CN109307698A - A kind of preparation method and application for the iron cobalt nitride sensing electrode detecting organo-chlorine pesticide - Google Patents
A kind of preparation method and application for the iron cobalt nitride sensing electrode detecting organo-chlorine pesticide Download PDFInfo
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- CN109307698A CN109307698A CN201811306542.6A CN201811306542A CN109307698A CN 109307698 A CN109307698 A CN 109307698A CN 201811306542 A CN201811306542 A CN 201811306542A CN 109307698 A CN109307698 A CN 109307698A
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Abstract
The invention discloses a kind of preparation methods of iron cobalt nitride sensing electrode for detecting organo-chlorine pesticide.Belong to Nano-function thin films and biosensory analysis technology field.The present invention is prepared for iron cobalt dual-metal nitride nano chip arrays can disposably throw first on electrode, using its big specific surface area and to the high adsorption activity of amino, and the amido functional group of poly-dopamine, using the method for growth in situ, directly it is prepared for the poly-dopamine film containing electron mediator in succession and using organo-chlorine pesticide as the molecularly imprinted polymer of template molecule on iron cobalt dual-metal nitride nano chip arrays in succession, after by template molecule elution, the position of template molecule originally has become hole, that is the molecularly imprinted polymer of eluted template molecule, thus, it is a kind of detect organo-chlorine pesticide iron cobalt nitride sensing electrode just prepare completion.
Description
Technical field
The present invention relates to a kind of preparation method and applications of electro-chemical analyzing sensor.Belong to Nano-function thin films with
Biosensory analysis technology field.
Background technique
Organo-chlorine pesticide is for preventing and treating the organic compound for containing organic chlorine element in the constituent of phytopathy, insect pest
Object.Organo-chlorine pesticide is mainly manifested in infringement nerve and parenchymatous organ to the toxicity of human body.Acute toxicity to people is mainly
Nerve center is stimulated, slow poisoning shows as loss of appetite, and weight loss also can produce small brain disorder, blood forming organ barrier sometimes
Hinder.Document report, some organo-chlorine pesticides have carcinogenicity to experimental animal.Poisoner has strong impulse symptom, main table
Be now headache, it is dizzy, furious it is congested, shed tears keep in dark place, cough, pharyngalgia, out of strength, perspiration, salivation, nausea, loss of appetite, insomnia with
And Head And Face cacesthesia etc., moderate intoxication person, there are also vomiting, abdominal pain, have aches in the limbs, twitch, is purple in addition to having with above-mentioned symptom
Dark purple, expiratory dyspnea, tachycardia etc.；Severe intoxication person in addition to above-mentioned symptom obviously aggravates, still have high fever, hidrosis, contraction of muscle,
Epilepsy seizure, stupor.It is even dead.Food containing Organochlorine Pesticide Residues causes cannot be neglected potential to human health
It threatens.Therefore, it is extremely important to publilc health to develop a kind of quick, highly selective and Sensitive Detection organo-chlorine pesticide method,
And there is wide market application prospect.
Molecular imprinting electrochemical sensor has high specific selectivity, excellent stability, excellent reproducibility, wide inspection
Survey range and floor detection limit.Due to the sensor prepare simple, easy to detect, high sensitivity, it is at low cost the advantages that it is extensive
Applied to the fields such as chromatographic isolation, film point, Solid Phase Extraction, medicine controlled releasing, chemical sensitisation.Molecularly imprinted polymer (MIP), also referred to as
It, being capable of specific recognition and the specific target molecule of selective absorption (i.e. template molecule) for " plastics antibody ".Due to molecular engram
Technology has many advantages that, such as organic reagent corrosion resistance, good stability, heat-resisting quantity and preparation are simple.Therefore, in mistake
In several years gone, electroanalysis is caused based on the MIP electrochemical sensor (MIP-ECS) that MIP is combined with electrochemical sensor
The detection of the focus of chemical field, especially small molecule contaminants.However, having in the preparation process of traditional MIP-ECS
The elution of template molecule difficulty, the disadvantages of thickness of blotting membrane is difficult to control, reproducibility is poor, limit molecular engram film and passed in electrochemistry
Application in sensor.These problems, especially molecular engram film thickness are not easy to control to lead to electrochemical sensor sensitivity decrease
And molecular engram film easily falls off from electrode surface the technical problem for causing stability and reproducibility to reduce during elution, limit
The application of MIP_ECS has been made, therefore, has found new molecularly imprinted polymer synthetic method, new molecular engram film electrode is repaired
The combination method of decorations method and molecular engram film and base material, to solve the preparation of MIP-ECS and have using problem important
Research significance and market value.
