CN107576716B - A kind of acupuncture needle base working electrode electrochemical sensor detecting trace heavy metal - Google Patents
A kind of acupuncture needle base working electrode electrochemical sensor detecting trace heavy metal Download PDFInfo
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Abstract
The present invention relates to electrochemical sensor field, specifically a kind of acupuncture needle base working electrode electrochemical sensor for detecting trace heavy metal.Specifically include acupuncture needle base working electrode, reference electrode and auxiliary electrode；The working electrode is made of stainless pin acupuncture needle, it is insulated with shank part of the polyvinyl chloride pipe to acupuncture needle, it is sealed with binding site of the silicon rubber to polyvinyl chloride pipe and shank, using the needle point of acupuncture needle as sensitive face, needle surface is covered with the cation-exchange membrane of metal nanoparticle and metal nanoparticle surface.Detection method is to be inserted into acupuncture needle base working electrode in sample to be tested together with reference electrode, auxiliary electrode, is detected using anodic stripping voltammetry to the concentration of heavy metal ion in sample to be tested.Acupuncture needle base working electrode electrochemical sensor prepared by the present invention, simple process and low cost, high sensitivity, selectivity and stability are good, can be widely used for the detection of trace heavy metal.
Description
Technical field
The present invention relates to electrochemical sensor field, specifically a kind of acupuncture needle base work for detecting trace heavy metal
Electrode electrochemical sensor.
Background technique
With the fast development of modern industrial or agricultural and the raising of living standards of the people, Heavy-Metal-Contaminated Environments problem is increasingly tight
Weight, has seriously affected the healthy and safe of the mankind.Sources of heavy metal in environment is extensive, as metal plating industry, mining,
Curriery, chemical fertilizer industry, paper-making industry, production of pesticide etc. can all generate a large amount of heavy metal in the process.Heavy metal is discharged into
In environment, the variation of the structure and function of the ecosystem can be caused by transmitting on food chain and accumulation.Heavy metal has
Toxicity is big, is not easy to be decomposed, is easily bioaccumulation the features such as simultaneously biomagnification, is entered in human body by food chain, Ke Yi
Accumulation in human body such as can cause anaemia, nervous function imbalance, injury of kidney, or even cause cancer at a variety of diseases, seriously threaten
The life and health safety of the mankind.As understanding of the people to Heavy Metal Pollution is more and more deep, each state all adopts various measures drop
The pollution of low heavy metal, therefore accurate fast and effeciently measurement content of beary metal has become the weight in analysis method research in recent years
Want content.
The detection method of heavy metal mainly has atomic spectroscopy, inductively coupled plasma mass spectrometry, neutron activation at present
Method and electrochemical methods.Every kind of method has its unique advantage, also there is its limiting factor.Spectroscopic methodology is measurement heavy metal
A kind of important method, is widely applied as standard method, but this method determination step is more, and the time is long, higher cost.And
Inductively coupled plasma mass spectrometry and neutron activation method need expensive large-scale instrument, and analysis cost is high, these are all limited
Their application range.And electrochemical methods instrument is simple, is easy to automate and continuously analyze, and is always Analysis of Heavy Metal
Common method.However electrochemical method detection heavy metal is often mercury electrode with the working electrode of electrochemical sensor, and mercury is ring
Border extremely toxic substance, and need specific instrument and equipment storage.With the reinforcement of environmental consciousness and going deep into for research, mercury is very
Multinational family has been prohibited from using.Therefore the electrode material of cheap, environmentally friendly, alternative mercury receives more and more attention.
Summary of the invention
Stainless pin acupuncture needle is the core devices of acupuncture medicine, have many advantages, such as it is cheap, easy to operate, except curing
Outside field, also it is widely applied in fields such as environmental protection, chemical industry.In view of its unique advantage, the present invention is prepared into
The core component of electrochemical sensor --- working electrode, and it is sensitive to the detection of determinand to overcome stainless pin acupuncture needle electrode
It spends low, is not able to satisfy the defect of the demand of actual sample heavy metal analysis.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of acupuncture needle base working electrode electrochemical sensor detecting trace heavy metal, including working electrode, reference electricity
Pole and auxiliary electrode, the working electrode are the acupuncture needle base electrode being made of stainless pin acupuncture needle.
