CN109254054B - Preparation method and application of chlordimeform sensor based on cobalt-based nitride nano array - Google Patents
Preparation method and application of chlordimeform sensor based on cobalt-based nitride nano array Download PDFInfo
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
Abstract
The invention discloses a preparation method of an chlordimeform sensor based on a cobalt-based nitride nano array. Belongs to the technical field of novel nanometer functional materials and biosensing analysis. Firstly, a cobalt-nickel bimetallic nitride nanosheet array is prepared on a disposable throwable electrode, and by utilizing the large specific surface area, the high adsorption activity to amino and the amino functional group of polydopamine, an in-situ growth method is adopted to successively and directly successively prepare a polydopamine film containing an electron mediator and a molecularly imprinted polymer taking chlordimeform as a template molecule on the cobalt-nickel bimetallic nitride nanosheet array, and after the template molecule is eluted, the original position of the template molecule is changed into a cavity, namely the molecularly imprinted polymer of the template molecule is eluted, so that the preparation of the chlordimeform sensor based on the cobalt-based nitride nanoarray is completed.
Description
Technical Field
The invention relates to a preparation method and application of an electrochemical analysis sensor. Belongs to the technical field of novel nanometer functional materials and biosensing analysis.
Background
Chlordimeform, also known as ampicillin, is a beta-lactam antibiotic, a semi-synthetic broad-spectrum penicillin, and can treat a variety of bacterial infections. Indications include respiratory infections, urinary tract infections, meningitis, salmonella infections, and endocarditis. Because of convenient use and low cost, the medicine is multi-purpose for treating infectious diseases caused by chicken sensitive bacteria, such as escherichia coli, salmonella, pasteurella, staphylococcus, streptococcus and the like. In 2017, 10 and 27, the list of carcinogens published by the international agency for research on cancer of the world health organization, ampicillin is on the list of 3 types of carcinogens. Therefore, the development of a method for quickly, highly selectively and sensitively detecting the chlordimeform is very important to public health and has wide market application prospect.
The molecular imprinting electrochemical sensor has high specificity selectivity, excellent stability, excellent reproducibility, wide detection range and bottom detection limit. The sensor has the advantages of simple preparation, convenient detection, high sensitivity, low cost and the like, and can be widely applied to the fields of chromatographic separation, membrane separation, solid-phase extraction, drug controlled release, chemical sensing and the like. Molecularly Imprinted Polymers (MIPs), also known as "plastic antibodies", are capable of specifically recognizing and selectively adsorbing a specific target molecule (i.e., template molecule). The molecular imprinting technology has many advantages, such as corrosion resistance of organic reagents, good stability, high temperature resistance and simple preparation. Thus, MIP electrochemical sensors based on MIP in combination with electrochemical sensors (MIP-ECS) have attracted a hot interest in the field of electroanalytical chemistry, especially the detection of small molecule contaminants, over the last few years. However, in the preparation process of the traditional MIP-ECS, the defects of difficult elution of template molecules, difficult control of the thickness of the imprinted membrane, poor reproducibility and the like exist, and the application of the molecularly imprinted membrane in an electrochemical sensor is limited. The problems, especially the technical problems that the sensitivity of the electrochemical sensor is reduced due to the fact that the thickness of the molecularly imprinted membrane is not easy to control, and the stability and the reproducibility are reduced due to the fact that the molecularly imprinted membrane is easy to fall off from the surface of an electrode in the elution process, limit the application of MIP _ ECS, so that the research of a new molecularly imprinted polymer synthesis method, a new molecularly imprinted membrane electrode modification method and a method for combining the molecularly imprinted membrane and a substrate material for solving the preparation and application problems of MIP-ECS has important research significance and market value.