Summary of the invention
The purpose of the present invention is to provide a kind of high specificity, prepare simple, easy to detect, high sensitivity, at low cost
Detect the preparation method of the iron cobalt nitride sensing electrode of organo-chlorine pesticide, prepared electrochemical sensing electrode, preparation is simple,
Favorable reproducibility, stability are strong, can be used as quick, Sensitive Detection of the electrochemical sensor for organo-chlorine pesticide.Based on this purpose,
The present invention is prepared for iron cobalt dual-metal nitride nano chip arrays can disposably throw first on electrode, utilize its big specific surface
Product and to the high adsorption activity of amino and the amido functional group of poly-dopamine, using the method for growth in situ, in succession in iron cobalt
Directly it is prepared for the poly-dopamine film containing electron mediator and in succession on bimetallic nitride nano-chip arrays with organochlorine
Pesticide is the molecularly imprinted polymer of template molecule, and after by template molecule elution, the position of template molecule originally becomes
Hole, the i.e. molecularly imprinted polymer of eluted template molecule, as a result, a kind of iron cobalt nitride sensing for detecting organo-chlorine pesticide
Electrode just prepares completion.When the iron cobalt nitride sensing for when detecting to organo-chlorine pesticide, will test organo-chlorine pesticide
Electrode is inserted into solution to be measured, and the organo-chlorine pesticide in solution to be measured can be adsorbed onto the hole of NIP.It is organic in solution to be measured
Chloro pesticide concentration is bigger, and it is more to be adsorbed onto organo-chlorine pesticide in the hole of NIP.When carrying out Electrochemical Detection, electric current is detected
Intensity can become smaller with increasing for organo-chlorine pesticide in the hole of NIP is adsorbed onto, thus according to the degree that current strength reduces,
It is capable of the concentration of organo-chlorine pesticide in qualitative, quantitative solution to be measured.
The technical solution adopted by the invention is as follows:
1. a kind of preparation method for the iron cobalt nitride sensing electrode for detecting organo-chlorine pesticide, the detection organo-chlorine pesticide
Iron cobalt nitride sensing electrode by growth in situ on iron cobalt dual-metal nitride nano chip arrays electrode FeCoN-nanoarray
What no template molecule molecularly imprinted polymer NIP was obtained；Described has been free from mould without template molecule molecularly imprinted polymer NIP
The molecularly imprinted polymer of plate molecule；The molecularly imprinted polymer without containing template molecule is by molecule containing template molecule
What imprinted polymer MIP was obtained by eluted template molecule；The MIP of molecularly imprinted polymer containing template molecule is containing mould
The molecularly imprinted polymer of plate molecule；The template molecule is organo-chlorine pesticide；
2. the preparation side of the chip arrays electrode of iron cobalt dual-metal nitride nano described in technical solution 1 FeCoN-nanoarray
Method includes following preparation step:
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 1 ~ 3 mmol Co (NO is weighed3)2With Fe (NO3)3Mixture and 3 ~ 9 mmol urea CO (NH2)2, it is put into
In 50 mL beakers, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 100 ~
It is reacted 9 ~ 12 hours at a temperature of 130 DEG C, iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electricity is prepared
Pole；
(4) 5 in the iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode insertion ammonium hydroxide obtained step (3) ~
It is taken out after 30 seconds, under ammonia environment, after being heated to 340 ~ 400 DEG C and being kept for 4 ~ 8 hours, continuation is dropped naturally under ammonia environment
To room temperature, it is then inserted into the phosphate buffer solution PBS containing dopamine, Ammonium Persulfate 98.5 and cobalt nitrate, 20 ~ 40
After being reacted 4 ~ 6 hours at a temperature of DEG C, takes out and embathed 2 ~ 4 times with deionized water, iron cobalt dual-metal nitride is prepared and receives
Rice chip arrays electrode FeCoN-nanoarray；
The described disposable electrode of throwing is selected from one of cycle unit: nickel foam, foam copper, pure nickel piece, pure copper sheet, pure cobalt piece,
Pure silicon piece, conductive carbon cloth；Co (the NO3)2With Fe (NO3)3Mixture in the molar ratio of cobalt and iron be 1:1；
In the phosphate buffer solution PBS containing dopamine, Ammonium Persulfate 98.5 and cobalt nitrate: dopamine concentration is 2 ~ 5