Acupuncture needle base working electrode, reference electrode and the insertion of auxiliary electrode one end have in the electrolytic cell of stirrer, another
End is connected to electrochemical workstation by conducting wire respectively.
The acupuncture needle base working electrode is made of stainless pin acupuncture needle, and there is insulating layer in the shank part of the acupuncture needle,
The needle surface of the acupuncture needle is covered with decorative material, and the needle handle of the acupuncture needle is as electrode cable.
The insulating layer of acupuncture needle shank part is polyvinyl chloride pipe, polyvinyl chloride pipe both ends nozzle and acupuncture needle
The binding site of shank is sealed by silicon rubber.
The decorative material of the acupuncture needle needle surface is that metal nanoparticle and metal nanoparticle surface cover
Cation-exchange membrane.
The metal nanoparticle is one kind of gold, platinum, palladium or bismuth.
For acupuncture pin electrode using needle point Jing Guo carrying out washing treatment as working electrode, platinized platinum is auxiliary electrode, and Ag/AgCl is ginseng
Than electrode, the precursor solution of metal nanoparticle is electrolyte, using constant potential technology, in the needle point deposited metal of acupuncture needle
Nano-particle modified layer.
The cation-exchange membrane is Nafion, and the needle point that surface is covered with the acupuncture pin electrode of metal nanoparticle is soaked
Enter certain time in cation-exchange membrane solution, dried after taking-up, cation is covered on needle point metal nanoparticle decorative layer
Exchange membrane.
The electrochemical sensor can be used for the detection of trace heavy metal copper, cadmium, lead.
The acupuncture needle base working electrode is made of stainless pin acupuncture needle, and there are insulating layer, acupuncture in the shank part of acupuncture needle
The needle surface of needle is covered with decorative material, and the needle handle of acupuncture needle is as electrode cable.Include following preparation step:
(1) preparation of acupuncture pin electrode: with the shank part of insulating materials cladding acupuncture needle, needle point is electrode sensing face,
Needle handle is electrode cable.
(2) pretreatment of acupuncture pin electrode: the needle point of acupuncture pin electrode is successively cleaned with ethyl alcohol, ultrapure water, nitrogen is blown
It is spare after dry.
(3) modification of metallic particles: acupuncture pin electrode using needle point Jing Guo carrying out washing treatment is as working electrode, supplemented by platinized platinum
Electrode is helped, Ag/AgCl is reference electrode, and the precursor solution of metal nanoparticle is electrolyte, using constant potential technology, in needle
The needle point depositing metallic nanoparticles decorative layer of acupuncture needle.
(4) modification of cation-exchange membrane: the needle point that surface is covered with the acupuncture pin electrode of metal nanoparticle is immersed
Certain time in cation-exchange membrane solution dries after taking-up, and cation is covered on needle point metal nanoparticle decorative layer and is handed over
Change film.Obtain the acupuncture needle base working electrode of metal nanoparticle and cation-exchange membrane modification.
The insulating materials of the preparation step (1) is polyvinyl chloride pipe, polyvinyl chloride pipe both ends nozzle and acupuncture needle shank
Binding site be sealed by silicon rubber.
The metal nanoparticle of the preparation step (3) be gold, platinum, palladium, bismuth, electrolyte be respectively gold chloride, chloroplatinic acid,
Chlorine palladium acid sodium and bismuth nitrate, sedimentation potential are-0.2-- 0.5V, and sedimentation time is 90-180s.
The cation-exchange membrane of the preparation step (4) is Nafion, and surface is covered with the acupuncture needle of metal nanoparticle
The time that the needle point of electrode is immersed is 3s.
The trace heavy metal of the acupuncture needle base working electrode electrochemical sensor measurement is the samples such as fresh water, seawater, food
Cu, Cd, Pb in product.