Disclosure of Invention
The invention aims to provide a preparation method of an acetamiprid sensor based on a cobalt-based nitride nano array, which has the advantages of strong specificity, simple preparation, convenient detection, high sensitivity and low cost. Based on the purpose, firstly, a cobalt-nickel bimetallic nitride nanosheet array is prepared on a disposable throwable electrode, a polydopamine film containing an electronic mediator and a molecularly imprinted polymer taking chlordimeform as a template molecule are sequentially and directly prepared on the cobalt-nickel bimetallic nitride nanosheet array by utilizing the large specific surface area, the high adsorption activity to amino and the amino functional group of the polydopamine through an in-situ growth method, and after the template molecule is eluted, the original position of the template molecule is changed into a cavity, namely the molecularly imprinted polymer of the template molecule is eluted, so that the chlordimeform sensor based on the cobalt-based nitride nanoarray is prepared. When the method is used for detecting the chlordimeform, the chlordimeform sensor based on the cobalt-based nitride nano array is inserted into a solution to be detected, and the chlordimeform in the solution to be detected is adsorbed into a cavity of the NIP. The greater the concentration of chlordimeform in the solution to be tested, the more chlordimeform that is adsorbed into the cavities of the NIP. When electrochemical detection is carried out, the intensity of detection current is reduced along with the increase of the chlordimeform adsorbed in the cavity of the NIP, so that the concentration of the chlordimeform in the solution to be detected can be qualitatively and quantitatively determined according to the reduction degree of the current intensity.
The technical scheme adopted by the invention is as follows:
1. a preparation method of an acetamiprid sensor based on a cobalt-based nitride nano array is provided, wherein the acetamiprid sensor based on the cobalt-based nitride nano array is obtained by in-situ growth of a template-free molecularly imprinted polymer NIP on a cobalt-nickel bimetal nitride nano sheet array electrode CoNiN-nanoarray; the template-free molecularly imprinted polymer NIP is a molecularly imprinted polymer without template molecules; the molecularly imprinted polymer without the template molecule is obtained by eluting the template molecule from a MIP containing the template molecularly imprinted polymer; the MIP containing the template molecule engram polymer is the MIP containing the template molecule; the template molecule is chlordimeform;
2. the preparation method of the cobalt-nickel bimetallic nitride nanosheet array electrode CoNiN-nanoarray in the technical scheme 1 comprises the following preparation steps:
(1) carrying out ultrasonic cleaning treatment on the disposable throwable electrode by respectively using dilute hydrochloric acid, absolute ethyl alcohol and deionized water so as to remove an oxide layer and surface impurities of the disposable throwable electrode;
(2) weighing 1-3 mmol of Ni (NO)3)2And Co (NO)3)2And 3 to 9mmol of urea CO (NH)2)2Placing the mixture into a 50mL beaker, adding 30mL deionized water, stirring until the mixture is clear, and then transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle;
(3) putting the disposable throwable electrode processed in the step (1) into the solution in the reaction kettle in the step (2), and reacting at the temperature of 100-130 ℃ for 9-12 hours to prepare a precursor electrode of the cobalt-nickel bimetal layered hydroxide nanosheet array;
(4) inserting the cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode obtained in the step (3) into ammonia water for 5-30 seconds, taking out, heating to 340-400 ℃ in an ammonia environment, keeping for 4-8 hours, continuing to naturally cool to room temperature in the ammonia environment, then inserting the electrode into phosphate buffer solution PBS containing dopamine, ammonium persulfate and cobalt nitrate, reacting for 4-6 hours at the temperature of 20-40 ℃, taking out, and performing immersion washing for 2-4 times by using deionized water to prepare a cobalt-nickel bimetal nitride nanosheet array electrode CoNiN-nanoarray;
the disposable and disposable electrode is selected from one of the following electrodes: foam nickel, foam copper, pure nickel sheets, pure copper sheets, pure cobalt sheets, pure silicon sheets and conductive carbon cloth; said Ni (NO)3)2And Co (NO)3)2In a mixture of nickel and cobalt in a molar ratio of 1: 1;