Mg/mL, the concentration of Ammonium Persulfate 98.5 are 3 ~ 8 mg/mL, and the concentration of cobalt nitrate is 0.1 ~ 0.5 mg/mL, phosphate buffer solution PBS
Concentration be 0.1 mol/L, pH value be 7.2 ~ 8.5；
3. the MIP of molecularly imprinted polymer containing template molecule of FeCoN-nanoarray growth in situ described in technical solution 1
Preparation method include following preparation step:
(1) 0.25 ~ 0.45mmol template molecule and 3 ~ 5 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, are added
Enter 8 ~ 15 mL acetonitriles, 30 min of ultrasound to whole dissolutions；
(2) 15 ~ 25 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound
To being uniformly mixed, precursor mixed solution is obtained；
(3) FeCoN-nanoarray prepared in technical solution 2 is clipped on Stirring device, before being inserted into step (2)
It drives in body mixed solution, in N2At a temperature of environment and 20 ~ 40 DEG C of water-bath, with 5 ~ 200 revolutions per seconds of speed Stirring, simultaneously
Initiation polymerization is carried out to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping with 1 ~ 20 drop/sec of speed, in FeCoN-
The MIP of molecularly imprinted polymer containing template molecule of growth in situ is obtained on nanoarray；
4. FeCoN-nanoarray growth in situ described in technical solution 1 without template molecule molecularly imprinted polymer NIP
Preparation step are as follows: by obtained in technical solution 3 on FeCoN-nanoarray growth in situ molecule containing template molecule print
Mark polymer MIP is immersed in eluant, eluent, and template molecule is carried out 5 ~ 20 min of elution at room temperature, then takes out, obtains
Without template molecule molecularly imprinted polymer NIP；The eluant, eluent is the mixed liquor of formic acid and methanol, wherein formic acid and methanol
Volume ratio is 9:(1 ~ 5)；
5. detecting the preparation step of the iron cobalt nitride sensing electrode of organo-chlorine pesticide described in technical solution 1 are as follows: by technology
In scheme 2 ~ 4 the obtained growth in situ on FeCoN-nanoarray without template molecule molecularly imprinted polymer NIP, spend
Ionized water embathes 2 ~ 4 times, dries at room temperature, obtains the iron cobalt nitride sensing electrode of detection organo-chlorine pesticide；
6. sensing electricity using the iron cobalt nitride of detection organo-chlorine pesticide prepared by technical solution described in technical solution 1 ~ 5
Pole, applied to the detection of organo-chlorine pesticide, including following applying step:
(1) standard solution is prepared: preparing the organo-chlorine pesticide standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: the iron cobalt nitride sensing electrode that will test organo-chlorine pesticide is working electrode, inserting step
(1) the organo-chlorine pesticide standard solution for the various concentration prepared in takes out after hatching 10 min, is embathed 3 times with deionized water；
(3) working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is used as to electrode, with step
(2) the working electrode composition three-electrode system modified, connects electrochemical workstation, 15 mL is successively added in a cell
Phosphate buffer solution PBS；Pass through the current-responsive of the working electrode of Differential Pulse Voltammetry DPV detection assembling；Blank standard specimen
Response current intensity be denoted asI 0, the response current intensity of the organo-chlorine pesticide standard solution containing various concentration is denoted asI i, response
The difference that current strength reduces is ΔI = I 0-I i, ΔIWith the mass concentration of organo-chlorine pesticide standard solutionCBetween linear pass
Δ is drawn by systemI?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；Described
Parameter setting when DPV is detected are as follows: range and direction are 0 ~ 1 V, and stride is 0.05 V, and the burst length is 0.05 s, when sampling
Between be 0.016 s, the pulse period be 0.5 s；
(4) in sample to be tested organo-chlorine pesticide detection: replace the organo-chlorine pesticide standard in step (1) molten with sample to be tested
Liquid is detected according to the method in step (2) and (3), the difference DELTA that current strength reduces according to responseIAnd working curve,
Obtain the content of organo-chlorine pesticide in sample to be tested；
7. organo-chlorine pesticide described in technical solution 1 ~ 6 is one of following organo-chlorine pesticide: double rubigan trichloroethanes
(DDT), hexachlorocyclohexanes (six six six), tetradiphon, dicofol, pentachloronitrobenzene, termil (hundred bacterium
Clearly), heptachlor indenes (heptachlor), octa-klor (Niran).
