC, and fixing the copper wire and the pencil lead together by using AB glue to prepare the MWCNT-PEC electrode;
step 2, preparing a 2, 4-dimethylaniline molecularly imprinted polymer membrane on the surface of the MWCNT-PEC electrode:
step 2.1, adopting a three-electrode system, taking an MWCNT-PEC electrode as a working electrode, a Saturated Calomel Electrode (SCE) as a reference electrode and a platinum electrode as an auxiliary electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, putting the three electrodes into a first electrolyte, introducing nitrogen to remove oxygen for 15min, wherein the first electrolyte contains 2, 4-dimethylaniline, acrylic acid and a PBS buffer solution, the concentration of the 2, 4-dimethylaniline is 0.005mol/L, the concentration of the acrylic acid is 0.01mol/L, the concentration ratio of the 2, 4-dimethylaniline to the acrylic acid is 1:2, and the pH value of the PBS buffer solution is 6.64;
and 2.2, electrifying the electrode subjected to oxygen removal in the step 2.1, circularly scanning for 12 circles at a scanning speed of 0.1V/s within a scanning potential range of-0.8V, wherein the effective conductive length of the MWCNT-PEC electrode is 1.0cm, and preparing a semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode.
And 2.3, eluting the semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode prepared in the step 2.2, taking the semi-finished product electrode out of the first electrolyte, and then putting the semi-finished product electrode into an ethanol-ammonia water (the volume ratio of ethanol to ammonia water is 19:1) solution for ultrasonic elution for 3min to obtain the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode.
Step 3, preparing the 2,4-DMA-MIP/PANI/NIHCF composite material on the surface of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode:
step 3.1, adopting a three-electrode system, taking a 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as an auxiliary electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, placing the three electrodes in a second electrolyte solution, introducing nitrogen to remove oxygen for 15min, wherein the second electrolyte solution contains aniline and H2SO4、Na2SO4、NiSO4And K3Fe(CN)6Aniline concentration of 0.1mol/L, H2SO4The concentration is 0.5mol/L, Na2SO4Concentration of 0.25mol/L, NiSO4The concentration is 0.002mol/L, K3Fe(CN)6The concentration is 0.002 mol/L;
and 3.2, electrifying the electrode subjected to deoxidization in the step 3.1, circularly scanning for 20 circles at a scanning speed of 0.1V/s within a scanning potential range of-0.2-0.85V, forming a 2,4-DMA-MIP/PANI/NIHCF composite material film on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode, and washing and drying after power failure to obtain the composite material film. Wherein the effective conductive length of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode is 1.0 cm.
The prepared 2,4-DMA-MIP/PANI/NIHCF composite material is also subjected to cyclic voltammetry and electrochemical impedance spectroscopy:
the method comprises the specific steps of adopting a three-electrode system, taking a 2,4-DMA-MIP/PANI/NIHCF electrode as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as an auxiliary electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, and putting the three-electrode system into 0.5mol/L H2SO4+0.5mol/L KNO3In the solution (pH is 0), the voltage range is-0.2-1.0V, the electrochemical performance test is carried out at the scanning rate of 0.05V/s, and the charge-charge value is calculated through the area of the cyclic voltammetry curve; and in the range of 0.1 to 105And (3) testing the electrochemical impedance spectrum of the 2,4-DMA-MIP/PANI/NIHCF under the Hz working frequency, obtaining an equivalent circuit diagram of the electrochemical impedance spectrum through fitting, and finally calculating the impedance value.