in the phosphate buffer solution PBS containing dopamine, ammonium persulfate and cobalt nitrate: the concentration of dopamine is 2-5 mg/mL, the concentration of ammonium persulfate is 3-8 mg/mL, the concentration of cobalt nitrate is 0.1-0.5 mg/mL, the concentration of phosphate buffer solution PBS is 0.1mol/L, and the pH value is 7.2-8.5;
3. the preparation method of the MIP containing the template molecularly imprinted polymer grown in situ by CoNiN-nanoarray in the technical scheme 1 comprises the following preparation steps:
(1) respectively weighing 0.25-0.45 mmol of template molecules and 3-5 mmol of 2-methacrylic acid MAA in an ampoule bottle, adding 8-15 mL of acetonitrile, and carrying out ultrasonic treatment for 30min until all the template molecules and the 2-methacrylic acid MAA are dissolved;
(2) adding 15-25 mmol of ethylene glycol dimethacrylate EDMA into the solution obtained in the step (1), and carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed to obtain a precursor mixed solution;
(3) clamping the CoNiN-nanoarray prepared in the technical scheme 2 onto a rotary stirrer, inserting the CoNiN-nanoarray into the precursor mixed solution in the step (2), and adding N into the precursor mixed solution2Rotating and stirring at the speed of 5-200 r/s in the environment and the temperature of 20-40 ℃ in a water bath, simultaneously dripping 1mmol of azobisisobutyronitrile AIBN into the mixed solution at the speed of 1-20 d/s for initiating polymerization to obtain the in-situ grown mold on CoNiN-nanoarrayPlate molecularly imprinted polymer MIPs;
4. the preparation steps of the template-free molecularly imprinted polymer NIP for CoNiN-nanoarray in-situ growth in the technical scheme 1 are as follows: immersing the MIP which is obtained in the technical scheme 3 and grows in situ on the CoNiN-nanoarray and contains the template molecularly imprinted polymer into an eluant, eluting the template molecules for 5-20 min at room temperature, and then taking out to obtain the NIP without the template molecularly imprinted polymer; the eluent is a mixed solution of formic acid and methanol, wherein the volume ratio of the formic acid to the methanol is 9 (1-5);
5. the preparation steps of the cobalt-based nitride nano-array-based chlordimeform sensor in the technical scheme 1 are as follows: washing the template-free molecularly imprinted polymer NIP which grows in situ on the CoNiN-nanoarray prepared in the technical scheme 2-4 with deionized water for 2-4 times, and airing at room temperature to prepare the cobalt-based nitride nano-array-based chlordimeform sensor;
6. the chlordimeform sensor based on the cobalt-based nitride nano array prepared by the technical scheme 1-5 is applied to detection of chlordimeform, and comprises the following application steps:
(1) preparing a standard solution: preparing a group of chlordimeform standard solutions with different concentrations including blank standard samples;
(2) modification of a working electrode: taking an amidine sensor based on a cobalt-based nitride nano array as a working electrode, inserting the amidine sensor into the amidine standard solutions with different concentrations prepared in the step (1), incubating for 10min, taking out, and washing for 3 times by using deionized water;
(3) drawing a working curve: taking a saturated calomel electrode as a reference electrode, taking a platinum wire electrode as a counter electrode, forming a three-electrode system with the modified working electrode in the step (2), connecting the three-electrode system with an electrochemical workstation, and sequentially adding 15mL phosphate buffer solution PBS into an electrolytic bath; detecting a current response of the assembled working electrode by Differential Pulse Voltammetry (DPV); the response current intensity of the blank sample is recordedI 0The response current intensity of standard solutions containing different concentrations of chlordimeform was recordedI iIn response to a decrease in current intensityHas a difference of ΔI = I 0-I i，ΔIAnd the mass concentration of chlordimeform standard solutionCWith a linear relationship therebetween, plotting ΔI－CA working curve; the concentration of the phosphate buffer solution PBS is 10mmol/L, pH, and the value is 7.4; the parameters during DPV detection are set as follows: the range and the direction are 0-1V, the step is 0.05V, the pulse time is 0.05s, the sampling time is 0.016s, and the pulse period is 0.5 s;
(4) detecting the chlordimeform in the sample to be detected: replacing the standard solution of chlordimeform in step (1) with the sample to be tested, detecting according to the method in steps (2) and (3), and determining according to the difference delta of the reduction of the response current intensityIAnd working curve to obtain the content of the chlordimeform in the sample to be detected.