Beneficial achievement of the invention
(1) the iron cobalt nitride sensing electrode preparation of detection organo-chlorine pesticide of the present invention is simple, easy to operate, realizes
Quick, sensitive, highly selective detection to sample, and it is at low cost, it can be applied to portable inspectiont, before there is market development
Scape；
(2) growth in situ divides the present invention on iron cobalt dual-metal nitride nano chip arrays electrode FeCoN-nanoarray for the first time
On the one hand sub- imprinted polymer can grow molecule more, more evenly using the big specific surface area of FeCoN-nanoarray and print
Mark polymer, and FeCoN-nanoarray has excellent electron transmission ability, to greatly improve detection sensitivity；Separately
On the one hand, when the present invention is by dopamine in-situ polymerization to iron cobalt dual-metal nitride nano chip arrays, creative is doped into
Cobalt ions directly generates electrochemical response electric current as electron mediator when detecting, allows sensor without being added
It is directly detected in the buffer solution of other media substance, thus further decreasing signal background, improving detection sensitivity
While, it greatly reduces testing cost and reduces environmental pollution；
(3) present invention specific surface area and dopamine big using high adsorption activity and nano-array electrode of the nitride to amino
It combines, so that dopamine in iron cobalt dual-metal nitride nano chip arrays in situ Polymerization, is forming sufficiently thin gather
While dopamine film, on uniform fold to iron cobalt dual-metal nitride nano chip arrays, thus to be more more preferable in next step
Polymerizable molecular imprinted polymer carry out place mat；Later using poly-dopamine to the strong of the amino being rich on molecularly imprinted polymer
Absorption connection function, then dexterously use FeCoN-nanoarray as blender, in molecular engram precursor mixed solution
In carry out immersion stirring, by control mixing speed, initiators for polymerization rate of addition and polymeric reaction temperature,
The surface FeCoN-nanoarray direct in-situ grows the molecularly imprinted polymer that can control film thickness, on the one hand makes
FeCoN-nanoarray can secured supporting molecular imprinted polymer, to significantly improve prepared electrochemical sensor
Stability and reproducibility；On the other hand molecularly imprinted polymer can be effectively controlled in the film forming thickness of electrode surface, solve
It is unable to control molecular engram film and is unable to control the technical problem so as to cause poor reproducibility in electrode surface film forming thickness；In addition,
More since preparation method of the invention is to the in-stiu coating of the effective control and electron mediator of film forming thickness, can sufficiently improve
The sensitivity of electrochemical sensor based on molecular engram and detection limit have important scientific meaning and application value.
Specific embodiment
The preparation of 1 FeCoN-nanoarray of embodiment
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 1 mmol Co (NO is weighed3)2With Fe (NO3)3Mixture and 3 mmol urea CO (NH2)2, it is put into 50
In mL beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 100
It is reacted 12 hours at a temperature of DEG C, iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode insertion that step (3) obtains is contained into DOPA
In the phosphate buffer solution PBS of amine, Ammonium Persulfate 98.5 and cobalt nitrate, 20 DEG C at a temperature of reaction 4 hours after, taking-up be used in combination
Deionized water is embathed 2 times, and iron cobalt dual-metal nitride nano chip arrays electrode FeCoN-nanoarray is prepared；
The electrode therein that can disposably throw is nickel foam；Co (the NO3)2With Fe (NO3)3Mixture in cobalt and iron rub
You are than being 1:1；Dopamine concentration is 2 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 3 mg/mL, and the concentration of cobalt nitrate is 0.1 mg/
The concentration of mL, phosphate buffer solution PBS are 0.1 mol/L, pH value 7.2.