Example 3
The embodiment discloses a preparation method of an electromagnetic composite material (2,4-DMA-MIP/PANI/NIHCF), which is implemented according to the following specific steps:
step 1, preparing MWCNT-PEC by using pencil lead and carbon nanotube powder, pretreating, and winding a conductive copper wire on the MWCNT-PEC to prepare an MWCNT-PEC electrode; the method specifically comprises the following steps:
step 1.1, cutting the 2B pencil lead into small sections of 1.5cm, and soaking in nitric acid water (HNO)3And H2The volume ratio of O is 1: 1) soaking in the solution for 20min to remove impurities, wood dust and colloid on the surface of the pencil lead, and air drying; soaking in anhydrous ethanol for 20min to remove nitric acid and other impurities on the surface of the pencil lead, and air drying; finally, soaking the pencil lead in distilled water for 20min, removing ethanol and impurities on the surface of the pencil lead, and drying the pencil lead in the air;
step 1.2, adding 25mg of carbon nano tube powder into 10ml of sodium dodecyl benzene sulfonate-ethanol solution, and dispersing in ultrasonic until uniform carbon nano tube water dispersion is obtained; 25mg of carbon nanotube powder was added to 10ml of molten paraffin and ultrasonically dispersed until a uniform carbon nanotube paraffin dispersion was obtained. Placing the pencil lead electrode prepared in the step 1.1 in a carbon nano tube water dispersion liquid for soaking for 10min, drying, then placing in a carbon nano tube paraffin wax dispersion liquid for soaking for 10min, and drying to obtain pretreated MWCNT-PEC for later use;
step 1.3, pretreating the MWCNT-PEC, polishing the MWCNT-PEC prepared in the step 1.2 by using weighing paper, then ultrasonically washing the MWCNT-PEC for 6min by using absolute ethyl alcohol and secondary distilled water respectively to remove impurities on the surface of the electrode, and airing;
step 1.4, shearing a 6cm copper wire, winding the copper wire at one end of the MWCNT-PEC, and fixing the copper wire and the pencil lead together by using AB glue to prepare the MWCNT-PEC electrode;
step 2, preparing a 2, 4-dimethylaniline molecularly imprinted polymer membrane on the surface of the MWCNT-PEC electrode:
step 2.1, adopting a three-electrode system, taking an MWCNT-PEC electrode as a working electrode, a Saturated Calomel Electrode (SCE) as a reference electrode and a platinum electrode as an auxiliary electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, putting the three electrodes into a first electrolyte, introducing nitrogen to remove oxygen for 15min, wherein the first electrolyte contains 2, 4-dimethylaniline, acrylic acid and a PBS buffer solution, the concentration of the 2, 4-dimethylaniline is 0.005mol/L, the concentration of the acrylic acid is 0.01mol/L, the concentration ratio of the 2, 4-dimethylaniline to the acrylic acid is 1:2, and the pH value of the PBS buffer solution is 6.64;
and 2.2, electrifying the electrode subjected to oxygen removal in the step 2.1, circularly scanning for 12 circles at a scanning speed of 0.1V/s within a scanning potential range of-0.8V, wherein the effective conductive length of the MWCNT-PEC electrode is 1.0cm, and preparing a semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode.
And 2.3, eluting the semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode prepared in the step 2.2, taking the semi-finished product electrode out of the first electrolyte, and then putting the semi-finished product electrode into an ethanol-ammonia water (the volume ratio of ethanol to ammonia water is 19:1) solution for ultrasonic elution for 3min to obtain the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode.
Step 3, preparing the 2,4-DMA-MIP/PANI/NIHCF composite material on the surface of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode:
step 3.1, adopting a three-electrode system, taking a 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as an auxiliary electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, placing the three electrodes in a second electrolyte solution, introducing nitrogen to remove oxygen for 15min, wherein the second electrolyte solution contains aniline and H2SO4、Na2SO4、NiSO4And K3Fe(CN)6Aniline concentration of 0.3mol/L, H2SO4The concentration is 0.4mol/L, Na2SO4Concentration of 0.25mol/L, NiSO4The concentration is 0.0025mol/L, K3Fe(CN)6The concentration is 0.0025 mol/L;
and 3.2, electrifying the electrode subjected to oxygen removal in the step 3.1, circularly scanning for 25 circles at a scanning speed of 0.05V/s within a scanning potential range of-0.2-0.85V, forming a 2,4-DMA-MIP/PANI/NIHCF composite material film on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode, and washing and drying after power is off to obtain the composite material film. Wherein the effective conductive length of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode is 1.25 cm.