Advantageous results of the invention
(1) The chlordimeform sensor based on the cobalt-based nitride nano array is simple to prepare, convenient to operate, low in cost, applicable to portable detection and has market development prospect, and a sample is quickly, sensitively and selectively detected;
(2) according to the invention, the molecular imprinting polymer is grown in situ on the CoNiN-nanoarray electrode for the first time, on one hand, more and more uniform molecular imprinting polymers can be grown by utilizing the large specific surface area of the CoNiN-nanoarray electrode, and the CoNiN-nanoarray electrode has excellent electron transfer capacity, so that the detection sensitivity is greatly improved; on the other hand, when dopamine is polymerized on a cobalt-nickel bimetallic nitride nanosheet array in situ, cobalt ions are creatively doped as an electronic mediator, and electrochemical response current is directly generated during detection, so that the sensor can directly detect in a buffer solution without adding other mediator substances, thereby further reducing the signal background, improving the detection sensitivity, greatly reducing the detection cost and reducing the environmental pollution;
(3) according to the preparation method, the high adsorption activity of the nitride on amino and the large specific surface area of the nano array electrode are combined with dopamine, so that when dopamine is polymerized in situ on the surface of a cobalt-nickel bimetallic nitride nanosheet array, a sufficiently thin polydopamine film is formed and simultaneously the polydopamine film is uniformly covered on the cobalt-nickel bimetallic nitride nanosheet array, and further, a better polymerized molecularly imprinted polymer is laid; then, strong adsorption and connection effects of polydopamine on amino groups rich in the molecularly imprinted polymer are utilized, CoNiN-nanoarray is skillfully used as a stirrer, the mixture is immersed and stirred in the molecularly imprinted precursor mixed solution, and the molecularly imprinted polymer with the film thickness can be controlled by directly growing in situ on the surface of the CoNiN-nanoarray by controlling the stirring speed, the dropping speed of a polymerization reaction initiator and the polymerization reaction temperature, so that the CoNiN-nanoarray can firmly load the molecularly imprinted polymer on the one hand, and the stability and the reproducibility of the prepared electrochemical sensor are obviously improved; on the other hand, the film forming thickness of the molecularly imprinted polymer on the surface of the electrode can be effectively controlled, and the technical problem of poor reproducibility caused by the fact that the film forming thickness of the molecularly imprinted film on the surface of the electrode cannot be controlled is solved; in addition, the preparation method of the invention has important scientific significance and application value for effectively controlling the thickness of the formed film and coating the electronic mediator in situ, and fully improving the sensitivity and detection limit of the electrochemical sensor based on the molecular imprinting.
Detailed Description
EXAMPLE 1 preparation of CoNiN-nanoarray
(1) Carrying out ultrasonic cleaning treatment on the disposable throwable electrode by respectively using dilute hydrochloric acid, absolute ethyl alcohol and deionized water so as to remove an oxide layer and surface impurities of the disposable throwable electrode;
(2) weighing 1mmol Ni (NO)3)2And Co (NO)3)2And 3mmol of urea CO (NH)2)2Placing the mixture into a 50mL beaker, adding 30mL deionized water, stirring until the mixture is clear, and then transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle;
(3) putting the disposable throwable electrode processed in the step (1) into the solution in the reaction kettle in the step (2), and reacting at the temperature of 100 ℃ for 12 hours to prepare a cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode;
(4) inserting the cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode obtained in the step (3) into phosphate buffer solution PBS containing dopamine, ammonium persulfate and cobalt nitrate, reacting for 4 hours at the temperature of 20 ℃, taking out and washing with deionized water for 2 times to prepare a cobalt-nickel bimetal nitride nanosheet array electrode CoNiN-nanoarray;
wherein the disposable throwable electrode is foamed nickel; said Ni (NO)3)2And Co (NO)3)2In a mixture of nickel and cobalt in a molar ratio of 1: 1; the concentration of dopamine is 2 mg/mL, the concentration of ammonium persulfate is 3 mg/mL, the concentration of cobalt nitrate is 0.1 mg/mL, the concentration of phosphate buffer solution PBS is 0.1mol/L, and the pH value is 7.2.