The preparation of 2 FeCoN-nanoarray of embodiment
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 2 mmol Ni (NO are weighed3)2With Co (NO3)2Mixture and 6 mmol urea CO (NH2)2, it is put into 50
In mL beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 110
It is reacted 11 hours at a temperature of DEG C, iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode insertion that step (3) obtains is contained into DOPA
In the phosphate buffer solution PBS of amine, Ammonium Persulfate 98.5 and cobalt nitrate, 30 DEG C at a temperature of reaction 5 hours after, taking-up be used in combination
Deionized water is embathed 3 times, and iron cobalt dual-metal nitride nano chip arrays electrode FeCoN-nanoarray is prepared；
The electrode therein that can disposably throw is pure copper sheet；Co (the NO3)2With Fe (NO3)3Mixture in cobalt and iron rub
You are than being 1:1；Dopamine concentration is 3.5 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 6.2 mg/mL, and the concentration of cobalt nitrate is 0.3
The concentration of mg/mL, phosphate buffer solution PBS are 0.1 mol/L, pH value 8.0.
The preparation of 3 FeCoN-nanoarray of embodiment
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 3 mmol Co (NO are weighed3)2With Fe (NO3)3Mixture and 9 mmol urea CO (NH2)2, it is put into 50
In mL beaker, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 130
It is reacted 9 hours at a temperature of DEG C, iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode is prepared；
(4) the iron cobalt dual-metal nitride nano chip arrays presoma electrode insertion obtained step (3) contains dopamine, over cure
In the phosphate buffer solution PBS of acid amide and cobalt nitrate, 40 DEG C at a temperature of reaction 6 hours after, take out and use deionized water
It embathes 4 times, iron cobalt dual-metal layered hydroxide nano-chip arrays electrode FeCoN-nanoarray is prepared；
The electrode therein that can disposably throw is conductive carbon cloth；Co (the NO3)2With Fe (NO3)3Mixture in cobalt and iron
Molar ratio is 1:1；Dopamine concentration is 5 mg/mL, and the concentration of Ammonium Persulfate 98.5 is 8 mg/mL, and the concentration of cobalt nitrate is 0.5 mg/
The concentration of mL, phosphate buffer solution PBS are 0.1 mol/L, pH value 8.5.
Embodiment 4 detects the preparation method of the iron cobalt nitride sensing electrode of organo-chlorine pesticide
(1) 0.25 mmol template molecule and 3 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 8 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 15 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) FeCoN-nanoarray prepared in embodiment 1 is clipped on Stirring device, the forerunner being inserted into step (2)
In body mixed solution, in N2At a temperature of environment and 20 DEG C of water-bath, with 200 revolutions per seconds of speed Stirring, while with 1 drop/
The speed of second carries out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, in FeCoN-nanoarray
On obtain the MIP of molecularly imprinted polymer containing template molecule of growth in situ；
(4) molecularly imprinted polymer containing template molecule of growth in situ on FeCoN-nanoarray for obtaining step (3)
MIP is immersed in eluant, eluent, and template molecule is carried out 5 min of elution at room temperature, is then taken out, no template molecule point is obtained
Sub- imprinted polymer NIP；Continue to be embathed 2 times with deionized water, dry at room temperature, obtains the iron cobalt nitrogen of detection organo-chlorine pesticide
Compound sensing electrode；
Eluant, eluent therein is the mixed liquor of formic acid and methanol, and wherein the volume ratio of formic acid and methanol is 9:1.
Embodiment 5 detects the preparation method of the iron cobalt nitride sensing electrode of organo-chlorine pesticide
(1) 0.35mmol template molecule and 4 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 12 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 18 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) FeCoN-nanoarray prepared in technical solution 2 is clipped on Stirring device, before being inserted into step (2)
It drives in body mixed solution, in N2At a temperature of environment and 30 DEG C of water-bath, with 60 revolutions per seconds of speed Stirring, while with 10 drops/
The speed of second carries out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, in FeCoN-nanoarray
On obtain the MIP of molecularly imprinted polymer containing template molecule of growth in situ；
(4) molecularly imprinted polymer containing template molecule of growth in situ on FeCoN-nanoarray for obtaining step (3)
MIP is immersed in eluant, eluent, and template molecule is carried out 10 min of elution at room temperature, then takes out, obtains no template molecule
Molecularly imprinted polymer NIP；Continue to be embathed 3 times with deionized water, dry at room temperature, obtains the iron cobalt of detection organo-chlorine pesticide
Nitride sensing electrode；
Eluant, eluent therein is the mixed liquor of formic acid and methanol, and wherein the volume ratio of formic acid and methanol is 9:3.