The prepared 2,4-DMA-MIP/PANI/NIHCF composite material is also subjected to cyclic voltammetry and electrochemical impedance spectroscopy:
the method comprises the specific steps of adopting a three-electrode system, taking a 2,4-DMA-MIP/PANI/NIHCF electrode as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as an auxiliary electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, and putting the three-electrode system into 0.5mol/L H2SO4+0.5mol/L KNO3In the solution (pH is 0), the voltage range is-0.2-1.0V, the electrochemical performance test is carried out at the scanning rate of 0.05V/s, and the charge-charge value is calculated through the area of the cyclic voltammetry curve; and in the range of 0.1 to 105And (3) testing the electrochemical impedance spectrum of the 2,4-DMA-MIP/PANI/NIHCF under the Hz working frequency, obtaining an equivalent circuit diagram of the electrochemical impedance spectrum through fitting, and finally calculating the impedance value.
Example 4
The embodiment discloses a preparation method of an electromagnetic composite material (2,4-DMA-MIP/PANI/NIHCF), which is implemented according to the following steps:
step 1, preparing MWCNT-PEC, pretreating, winding conductive copper wire on the MWCNT-PEC to prepare MWCNT-PEC electrode:
step 1.1, cutting the 2B pencil lead into small sections of 1.5cm, and soaking in nitric acid water (HNO)3And H2The volume ratio of O is 1: 1) soaking in the solution for 20min to remove impurities, wood dust and colloid on the surface of the pencil lead, and air drying; soaking in anhydrous ethanol for 20min to remove nitric acid and other impurities on the surface of the pencil lead, and air drying; finally, soaking the pencil lead in distilled water for 20min, removing ethanol and impurities on the surface of the pencil lead, and drying the pencil lead in the air;
step 1.2, adding 25mg of carbon nano tube powder into 10ml of sodium dodecyl benzene sulfonate-ethanol solution, and dispersing in ultrasonic until uniform carbon nano tube water dispersion is obtained; adding 25mg of carbon nanotube powder into 10ml of molten paraffin for ultrasonic dispersion until uniform carbon nanotube paraffin dispersion liquid is obtained; then, placing the pencil lead prepared in the step 1.1 in a carbon nano tube water dispersion liquid for soaking for 10min, drying, then placing in a carbon nano tube paraffin wax dispersion liquid for soaking for 10min, and drying to obtain pretreated MWCNT-PEC for later use;
step 1.3, pretreating the MWCNT-PEC, polishing the MWCNT-PEC prepared in the step 1.2 by using weighing paper, then ultrasonically washing the MWCNT-PEC for 6min by using absolute ethyl alcohol and secondary distilled water respectively to remove impurities on the surface of the electrode, and airing;
step 1.4, shearing a 6cm copper wire, winding the copper wire at one end of the MWCNT-PEC, and fixing the copper wire and the pencil lead together by using AB glue to prepare the MWCNT-PEC electrode;
step 2, preparing a 2, 4-dimethylaniline molecularly imprinted polymer membrane on the surface of the MWCNT-PEC electrode:
step 2.1, adopting a three-electrode system, taking an MWCNT-PEC electrode as a working electrode, a Saturated Calomel Electrode (SCE) as a reference electrode and a platinum electrode as an auxiliary electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, placing the three electrodes in a first electrolyte, introducing nitrogen to remove oxygen for 10min, wherein the first electrolyte contains 2, 4-dimethylaniline, acrylic acid and a PBS buffer solution, the concentration of the 2, 4-dimethylaniline is 0.005mol/L, the concentration of the acrylic acid is 0.01mol/L, the concentration ratio of the 2, 4-dimethylaniline to the acrylic acid is 1:2, and the pH value of the PBS buffer solution is 6.64;
and 2.2, electrifying the electrode subjected to oxygen removal in the step 2.1, circularly scanning for 12 circles at a scanning speed of 0.1V/s within a scanning potential range of-0.8V, wherein the effective conductive length of the MWCNT-PEC electrode is 1.0cm, and preparing a semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode.
And 2.3, eluting the semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode prepared in the step 2.2, taking the semi-finished product electrode out of the first electrolyte, and then putting the semi-finished product electrode into a solution of ethanol-ammonia water (the volume ratio of ethanol to ammonia water is 19:1) for ultrasonic elution for 3min to obtain the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode.