EXAMPLE 2 preparation of CoNiN-nanoarray
(1) Carrying out ultrasonic cleaning treatment on the disposable throwable electrode by respectively using dilute hydrochloric acid, absolute ethyl alcohol and deionized water so as to remove an oxide layer and surface impurities of the disposable throwable electrode;
(2) weighing 2 mmol of Ni (NO)3)2And Co (NO)3)2And 6 mmol of urea CO (NH)2)2Placing the mixture into a 50mL beaker, adding 30mL deionized water, stirring until the mixture is clear, and then transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle;
(3) putting the disposable throwable electrode processed in the step (1) into the solution in the reaction kettle in the step (2), and reacting for 11 hours at the temperature of 110 ℃ to prepare a cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode;
(4) inserting the cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode obtained in the step (3) into phosphate buffer solution PBS containing dopamine, ammonium persulfate and cobalt nitrate, reacting for 5 hours at the temperature of 30 ℃, taking out and washing with deionized water for 3 times to prepare a cobalt-nickel bimetal nitride nanosheet array electrode CoNiN-nanoarray;
wherein the disposable throwable electrode is a pure copper sheet; said Ni(NO3)2And Co (NO)3)2In a mixture of nickel and cobalt in a molar ratio of 1: 1; the concentration of dopamine is 3.5 mg/mL, the concentration of ammonium persulfate is 6.2 mg/mL, the concentration of cobalt nitrate is 0.3 mg/mL, the concentration of phosphate buffer solution PBS is 0.1mol/L, and the pH value is 8.0.
EXAMPLE 3 preparation of CoNiN-nanoarray
(1) Carrying out ultrasonic cleaning treatment on the disposable throwable electrode by respectively using dilute hydrochloric acid, absolute ethyl alcohol and deionized water so as to remove an oxide layer and surface impurities of the disposable throwable electrode;
(2) weighing 3mmol Ni (NO)3)2And Co (NO)3)2And 9mmol of urea CO (NH)2)2Placing the mixture into a 50mL beaker, adding 30mL deionized water, stirring until the mixture is clear, and then transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle;
(3) putting the disposable throwable electrode processed in the step (1) into the solution in the reaction kettle in the step (2), and reacting at the temperature of 130 ℃ for 9 hours to prepare a cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode;
(4) inserting the cobalt-nickel bimetal nitride nanosheet array precursor electrode obtained in the step (3) into phosphate buffer solution PBS containing dopamine, ammonium persulfate and cobalt nitrate, reacting for 6 hours at the temperature of 40 ℃, taking out and washing with deionized water for 4 times to prepare a cobalt-nickel bimetal layered hydroxide nanosheet array electrode CoNiN-nanoarray;
wherein the disposable throwable electrode is a conductive carbon cloth; said Ni (NO)3)2And Co (NO)3)2In a mixture of nickel and cobalt in a molar ratio of 1: 1; the concentration of dopamine is 5mg/mL, the concentration of ammonium persulfate is 8mg/mL, the concentration of cobalt nitrate is 0.5 mg/mL, the concentration of phosphate buffer solution PBS is 0.1mol/L, and the pH value is 8.5.
Embodiment 4 preparation method of chlordimeform sensor based on cobalt-based nitride nano array
(1) Respectively weighing 0.25 mmol of template molecules and 3mmol of 2-methacrylic acid MAA in an ampoule bottle, adding 8 mL of acetonitrile, and performing ultrasonic treatment for 30min until all the template molecules and the 3mmol of 2-methacrylic acid MAA are dissolved;
(2) adding 15 mmol of ethylene glycol dimethacrylate EDMA into the solution obtained in the step (1), and carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed to obtain a precursor mixed solution;
(3) CoNiN-nanoarray prepared in example 1 was clamped to a rotary stirrer and inserted into the precursor mixed solution in step (2) in N2Under the temperature of environment and water bath 20 ℃, stirring in a rotating way at the speed of 200 r/s, simultaneously dripping 1mmol of azobisisobutyronitrile AIBN into the mixed solution at the speed of 1 d/s to initiate polymerization, and obtaining the in-situ grown MIP containing the template molecularly imprinted polymer on CoNiN-nanoarray;
(4) immersing the MIP which is obtained in the step (3) and grows in situ on the CoNiN-nanoarray and contains the molecular imprinting polymer of the template into an eluant, eluting the molecular of the template for 5 min at room temperature, and then taking out to obtain the NIP of the molecular imprinting polymer without the template; continuously washing with deionized water for 2 times, and airing at room temperature to obtain the cobalt-based nitride nano-array-based chlordimeform sensor;
the eluent is a mixed solution of formic acid and methanol, wherein the volume ratio of the formic acid to the methanol is 9: 1.