Beneficial effects of the present invention:
The present invention uses stainless pin acupuncture needle for matrix, in conjunction with metal nanoparticle and cation-exchange membrane, is fabricated to needle
Acupuncture needle base working electrode constructs electrochemical sensor, and it is good to make simple, low in cost, high sensitivity, stability, can be in environment
The fields such as monitoring, food safety and clinic are used for the detection of trace heavy metal Cu, Cd, Pb.
The present invention passes through will be after the shank part insulating layer in addition to the needle point of acupuncture needle, needle handle coats sealing, stainless
The needle surface of steel needle acupuncture needle modifies one layer of metal nanoparticle, then the metal nano in needle surface by the method for electrochemistry
One layer of cation-exchange membrane is modified on particle, obtains acupuncture needle base working electrode, constructs electrochemical sensor.Metal nanoparticle
There is extraordinary catalytic effect to the Electrochemical Detection of heavy metal, and cation-exchange membrane Nafion has heavy metal cation
There is very good enrichment performance, by the synergistic effect of the two, substantially increases the sensitivity of heavy metal analysis.Meanwhile by
In the excellent filming performance of Nafion, firmly metal nanoparticle can be fixed on the needle point of acupuncture pin electrode, in conjunction with
It is very firm, substantially increase the stability and reproducibility of acupuncture needle base working electrode electrochemical sensor.
Detailed description of the invention
Fig. 1 is acupuncture needle base working electrode electrochemical sensor schematic diagram provided in an embodiment of the present invention.
Fig. 2 is acupuncture needle base working electrode schematic diagram provided in an embodiment of the present invention
Fig. 3 is acupuncture needle base working electrode provided in an embodiment of the present invention and naked acupuncture pin electrode and is modified with gold nano
Stripping Voltammetry figure of the acupuncture pin electrode of grain to same concentrations Cu.
Fig. 4 is acupuncture needle base working electrode electrochemical sensor provided in an embodiment of the present invention to various concentration heavy metal
Cu2+Stripping Voltammetry figure and corresponding working curve diagram.
Specific embodiment
Summary of the invention of the invention is described further with reference to the accompanying drawings and examples.
Embodiment 1
Acupuncture needle base working electrode electrochemical sensor is constructed using gold as metal nanoparticle:
Sensor as illustrated in fig. 1 and 2: working electrode 1, reference electrode 2 and auxiliary electrode 3 are inserted into the electrolysis for filling detection liquid
In pond 4, be magnetic stirrer 5 in electrolytic cell 4, is configured with magnetic stirring apparatus below electrolytic cell；Working electrode 1,2 and of reference electrode
Auxiliary electrode 3 is connected to electrochemical workstation 6 by conducting wire respectively.
The auxiliary electrode is platinum plate electrode, and reference electrode is Ag/AgCl electrode, and electrochemical workstation measures current-responsive
Value.
Acupuncture needle base working electrode of the gold as metal nanoparticle, needle handle 7 are used as conducting wire, and 9 surface of shank is by gathering
Vinyl chloride pipe 10 insulate, and shank 9 and the binding site of polyvinyl chloride pipe 10 are sealed by silicon rubber 8,13 surface of needle point
It is covered by gold nano grain 11,11 surface of gold nano grain is covered by cation-exchange membrane (Nafion) 12.Its preparation step is such as
Under:
(1) preparation of acupuncture pin electrode: the shank part of acupuncture needle is coated with polyvinyl chloride pipe 10, with silicon rubber 8 to needle
Bar 9 and the binding site of polyvinyl chloride pipe 10 are sealed, and with needle point 13 for electrode sensing face, needle handle 7 is electrode cable.
(2) pretreatment of acupuncture pin electrode: the needle point 13 of acupuncture pin electrode is successively cleaned with ethyl alcohol, ultrapure water, nitrogen
It is spare after drying.