Step 3, preparing a 2,4-DMA-MIP/PANI/NIHCF imprinted composite material on the surface of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode:
step 3.1, adopting a three-electrode system, taking a 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as an auxiliary electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, putting the three electrodes into a second electrolyte solution, introducing nitrogen for removing for 15min, wherein the second electrolyte solution contains aniline and H2SO4、Na2SO4、NiSO4And K3Fe(CN)6Wherein the aniline concentration is 0.3mol/L, H2SO4The concentration is 0.4mol/L, Na2SO4Concentration of 0.25mol/L, NiSO4The concentration is 0.0025mol/L, K3Fe(CN)6The concentration is 0.0025 mol/L;
and 3.2, electrifying the electrode subjected to oxygen removal in the step 3.1, circularly scanning for 25 circles at a scanning speed of 0.05V/s within a scanning potential range of-0.2-0.85V, forming a 2,4-DMA-MIP/PANI/NIHCF composite material film on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer film electrode, and washing and drying after power is off to obtain the composite material film. Wherein the effective conductive length of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode is 1.25 cm.
In this example, cyclic voltammetry and electrochemical impedance spectroscopy were also performed on the prepared 2,4-DMA-MIP/PANI/NIHCF composite material:
the method comprises the following steps of adopting a three-electrode system, taking a 2,4-DMA-MIP/PANI/NIHCF electrode (namely, an imprinted polymer thin film electrode with a 2,4-DMA-MIP/PANI/NIHCF composite material film formed on the surface thereof) as a working electrode, taking a saturated calomel electrode as a reference electrode, taking a platinum electrode as an auxiliary electrode, and then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop; the three-electrode system is put into 0.5mol/L H2SO4+1.0mol/L KNO3In the solution (pH is 0), the voltage range is-0.2-1.0V, the electrochemical performance test is carried out at the scanning rate of 0.05V/s, and the charge-charge value is calculated through the area of the cyclic voltammetry curve; and in the range of 0.1 to 105And (3) testing the electrochemical impedance spectrum of the 2,4-DMA-MIP/PANI/NIHCF under the Hz working frequency, obtaining an equivalent circuit diagram of the electrochemical impedance spectrum through fitting, and finally calculating the impedance value. FIG. 41(a) is a fitted equivalent circuit diagram of MWCNT, FIG. 41(b) is MWCNT-2,4-DMA-MIP, FIG. 41(c) is 2,4-DMA-MIP/PANI and 2,4-DMA-MIP/PANI/NIHCF, and the data are shown in Table 1; as can be seen from Table 1, among the four materials, the impedance of MWCNT is the largest, the impedance of MWCNT-2,4-DMA-MIP is the second, and the impedance of MWCNT-2, 4-DMA-MIP/PANI/NIHCF is the smallest, thus indicating that the conductivity of 2,4-DMA-MIP/PANI/NIHCF is better than that of MWCNT, MWCNT-2,4-DMA-MIP and 2,4-DMA-MIP/PANI, therefore, the practical value of 2,4-DMA-MIP/PANI/NIHCF is larger.
TABLE 1 impedance equivalent Circuit data for four materials
Figure BDA0002118827340000191
The invention also researches the influence of each condition on the performance of the prepared 2,4-DMA-MIP/PANI/NIHCF composite material through a plurality of comparative experiments.
Wherein, FIGS. 1-14 show the influence of the preparation conditions of 2,4-DMA-MIP on the charge capacity of 2, 4-DMA-MIP/PANI/NIHCF; preparation of aniline/nickel ferricyanide on 2, 4-dimethylaniline imprinted polymer electrodeThe conditions are as follows: 0.1mol/L aniline, 0.5mol/L H2SO40.25mol/L of Na2SO40.002mol/L of NiSO40.002mol/L of K3Fe(CN)6In the method, the scanning speed is 0.1V/s and the scanning is continuously and circularly carried out for 20 circles within the potential range of-0.2 to 0.85V.