Example 5 preparation method of cobalt-based nitride nanoarray-based chlordimeform sensor
(1) Respectively weighing 0.35mmol of template molecules and 4 mmol of 2-methacrylic acid MAA in an ampoule bottle, adding 12 mL of acetonitrile, and carrying out ultrasonic treatment for 30min until all the template molecules and the 2-methacrylic acid MAA are dissolved;
(2) adding 18 mmol of ethylene glycol dimethacrylate EDMA into the solution obtained in the step (1), and carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed to obtain a precursor mixed solution;
(3) clamping the CoNiN-nanoarray prepared in the technical scheme 2 onto a rotary stirrer, inserting the CoNiN-nanoarray into the precursor mixed solution in the step (2), and adding N into the precursor mixed solution2Stirring at 60 r/s in water bath at 30 deg.C, and adding 1mmol of azobisisobutyronitrile AIBN dropwise into the mixed solution at 10 drops/s to initiate polymerizationObtaining an in-situ grown MIP containing the molecular imprinting polymer of the template on the CoNiN-nanoarray;
(4) immersing the MIP which is obtained in the step (3) and grows in situ on the CoNiN-nanoarray and contains the molecular imprinting polymer of the template into an eluant, eluting the molecular of the template for 10min at room temperature, and then taking out to obtain the NIP of the molecular imprinting polymer without the template; continuously washing with deionized water for 3 times, and airing at room temperature to obtain the cobalt-based nitride nano-array-based chlordimeform sensor;
the eluent is a mixed solution of formic acid and methanol, wherein the volume ratio of the formic acid to the methanol is 9: 3.
Example 6 preparation method of cobalt-based nitride nanoarray-based chlordimeform sensor
(1) Respectively weighing 0.45mmol of template molecules and 5mmol of 2-methacrylic acid MAA in an ampoule bottle, adding 15mL of acetonitrile, and carrying out ultrasonic treatment for 30min until all the template molecules and the 5mmol of 2-methacrylic acid MAA are dissolved;
(2) adding 25mmol of ethylene glycol dimethacrylate EDMA into the solution obtained in the step (1), and carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed to obtain a precursor mixed solution;
(3) clamping the CoNiN-nanoarray prepared in the technical scheme 2 onto a rotary stirrer, inserting the CoNiN-nanoarray into the precursor mixed solution in the step (2), and adding N into the precursor mixed solution2Under the temperature of environment and water bath 40 ℃, rotationally stirring at the speed of 5 r/s, simultaneously dripping 1mmol of azobisisobutyronitrile AIBN into the mixed solution at the speed of 20 drops/s to initiate polymerization, and obtaining the in-situ grown MIP containing the template molecularly imprinted polymer on CoNiN-nanoarray;
(4) immersing the MIP which is obtained in the step (3) and grows in situ on the CoNiN-nanoarray and contains the molecular imprinting polymer of the template into an eluant, eluting the molecular of the template for 20min at room temperature, and then taking out to obtain the NIP of the molecular imprinting polymer without the template; continuously washing with deionized water for 4 times, and airing at room temperature to obtain the cobalt-based nitride nano-array-based chlordimeform sensor;
the eluent is a mixed solution of formic acid and methanol, wherein the volume ratio of the formic acid to the methanol is 9: 5.
Example 7 the cobalt-based nitride nanoarray-based chlordimeform sensor prepared in examples 1 to 6 is applied to detection of chlordimeform, and comprises the following steps:
(1) preparing a standard solution: preparing a group of chlordimeform standard solutions with different concentrations including blank standard samples;
(2) modification of a working electrode: taking an amidine sensor based on a cobalt-based nitride nano array as a working electrode, inserting the amidine sensor into the amidine standard solutions with different concentrations prepared in the step (1), incubating for 10min, taking out, and washing for 3 times by using deionized water;
(3) drawing a working curve: taking a saturated calomel electrode as a reference electrode, taking a platinum wire electrode as a counter electrode, forming a three-electrode system with the modified working electrode in the step (2), connecting the three-electrode system with an electrochemical workstation, and sequentially adding 15mL PBS into an electrolytic bath; detecting a current response of the assembled working electrode by Differential Pulse Voltammetry (DPV); the response current intensity of the blank sample is recordedI 0The response current intensity of standard solutions containing different concentrations of chlordimeform was recordedI iThe difference in response to the decrease in current intensity is ΔI = I 0-I i，ΔIAnd the mass concentration of chlordimeform standard solutionCWith a linear relationship therebetween, plotting ΔI－CA working curve; the PBS is 10mmol/L phosphate buffer solution, and the pH value of the phosphate buffer solution is 7.4; the parameters during DPV detection are set as follows: the range and the direction are 0-1V, the step is 0.05V, the pulse time is 0.05s, the sampling time is 0.016s, and the pulse period is 0.5 s;
(4) detecting the chlordimeform in the sample to be detected: replacing the standard solution of chlordimeform in step (1) with the sample to be tested, detecting according to the method in steps (2) and (3), and determining according to the difference delta of the reduction of the response current intensityIAnd working curve to obtain the content of the chlordimeform in the sample to be detected.