(3) modification of gold nano grain: acupuncture pin electrode using needle point 13 Jing Guo carrying out washing treatment is as working electrode, Ag/
AgCl electrode is reference electrode 2, and platinized platinum is auxiliary electrode 3,1mM chlorauric acid solution (0.5M H2SO4Dilution) it is electrolyte, it uses
Constant potential technology deposits 120s in -0.3V under agitation, obtains the acupuncture needle electricity that needle point 13 is covered with gold nano grain 11
Pole.
(4) needle point that surface is covered with the acupuncture pin electrode of gold nano grain the modification of cation-exchange membrane: is immersed into sun
3s in amberplex (Nafion) solution, dries after taking-up, obtains what gold nano grain 11 and cation-exchange membrane 12 were modified
Acupuncture needle base working electrode.
Embodiment 2
Acupuncture needle base working electrode electrochemical sensor is constructed using platinum as metal nanoparticle:
Difference from Example 1 is that the metal nanoparticle 11 on 13 surface of needle point is Pt nanoparticle.
For acupuncture pin electrode using needle point 13 Jing Guo carrying out washing treatment as working electrode, Ag/AgCl electrode is reference electrode 2,
Platinized platinum is auxiliary electrode 3,2mM platinum acid chloride solution (0.5M H2SO4Dilution) it is electrolyte, using constant potential technology, in -0.25V
100s is deposited under agitation, obtains the acupuncture pin electrode that needle point 13 is covered with Pt nanoparticle 11.
The needle point that surface is covered with the acupuncture pin electrode of Pt nanoparticle is immersed into cation-exchange membrane (Nafion) solution
Middle 3s dries after taking-up, obtains the acupuncture needle base working electrode that Pt nanoparticle 11 and cation-exchange membrane 12 are modified.
Embodiment 3
Acupuncture needle base working electrode electrochemical sensor is constructed using palladium as metal nanoparticle:
Difference from Example 1 is that the metal nanoparticle 11 on 13 surface of needle point is palladium nano-particles.
For acupuncture pin electrode using needle point 13 Jing Guo carrying out washing treatment as working electrode, Ag/AgCl is reference electrode 2, platinized platinum
For auxiliary electrode 3,1mM chlorine palladium acid sodium solution (0.5M H2SO4Dilution) it is that electrolyte is being stirred using constant potential technology in -0.3V
90s is deposited under the conditions of mixing, and obtains the acupuncture pin electrode that needle point 13 is covered with palladium nano-particles 11.
The needle point that surface is covered with the acupuncture pin electrode of palladium nano-particles is immersed into cation-exchange membrane (Nafion) solution
Middle 3s dries after taking-up, obtains the acupuncture needle base working electrode that palladium nano-particles 11 and cation-exchange membrane 12 are modified.
Embodiment 4
Acupuncture needle base working electrode electrochemical sensor is constructed using bismuth as metal nanoparticle:
Difference from Example 1 is that the metal nanoparticle 11 on 13 surface of needle point is bismuth nano particle.
For acupuncture pin electrode using needle point 13 Jing Guo carrying out washing treatment as working electrode, Ag/AgCl is reference electrode 2, platinized platinum
For auxiliary electrode 3,10mM bismuth nitrate solution (dilution of HAc-NaAc buffer solution) is electrolyte, using cyclic voltammetry, in-
0.5V deposits 180s under agitation, obtains the acupuncture pin electrode that needle point 13 is covered with bismuth nano particle 11.
The needle point that surface is covered with the acupuncture pin electrode of bismuth nano particle is immersed into cation-exchange membrane (Nafion) solution
Middle 3s dries after taking-up, obtains the acupuncture needle base working electrode of palladium bismuth rice grain 11 and the modification of cation-exchange membrane 12.
Application examples 1
Cu is detected using acupuncture needle base working electrode electrochemical sensor described in embodiment 1:
Using sensor described in embodiment 1, above-mentioned acupuncture needle base working electrode is successively cleaned with ethyl alcohol, ultrapure water,
Then containing in 0.1M HAc-NaAc (pH4.5) buffer, 0.6V range is arrived in -0.4V by control electrochemical workstation
Interior progress cyclic voltammetric linear scan achievees the purpose that activated electrode, can be used for until cyclic voltammetry curve is overlapped preferably
The detection of Cu.