FIG. 1 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF composites at different electrolyte pH (7.73, 7.17, 5.91, 6.98, 6.81, 6.47, 6.64 for 1-7) and FIG. 2 is a plot of charge versus FIG. 1; FIG. 3 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF at different carbon nanotube contents (1-5 indicate the carbon nanotube concentrations of 10mg/mL, 0mg/mL, 7.5mg/mL, 5mg/mL, 2.5mg/mL, respectively); FIG. 4 is a graph comparing the charge of FIG. 3; FIG. 5 shows cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF composite materials at different ratios (1-5 indicates that the concentration ratios of 2, 4-dimethylaniline to acrylic acid are 1: 8, 1: 6, 1: 1, 1:4 and 1:2, respectively); FIG. 6 is a graph comparing the charge of FIG. 5; FIG. 7 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF at different scan cycles (1-5 refer to scan cycles of 24, 20, 16, 8, 12 respectively), and FIG. 8 is a plot of charge versus FIG. 7; FIG. 9 is a cyclic voltammogram of 2,4-DMA-MIP/PANI/NIHCF under different potential scanning ranges (1-5 indicates that the scanning voltage ranges are-1.6V, -0.6V, -1.4V, -1.2V, -0.8V, respectively), and FIG. 10 is a charge quantity comparison graph of FIG. 9; FIG. 11 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF at different scan rates (scan rates 1-5 are 0.4V/s, 0.25V/s, 0.15V/s, 0.05V/s, 0.1V/s, respectively), and FIG. 12 is a plot of charge versus FIG. 11; FIG. 13 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF at different elution times (elution times of 2min, 6min, 5min, 4min, 3min, respectively, for 1-5), and FIG. 14 is a plot of charge versus FIG. 13.
Wherein, FIGS. 15-32 are the research experiments of the influence of PANI/NIHCF polymerization conditions on the charge capacity of 2, 4-DMA-MIP/PANI/NIHCF; the preparation conditions of the 2, 4-dimethylaniline imprinted polymer electrode are as follows: the electrolyte solution contains 0.005mol/L of 2, 4-dimethylaniline, 0.01mol/L of acrylic acid, 1:2 of concentration ratio of the 2, 4-dimethylaniline to the acrylic acid, 6.64 of pH value of PBS buffer solution, and the 2,4-DMA-MIP-MWCNT-PEC is prepared by circularly scanning for 12 circles at a scanning speed of 0.1V/s within a scanning potential range of-0.8V.
FIG. 15 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF at different aniline concentrations (1-5 aniline concentrations 0.05mol/L, 0.1mol/L, 0.15mol/L, 0.2mol/L and 0.3mol/L, respectively), FIG. 16 is a plot of charge versus FIG. 15;
FIG. 17 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF at different sulfuric acid concentrations (curves 1-5 show sulfuric acid concentrations of 0.2mol/L, 0.8mol/L, 0.6mol/L, 0.5mol/L and 0.4mol/L, respectively), FIG. 18 is a plot of charge versus FIG. 17;
FIG. 19 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF at different nickel sulfate concentrations (curves 1-5 show nickel sulfate concentrations of 0.001mol/L, 0.0015mol/L, 0.003mol/L, 0.002mol/L and 0.0025mol/L, respectively), and FIG. 20 is a plot of charge versus FIG. 19;
FIG. 21 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF at different sodium sulfate concentrations (curves 1-5 show sodium sulfate concentrations of 0.15mol/L, 0.2mol/L, 0.35mol/L, 0.2mol/L and 0.25mol/L, respectively), and FIG. 22 is a plot of charge versus FIG. 21;
FIG. 23 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF at different potassium ferricyanide concentrations (curves 1-5 show potassium ferricyanide concentrations of 0.001mol/L, 0.0015mol/L, 0.002mol/L, 0.003mol/L and 0.0025mol/L, respectively), and FIG. 24 is a plot of charge versus FIG. 23;
FIG. 25 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF under different potential sweep ranges (1-5 refer to sweep voltages ranging from-0.2V to 0.65V, 0.75V, 0.8V, 0.95V, 0.85V, respectively), and FIG. 26 is a plot comparing the charge in FIG. 25;
FIG. 27 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF at different scan cycles (lines 1-5 refer to scan cycles 10, 15, 20, 30, 25 respectively), and FIG. 28 is a plot of charge versus FIG. 27;
FIG. 29 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF at different scan rates (scan rates 1-4 are 0.2V/s, 0.15V/s, 0.1V/s, 0.04V/s and 0.05V/s, respectively), and FIG. 30 is a plot of charge versus FIG. 29;
FIG. 31 is a cyclic voltammogram of 2,4-DMA-MIP/PANI/NIHCF at different MWCNT-PEC effective conduction lengths (1-5 means MWCNT-PEC effective conduction lengths of 0.5, 0.75, 1.0, 1.5 and 1.25cm, respectively), and FIG. 32 is a charge amount comparison graph of FIG. 31.