Example 8 the cobalt-based nitride nanoarray-based pesticidal amidine sensor prepared in examples 1 to 6 was applied to the detection of pesticidal amidine according to the detection procedure of example 7, with a linear range of 0.0008 to 500 mmol/L and a detection limit of 25 nmol/L.
Example 9 detection of Imidacloprid in Water samples
Accurately transferring an environmental water sample, adding an acetamiprid standard solution with a certain mass concentration, taking the water sample without the acetamiprid as a blank, performing a standard addition recovery experiment, detecting the acetamiprid sensor based on the cobalt-based nitride nano-array prepared in the embodiments 1-6 according to the steps of the embodiment 7, determining the recovery rate of the acetamiprid in the water sample, wherein the detection results are shown in table 1:
TABLE 1 detection results of chlordimeform in water samples
The detection results in table 1 show that the Relative Standard Deviation (RSD) of the results is less than 3.1%, the average recovery rate is 98.2-99.6%, and the method can be used for detecting the chlordimeform in the water sample, and is high in sensitivity, strong in specificity, and accurate and reliable in result.
Claims (5)
1. The preparation method of the chlordimeform sensor based on the cobalt-based nitride nano array is characterized in that the chlordimeform sensor based on the cobalt-based nitride nano array is obtained by growing a template-free molecularly imprinted polymer NIP in situ on a cobalt-nickel bimetal nitride nano sheet array electrode CoNiN-nanoarray; the template-free molecularly imprinted polymer NIP is a molecularly imprinted polymer without template molecules; the molecularly imprinted polymer without the template molecule is obtained by eluting the template molecule from a MIP containing the template molecularly imprinted polymer; the MIP containing the template molecule engram polymer is the MIP containing the template molecule; the template molecule is chlordimeform; the MIP containing the template molecular imprinting polymer directly grows on the CoNiN-nanoarray in situ, and the preparation method comprises the following preparation steps:
(1) respectively weighing 0.25-0.45 mmol of template molecules and 3-5 mmol of 2-methacrylic acid MAA in an ampoule bottle, adding 8-15 mL of acetonitrile, and carrying out ultrasonic treatment for 30min until all the template molecules and the 2-methacrylic acid MAA are dissolved;
(2) adding 15-25 mmol of ethylene glycol dimethacrylate EDMA into the solution obtained in the step (1), and carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed to obtain a precursor mixed solution;
(3) clamping CoNiN-nanoarray on a rotary stirrer, and inserting the CoNiN-nanoarray into the precursor mixed solution in the step (2), wherein N is2And (2) rotationally stirring at the speed of 5-200 r/s in an environment and at the temperature of 20-40 ℃ in a water bath, and simultaneously dropwise adding 1mmol of azobisisobutyronitrile AIBN into the mixed solution at the speed of 1-20 d/s to initiate polymerization to obtain the in-situ grown MIP on the CoNiN-nanoarray.