Embodiment 6 detects the preparation method of the iron cobalt nitride sensing electrode of organo-chlorine pesticide
(1) 0.45mmol template molecule and 5 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, and 15 mL second are added
Nitrile, 30 min of ultrasound to whole dissolutions；
(2) 25 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound are to mixed
It closes uniformly, obtains precursor mixed solution；
(3) FeCoN-nanoarray prepared in technical solution 2 is clipped on Stirring device, before being inserted into step (2)
It drives in body mixed solution, in N2At a temperature of environment and 40 DEG C of water-bath, with 5 revolutions per seconds of speed Stirring, while with 20 drops/
The speed of second carries out initiation polymerization to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, in FeCoN-nanoarray
On obtain the MIP of molecularly imprinted polymer containing template molecule of growth in situ；
(4) molecularly imprinted polymer containing template molecule of growth in situ on FeCoN-nanoarray for obtaining step (3)
MIP is immersed in eluant, eluent, and template molecule is carried out 20 min of elution at room temperature, then takes out, obtains no template molecule
Molecularly imprinted polymer NIP；Continue to be embathed 4 times with deionized water, dry at room temperature, obtains the iron cobalt of detection organo-chlorine pesticide
Nitride sensing electrode；
Eluant, eluent therein is the mixed liquor of formic acid and methanol, and wherein the volume ratio of formic acid and methanol is 9:5.
The iron cobalt nitride sensing electrode of the detection organo-chlorine pesticide of 7 embodiment 1 ~ 6 of embodiment preparation, is applied to organic
The detection of chloro pesticide, steps are as follows:
(1) standard solution is prepared: preparing the organo-chlorine pesticide standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: the iron cobalt nitride sensing electrode that will test organo-chlorine pesticide is working electrode, inserting step
(1) the organo-chlorine pesticide standard solution for the various concentration prepared in takes out after hatching 10 min, is embathed 3 times with deionized water；
(3) working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is used as to electrode, with step
(2) the working electrode composition three-electrode system modified, connects electrochemical workstation, 15 mL is successively added in a cell
PBS；Pass through the current-responsive of the working electrode of Differential Pulse Voltammetry DPV detection assembling；The response current intensity of blank standard specimen
It is denoted asI 0, the response current intensity of the organo-chlorine pesticide standard solution containing various concentration is denoted asI i, response current strength reduction
Difference is ΔI = I 0-I i, ΔIWith the mass concentration of organo-chlorine pesticide standard solutionCBetween it is linear, draw ΔI?C
Working curve；The PBS is the phosphate buffer solution of 10 mmol/L, and the pH value of the phosphate buffer solution is
7.4；Parameter setting when the described DPV detection are as follows: range and direction are 0 ~ 1 V, and stride is 0.05 V, burst length 0.05
S, sampling time are 0.016 s, and the pulse period is 0.5 s；
(4) in sample to be tested organo-chlorine pesticide detection: replace the organo-chlorine pesticide standard in step (1) molten with sample to be tested
Liquid is detected according to the method in step (2) and (3), the difference DELTA that current strength reduces according to responseIAnd working curve,
Obtain the content of organo-chlorine pesticide in sample to be tested.
The iron cobalt nitride sensing electrode of the detection organo-chlorine pesticide of 8 embodiment 1 ~ 6 of embodiment preparation, according to embodiment
7 detecting step is applied to the detection of different organo-chlorine pesticides, and the range of linearity and detection limit are shown in Table 1:
The detection technique index of 1 organo-chlorine pesticide of table
The detection of organo-chlorine pesticide in 9 water sample of embodiment
Water sample is accurately pipetted, the organo-chlorine pesticide standard solution of certain mass concentration is added, the water of organo-chlorine pesticide not to be added
Sample is blank, carries out recovery testu, and the iron cobalt nitride of the detection organo-chlorine pesticide prepared with embodiment 1 ~ 6 senses electricity
Pole is detected according to the step of embodiment 7, measures the rate of recovery of organo-chlorine pesticide in water sample, and testing result is shown in Table 2:
The testing result of organo-chlorine pesticide in 2 water sample of table
2 testing result of table it is found that the relative standard deviation (RSD) of result less than 3.5 %, average recovery rate is 98.0 ~
101.6%, show that the present invention can be used for the detection of Organochlorine Pesticides in pig urine, the high sensitivity of method, high specificity, knot
Fruit is accurate and reliable.