The invention also researches the influence of the conditions of each test solution on the cyclic voltammetry and electrochemical impedance spectroscopy performance of the 2,4-DMA-MIP/PANI/NIHCF composite material through a plurality of comparative experiments.
Wherein, FIGS. 33-38 are the investigation experiments of the effect of the test solution conditions on the charge capacity of 2, 4-DMA-MIP/PANI/NIHCF; the preparation conditions of the 2,4-DMA-MIP/PANI/NIHCF are as follows: putting the MWCNT-PEC into a first electrolyte (the concentration of 2, 4-dimethylaniline is 0.005mol/L, the concentration of acrylic acid is 0.01mol/L, the concentration ratio of 2, 4-dimethylaniline to acrylic acid is 1:2, and the pH value of a PBS buffer solution is 6.64), circularly scanning for 12 circles within the scanning potential range of-0.8V at the scanning speed of 0.1V/s, ultrasonically eluting in an ethanol-ammonia water (the volume ratio of ethanol to ammonia water is 19:1) solution for 3min, and preparing 2, 4-DMA-MIP-MWCNT-PEC; the prepared 2,4-DMA-MIP-MWCNT-PEC is put into a second electrolyte (0.3mol/L aniline, 0.4mol/L H)2SO40.25mol/L of Na2SO40.0025mol/L of NiSO4And 0.0025mol/L of K3Fe(CN)6) In the method, after continuous cyclic scanning is carried out for 25 circles within a potential range of-0.2-0.85V at a scanning speed of 0.05V/s, the effective conductive length of the 2,4-DMA-MIP-MWCNT-PEC is 1.25cm, and the 2,4-DMA-MIP/PANI/NIHCF composite membrane material is prepared on the surface of the 2,4-DMA-MIP-MWCNT-PEC electrode.
FIG. 33 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF under different types of potassium salts (1-3 are potassium sulfate, potassium chloride and potassium nitrate, respectively), and FIG. 34 is a plot of charge versus FIG. 33;
FIG. 35 is a plot of cyclic voltammograms of 2,4-DMA-MIP/PANI/NIHCF under different acidic conditions (0.5 ml/L potassium nitrate solution, 0.5ml/L sulfuric acid +0.5ml/L potassium nitrate solution for 1 and 2, respectively), and FIG. 36 is a graph comparing the charge of FIG. 35;
FIG. 37 is a cyclic voltammogram of 2,4-DMA-MIP/PANI/NIHCF composites of sulfuric acid and potassium nitrate at different concentration ratios (1-5 indicate that the concentration ratios of sulfuric acid to potassium nitrate are 2: 1, 1:4, 1: 3, 1: 1, 1:2, respectively); FIG. 38 is a graph comparing the charge levels of FIG. 37;
the invention also adopts cyclic voltammetry to compare the electrochemical performances of three different composite materials.
Wherein, FIG. 39 is the cyclic voltammograms of three different composites (wherein, A: 2, 4-DMA-MIP/PANI/NIHCF; B: 2, 4-DMA-MIP/PANI; C: 2, 4-DMA-MIP/NIHCF); FIG. 40 is a graph comparing the charge amounts of FIG. 39, and it can be seen from FIG. 40 that the electrochemical performance of 2,4-DMA-MIP/PANI/NIHCF is optimal compared to the other two composites.