2. The method for preparing an insecticidal amidine sensor based on cobalt-based nitride nanoarrays according to claim 1, wherein the method for preparing CoNiN-nanoarray comprises the following steps:
(1) carrying out ultrasonic cleaning treatment on the disposable throwable electrode by respectively using dilute hydrochloric acid, absolute ethyl alcohol and deionized water so as to remove an oxide layer and surface impurities of the disposable throwable electrode;
(2) weighing 1-3 mmol of Ni (NO)3)2And Co (NO)3)2And 3 to 9mmol of urea CO (NH)2)2Placing the mixture into a 50mL beaker, adding 30mL deionized water, stirring until the mixture is clear, and then transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle;
(3) putting the disposable throwable electrode processed in the step (1) into the solution in the reaction kettle in the step (2), and reacting at the temperature of 100-130 ℃ for 9-12 hours to prepare a precursor electrode of the cobalt-nickel bimetal layered hydroxide nanosheet array;
(4) inserting the cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode obtained in the step (3) into ammonia water for 5-30 seconds, taking out, heating to 340-400 ℃ in an ammonia environment, keeping for 4-8 hours, continuing to naturally cool to room temperature in the ammonia environment, then inserting the electrode into phosphate buffer solution PBS containing dopamine and ammonium persulfate, reacting for 4-6 hours at the temperature of 20-40 ℃, taking out, and performing immersion washing for 2-4 times by using deionized water to prepare a cobalt-nickel bimetal nitride nanosheet array electrode CoNiN-nanoarray;
the disposable and disposable electrode is selected from one of the following electrodes: foam nickel, foam copper, pure nickel sheets, pure copper sheets, pure cobalt sheets, pure silicon sheets and conductive carbon cloth; said Ni (NO)3)2And Co (NO)3)2In a mixture of nickel and cobalt in a molar ratio of 1: 1;
in phosphate buffer solution PBS containing dopamine and ammonium persulfate: the concentration of dopamine is 2-5 mg/mL, the concentration of ammonium persulfate is 3-8 mg/mL, the concentration of phosphate buffer solution PBS is 0.1mol/L, and the pH value is 7.2-8.5.
3. The preparation method of the cobalt-based nitride nanoarray-based chlordimeform sensor as claimed in claim 1, wherein the preparation of the template-free molecularly imprinted polymer NIP comprises the following steps: immersing the obtained MIP which grows in situ on CoNiN-nanoarray and contains the template molecularly imprinted polymer in an eluant, eluting the template molecules for 5-20 min at room temperature, and then taking out to obtain the NIP without the template molecularly imprinted polymer; the eluent is a mixed solution of formic acid and methanol, wherein the volume ratio of the formic acid to the methanol is 9 (1-5).
4. The method for preparing an acetamiprid sensor based on a cobalt-based nitride nano-array as claimed in claim 1, wherein the cobalt-based nitride nano-array is prepared by the steps of: and (3) washing the obtained template-free molecularly imprinted polymer NIP growing in situ on the CoNiN-nanoarray for 2-4 times by using deionized water, and airing at room temperature to obtain the cobalt-based nitride nanoarray-based chlordimeform sensor.
5. The application of the cobalt-based nitride nano-array-based chlordimeform sensor prepared by the preparation method according to any one of claims 1 to 4 in the detection of chlordimeform is characterized in that the detection steps are as follows:
(1) preparing a standard solution: preparing a group of chlordimeform standard solutions with different concentrations including blank standard samples;
(2) modification of a working electrode: taking an amidine sensor based on a cobalt-based nitride nano array as a working electrode, inserting the amidine sensor into the amidine standard solutions with different concentrations prepared in the step (1), incubating for 10min, taking out, and washing for 3 times by using deionized water;
(3) drawing a working curve: taking a saturated calomel electrode as a reference electrode, taking a platinum wire electrode as a counter electrode, forming a three-electrode system with the modified working electrode in the step (2), connecting the three-electrode system with an electrochemical workstation, and sequentially adding 15mL phosphate buffer solution PBS into an electrolytic bath; detecting a current response of the assembled working electrode by Differential Pulse Voltammetry (DPV); the response current intensity of the blank sample is recorded as I0The response current intensity of standard solutions containing different concentrations of chlordimeform is denoted as IiThe difference of response current intensity is Δ I ═ I0-IiThe mass concentration C of the standard chlordimeform solution is linearly related to the mass concentration of the Δ I, and a Δ I-C working curve is drawn; the concentration of the phosphate buffer solution PBS is 10mmol/L, and the pH value is 7.4; the parameters during DPV detection are set as follows: the range and the direction are 0-1V, the step is 0.05V, the pulse time is 0.05s, the sampling time is 0.016s, and the pulse period is 0.5 s;
(4) detecting the chlordimeform in the sample to be detected: and (3) replacing the standard solution of the chlordimeform in the step (1) with a sample to be detected, detecting according to the methods in the steps (2) and (3), and obtaining the content of the chlordimeform in the sample to be detected according to the difference value delta I of the reduction of the response current intensity and the working curve.
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