Claims (7)
1. a kind of preparation method for the iron cobalt nitride sensing electrode for detecting organo-chlorine pesticide, which is characterized in that the detection
The iron cobalt nitride sensing electrode of organo-chlorine pesticide is by iron cobalt dual-metal nitride nano chip arrays electrode FeCoN-nanoarray
Upper growth in situ is obtained without template molecule molecularly imprinted polymer NIP；It is described without template molecule molecularly imprinted polymer NIP
It is free from the molecularly imprinted polymer of template molecule；The molecularly imprinted polymer without containing template molecule is by containing mould
What plate molecular imprinted polymer MIP was obtained by eluted template molecule；The molecularly imprinted polymer containing template molecule
MIP is the molecularly imprinted polymer containing template molecule；The template molecule is organo-chlorine pesticide.
2. iron cobalt dual-metal nitride nano chip arrays electrode FeCoN-nanoarray as described in claim 1, feature exist
In the preparation method of the FeCoN-nanoarray includes following preparation step:
(1) it will can disposably throw electrode and carry out ultrasonic cleaning processing using dilute hydrochloric acid, dehydrated alcohol and deionization respectively, to go
Except the oxide layer and surface impurity that can disposably throw electrode；
(2) 1 ~ 3 mmol Co (NO is weighed3)2With Fe (NO3)3Mixture and 3 ~ 9 mmol urea CO (NH2)2, it is put into
In 50 mL beakers, 30 mL deionized waters are added and stir to clarify, are then transferred into 50 mL ptfe autoclaves；
(3) in the disposable solution thrown in the reaction kettle that electrode is put into step (2) for handling step (1) well, 100 ~
It is reacted 9 ~ 12 hours at a temperature of 130 DEG C, iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electricity is prepared
Pole；
(4) 5 in the iron cobalt dual-metal layered hydroxide nano-chip arrays presoma electrode insertion ammonium hydroxide obtained step (3) ~
It is taken out after 30 seconds, under ammonia environment, after being heated to 340 ~ 400 DEG C and being kept for 4 ~ 8 hours, continuation is dropped naturally under ammonia environment
To room temperature, it is then inserted into the phosphate buffer solution PBS containing dopamine, Ammonium Persulfate 98.5 and cobalt nitrate, 20 ~ 40
After being reacted 4 ~ 6 hours at a temperature of DEG C, takes out and embathed 2 ~ 4 times with deionized water, iron cobalt dual-metal nitride is prepared and receives
Rice chip arrays electrode FeCoN-nanoarray；
The described disposable electrode of throwing is selected from one of cycle unit: nickel foam, foam copper, pure nickel piece, pure copper sheet, pure cobalt piece,
Pure silicon piece, conductive carbon cloth；Co (the NO3)2With Fe (NO3)3Mixture in the molar ratio of cobalt and iron be 1:1；
In the phosphate buffer solution PBS containing dopamine, Ammonium Persulfate 98.5 and cobalt nitrate: dopamine concentration is 2 ~ 5
Mg/mL, the concentration of Ammonium Persulfate 98.5 are 3 ~ 8 mg/mL, and the concentration of cobalt nitrate is 0.1 ~ 0.5 mg/mL, phosphate buffer solution PBS
Concentration be 0.1 mol/L, pH value be 7.2 ~ 8.5.