Claims (4)

1. The preparation method of the electromagnetic composite material is characterized by comprising the following steps of:
step 1, preparing MWCNT-PEC by using pencil core and carbon nanotube powder, and winding a conductive wire on the MWCNT-PEC after pretreatment to prepare an MWCNT-PEC electrode;
step 2, preparing a 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode on the surface of the MWCNT-PEC electrode;
step 3, polymerizing PANI/NIHCF on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode to obtain the electromagnetic composite material;
the step 2 specifically comprises the following steps:
step 2.1, adopting a three-electrode system, taking the MWCNT-PEC electrode as a working electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, putting the three-electrode system into a first electrolyte to carry out nitrogen introduction and oxygen removal, wherein the first electrolyte contains 2, 4-dimethylaniline, acrylic acid and PBS buffer solution, and the concentration of the 2, 4-dimethylaniline is 9 x 10-6～7.5×10-3mol/L, acrylic acid concentration 7.2X 10-5～3×10-2mol/L, and the concentration ratio of the 2, 4-dimethylaniline and acrylic acid is 1: (1-8), wherein the pH value of the PBS buffer solution is 5.91-7.73;
step 2.2, conducting power-on circular scanning on the MWCNT-PEC electrode to obtain a semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode;
step 2.3, carrying out elution treatment on the semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode to obtain the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode;
the step 3 specifically comprises the following steps:
step 3.1, adopting a three-electrode system, taking the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode as a working electrode, then respectively connecting the three electrodes with an electrochemical workstation to form an ohmic loop, putting the three-electrode system into a second electrolyte to carry out nitrogen introduction and oxygen removal, wherein the second electrolyte contains aniline and H2SO4、Na2SO4、NiSO4And K3Fe(CN)6Wherein the concentration of the aniline is 0.05-0.3 mol/L, H2SO4Na with a concentration of 0.2-0.8 mol/L2SO4A concentration of 0.15-0.35 mol/L, NiSO4The concentration is 0.001 to 0.003mol/L, K3Fe(CN)6The concentration is 0.001-0.003 mol/L;
and 3.2, performing power-on circular scanning on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode, forming a 2,4-DMA-MIP/PANI/NIHCF composite material film on the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode, and washing and drying after power is off to obtain the electromagnetic composite material.
2. The method for preparing an electromagnetic composite material according to claim 1, wherein the step 1 specifically comprises:
step 1.1, cleaning pencil leads;
step 1.2, adding carbon nanotube powder into sodium dodecyl benzene sulfonate-ethanol solution according to the proportion of respectively adding 0-100 mg of multi-walled carbon nanotube powder into each 10ml of sodium dodecyl benzene sulfonate-ethanol solution for ultrasonic dispersion treatment to obtain uniform carbon nanotube water dispersion; adding carbon nanotube powder into molten paraffin according to the proportion of respectively adding 0-100 mg of multi-walled carbon nanotube powder into each 10ml of molten paraffin for ultrasonic dispersion treatment to obtain uniform carbon nanotube paraffin dispersion liquid; soaking the pencil lead cleaned in the step 1.1 in the carbon nano tube water dispersion liquid for a period of time, taking out and drying the pencil lead, then soaking the pencil lead in the carbon nano tube paraffin dispersion liquid for a period of time, taking out and drying the pencil lead to obtain the MWCNT-PEC;
step 1.3, pretreating the MWCNT-PEC, specifically polishing the MWCNT-PEC, performing ultrasonic cleaning by using absolute ethyl alcohol and distilled water respectively, and finally drying in the air;
and step 1.4, winding a conductive wire on the MWCNT-PEC pretreated in the step 1.3 to prepare the MWCNT-PEC electrode.
3. The method for preparing the electromagnetic composite material according to claim 1, wherein in the step 2.2, when the MWCNT-PEC electrode is subjected to circular scanning of electricity, the scanning potential is-0.2V-1.0V, the scanning speed is 0.04V/s-0.2V/s, and the circular scanning is performed for 10-30 circles;
and in the step 2.3, when the semi-finished product of the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode is subjected to elution treatment, the elution time is 2-6 min.
4. The method for preparing the electromagnetic composite material according to claim 1, wherein in the step 3.2, when the 2,4-DMA-MIP-MWCNT-PEC imprinted polymer thin film electrode is subjected to circular scanning of electricity, the scanning potential is-0.2V-1.05V, the scanning speed is 0.04V/s-0.2V/s, and the circular scanning is carried out for 10-30 circles.
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