Using above-mentioned electrochemical sensor, insertion fills the electrolytic cell of HAc-NaAc (10mL, 0.1M, pH4.5) buffer
In, under the conditions of magnetic agitation, it is enriched with 240s in -0.3V, dissolution scanning is carried out within the scope of -0.2V to 0.7V, obtains Cu's
Electrochemical Stripping current signal.
It is molten using square wave to investigate influence of the different modifying material to acupuncture needle base working electrode Electrochemical Detection Cu performance
Voltammetry tests acupuncture needle base working electrode, naked acupuncture pin electrode and is modified with the acupuncture pin electrode of gold nano grain to Cu's out
(referring to Fig. 3, a in figure: b: naked acupuncture pin electrode is modified with the acupuncture pin electrode of gold nano grain, c: needle to electrochemical response signal
Acupuncture needle base working electrode).Constructed acupuncture needle base electrode can be evident that in Jenner by the Stripping Voltammetry test of Fig. 3
In the case that rice grain and cation-exchange membrane carry out functionalized modification, there is optimum efficiency to the Electrochemical Detection of Cu.It is right respectively
The Cu standard solution of various concentration is measured, and the work of Cu response is drawn by the size of the dissolution peak to peak current of various concentration Cu
Make curve (referring to fig. 4).Wherein: the concentration of Cu standard solution is followed successively by 0.05,0.07,0.1,0.3,0.5 from bottom to top,
0.7,1,3,5,7,10nM.From figure four it is found that acupuncture needle base working electrode electrochemical sensor of the invention exists to Cu ion
There is good linear response in 0.05-1nM concentration range, detection sensitivity is high, and detection limit can be applied down to 0.01nM
The measurement of Cu in seawater.
Application examples 2
Cd or Pb is detected using acupuncture needle base working electrode electrochemical sensor described in embodiment 1:
Using sensor described in embodiment 1, above-mentioned acupuncture needle base working electrode is successively cleaned with ethyl alcohol, ultrapure water,
Then containing in 0.1M HAc-NaAc (pH4.5) buffer, 0.6V range is arrived in -0.4V by control electrochemical workstation
Interior progress cyclic voltammetric linear scan achievees the purpose that activated electrode, can be used for until cyclic voltammetry curve is overlapped preferably
The detection of Cd or Pb.
Under the conditions of magnetic agitation with above-mentioned electrode, in Xiang Shengyou 10mL 0.1M HAc-NaAc (pH4.5) buffer solution
5 μ L 10 are added-2Cd the or Pb standard solution of M.It inserts the sensors into measuring cell, measures Cd or Pb with square wave stripping voltammetry
Electrochemical Stripping signal, the dissolution signal phase with naked acupuncture pin electrode, the acupuncture needle determination of electrode for being modified with gold nano grain
Than the current signal that acupuncture needle base working electrode of the invention measures is remarkably reinforced.It is worked using acupuncture needle base of the invention electric
Pole electrochemical sensor also has good response to the detection of heavy metal Cd or Pb.