3. the MIP of molecularly imprinted polymer containing template molecule as described in claim 1, which is characterized in that described containing template point
Sub- molecularly imprinted polymer MIP is that direct in-situ is grown on FeCoN-nanoarray, and preparation method includes following preparation step
It is rapid:
(1) 0.25 ~ 0.45mmol template molecule and 3 ~ 5 mmol 2- methacrylic acid MAA are weighed respectively in peace times bottle, are added
Enter 8 ~ 15 mL acetonitriles, 30 min of ultrasound to whole dissolutions；
(2) 15 ~ 25 mmol ethylene glycol dimethacrylate EDMA are added in the solution of step (1), 30 min of ultrasound
To being uniformly mixed, precursor mixed solution is obtained；
(3) FeCoN-nanoarray is clipped on Stirring device, is inserted into the precursor mixed solution in step (2),
N2At a temperature of environment and 20 ~ 40 DEG C of water-bath, with 5 ~ 200 revolutions per seconds of speed Stirring, while with 1 ~ 20 drop/sec of speed
Initiation polymerization is carried out to 1 mmol azodiisobutyronitrile AIBN of mixed solution and dripping, original is obtained on FeCoN-nanoarray
The MIP of molecularly imprinted polymer containing template molecule of position growth.
4. as described in claim 1 without template molecule molecularly imprinted polymer NIP, it is characterised in that the no template point
The preparation step of sub- molecularly imprinted polymer NIP are as follows: will be given birth in situ on FeCoN-nanoarray obtained in claim 3
The long MIP of molecularly imprinted polymer containing template molecule is immersed in eluant, eluent, and template molecule is carried out elution 5 ~ 20 at room temperature
Min then takes out, and obtains no template molecule molecularly imprinted polymer NIP；The eluant, eluent is the mixing of formic acid and methanol
Liquid, wherein the volume ratio of formic acid and methanol is 9:(1 ~ 5).
5. the preparation step of the iron cobalt nitride sensing electrode of detection organo-chlorine pesticide as described in claim 1 are as follows: by right
It is required that in 2 ~ 4 the obtained growth in situ on FeCoN-nanoarray without template molecule molecularly imprinted polymer NIP, spend
Ionized water embathes 2 ~ 4 times, dries at room temperature, obtains the iron cobalt nitride sensing electrode of detection organo-chlorine pesticide.
6. sensing electricity using the iron cobalt nitride of detection organo-chlorine pesticide prepared by preparation method described in claim 1 ~ 5
Pole, the detection applied to organo-chlorine pesticide, which is characterized in that the detecting step is as follows:
(1) standard solution is prepared: preparing the organo-chlorine pesticide standard solution of one group of various concentration including blank standard specimen；
(2) working electrode is modified: the iron cobalt nitride sensing electrode that will test organo-chlorine pesticide is working electrode, inserting step
(1) the organo-chlorine pesticide standard solution for the various concentration prepared in takes out after hatching 10 min, is embathed 3 times with deionized water；
(3) working curve is drawn: using saturated calomel electrode electrode as reference electrode, platinum electrode is used as to electrode, with step
(2) the working electrode composition three-electrode system modified, connects electrochemical workstation, 15 mL is successively added in a cell
Phosphate buffer solution PBS；Pass through the current-responsive of the working electrode of Differential Pulse Voltammetry DPV detection assembling；Blank standard specimen
Response current intensity be denoted asI 0, the response current intensity of the organo-chlorine pesticide standard solution containing various concentration is denoted asI i, response
The difference that current strength reduces is ΔI = I 0-I i, ΔIWith the mass concentration of organo-chlorine pesticide standard solutionCBetween linear pass
Δ is drawn by systemI?CWorking curve；The phosphate buffer solution PBS concentration is 10 mmol/L, pH value 7.4；It is described
DPV detection when parameter setting are as follows: range and direction are 0 ~ 1 V, and stride is 0.05 V, and the burst length is 0.05 s, sampling
Time is 0.016 s, and the pulse period is 0.5 s；
(4) in sample to be tested organo-chlorine pesticide detection: replace the organo-chlorine pesticide standard in step (1) molten with sample to be tested
Liquid is detected according to the method in step (2) and (3), the difference DELTA that current strength reduces according to responseIAnd working curve,
Obtain the content of organo-chlorine pesticide in sample to be tested.
7. the organo-chlorine pesticide as described in claim 1 ~ 6 is one of following organo-chlorine pesticide: double rubigan trichloroethanes
(DDT), hexachlorocyclohexanes (six six six), tetradiphon, dicofol, pentachloronitrobenzene, termil (hundred bacterium
Clearly), heptachlor indenes (heptachlor), octa-klor (Niran).
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