Claims (3)
1. a kind of acupuncture needle base working electrode electrochemical sensor for detecting trace heavy metal, including working electrode, reference electrode
And auxiliary electrode, it is characterised in that: the working electrode is the acupuncture needle base electrode being made of stainless pin acupuncture needle；Acupuncture needle base
With in the electrolytic cell of stirrer, the other end is connected by conducting wire respectively for working electrode, reference electrode and the insertion of auxiliary electrode one end
It is connected to electrochemical workstation；The acupuncture needle base working electrode is made of stainless pin acupuncture needle, the shank part of the acupuncture needle
There is insulating layer, the needle surface of the acupuncture needle is covered with decorative material, and the needle handle of the acupuncture needle is as electrode cable；It is described
The insulating layer of acupuncture needle shank part is polyvinyl chloride pipe, the engaging portion of polyvinyl chloride pipe both ends nozzle and acupuncture needle shank
Position is sealed by silicon rubber；The decorative material of the acupuncture needle needle surface is metal nanoparticle and metal nanoparticle
The cation-exchange membrane of surface covering；
The acupuncture needle base working electrode preparation step are as follows:
(1) preparation of acupuncture pin electrode: with the shank part of insulating materials cladding acupuncture needle, needle point is electrode sensing face, needle handle
For electrode cable；
(2) pretreatment of acupuncture pin electrode: the needle point of acupuncture pin electrode is successively cleaned with ethyl alcohol, ultrapure water, after being dried with nitrogen
It is spare；
(3) modification of metallic particles: for the acupuncture pin electrode using needle point Jing Guo carrying out washing treatment as working electrode, platinized platinum is auxiliary electricity
Pole, Ag/AgCl are reference electrode, and the precursor solution of metal nanoparticle is electrolyte, using constant potential technology, in acupuncture needle
Needle point depositing metallic nanoparticles decorative layer；
(4) modification of cation-exchange membrane: by surface be covered with the acupuncture pin electrode of metal nanoparticle needle point immerse sun from
Certain time in proton exchange solution dries after taking-up, covers cation-exchange membrane on needle point metal nanoparticle decorative layer；
Obtain the acupuncture needle base working electrode of metal nanoparticle and cation-exchange membrane modification；The insulation material of the preparation step (1)
Material is polyvinyl chloride pipe, and polyvinyl chloride pipe both ends nozzle and the binding site of acupuncture needle shank are sealed by silicon rubber；It is described
The metal nanoparticle of preparation step (3) is gold, platinum, palladium, bismuth, and electrolyte is respectively gold chloride, chloroplatinic acid, chlorine palladium acid sodium and nitre
Sour bismuth, sedimentation potential are-0.2-- 0.5V, and sedimentation time is 90-180s.
2. a kind of acupuncture needle base working electrode electrochemical sensor for detecting trace heavy metal according to claim 1, special
Sign is: the cation-exchange membrane is Nafion, and the needle point that surface is covered with the acupuncture pin electrode of metal nanoparticle is soaked
Enter certain time in cation-exchange membrane solution, dried after taking-up, cation is covered on needle point metal nanoparticle decorative layer
Exchange membrane.
3. a kind of acupuncture needle base working electrode electrochemical sensor for detecting trace heavy metal according to claim 1, special
Sign is: the electrochemical sensor can be used for the detection of trace heavy metal copper, cadmium, lead.
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| CN108680635A (en) * | 2018-05-22 | 2018-10-19 | 中国科学院烟台海岸带研究所 | One kind can be used for Cu2+Functionalized modification acupuncture pin electrode of detection and preparation method thereof |
| RU2717705C1 (en) * | 2019-05-16 | 2020-03-25 | Артем Олегович Бахметьев | Method of sorption and removal of heavy metal particles from human body using reflexotherapy and acupuncture needle for method implementation |
| CN111257396A (en) * | 2020-01-16 | 2020-06-09 | 浙江大学 | Miniature electrochemical system based on near field communication technology and detection method |
| CN114235924B (en) * | 2021-12-16 | 2023-10-17 | 杭州电子科技大学 | Enzyme-free blood glucose sensor microelectrode of Pt/Au nano-alloy modified acupuncture needle with cabbage structure and preparation method thereof |
| CN115236153A (en) * | 2022-07-26 | 2022-10-25 | 中山大学 | For measuring Cl - Ratio type functional acupuncture needle electrode and preparation method thereof |
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| CN101706471B (en) * | 2008-12-12 | 2012-10-03 | 中国科学院烟台海岸带研究所 | Electrochemical sensor for determining concentration of heavy metal ions in water sample |
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| CN103278551A (en) * | 2013-04-26 | 2013-09-04 | 浙江大学 | Active carbon double-electrode system-based heavy metal electrochemical sensor and method for detection of heavy metals by the active carbon double-electrode system-based heavy metal electrochemical sensor |
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