CN104655699B - Renewable metal nanoparticle electrochemical sensor and preparation method thereof - Google Patents
Renewable metal nanoparticle electrochemical sensor and preparation method thereof Download PDFInfo
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- CN104655699B CN104655699B CN201510081228.2A CN201510081228A CN104655699B CN 104655699 B CN104655699 B CN 104655699B CN 201510081228 A CN201510081228 A CN 201510081228A CN 104655699 B CN104655699 B CN 104655699B
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Abstract
The invention discloses a renewable metal nanoparticle electrochemical sensor and a preparation method thereof. The sensor mainly comprises a bare glassy carbon electrode, a layer of sulfonated poly(aryle ether ketone) polymer cation exchange thin-layer template precursor and carrier film, and a layer of nickel nanoparticle high electric catalytic activity film. By utilizing the strong matching function and ion exchange effect of a sulfonic acid group on the sulfonated poly(aryle ether ketone) (SPAEK) thin-layer precursor film and transition metal ions, taking a nickel sulfate solution as a deposition solution, and using an in situ electrochemical reduction method, nickel nanoparticles are loaded on a SPAEK thin film modified electrode. Glucose has a significantly enhanced electric catalytic oxidation effect, and the production repeatability of the sensor is high. When the sensor is applied to glucose electrochemical analysis, the sensor has high response sensitivity, and good determination stability and reproducibility, and can be used for accurately and quickly analyzing the content of low concentration glucose.
Description
Technical field
It is one kind with sulfonated poly aryl ether ketone cation exchange specifically the invention belongs to Electroanalytical Chemistry technical field
Film (SPAEK) is the preparation of the renewable nano metal particles modified electrode electrochemical sensor of precursor and carrier film and its answers
For sensitive, the stable and accurate electrochemical gaging of concentration of glucose.
Background technology
The key that sensitivity for analysis, reappearance and accuracy are determined in electrochemical analysis is working electrode, i.e., electrochemistry is passed
Sensor, it is electrochemical analysis system " heart ".Conventional glass carbon, gold and the solid electrode such as platinum after analysis test, because of electricity
Chemical reaction product absorption causes the pollution and passivation of electrode surface in electrode surface, or because of Long-Time Service rear electrode surface sheet
The physical and chemical changes that body occurs, even if the troublesome operation step such as Jing artificial mechanisms polishing after determining every time, also cannot obtain
Completely, the electrode surface for effectively updating, reappearance, stability and the degree of accuracy for causing testing result is substantially reduced, so as to
Do not possess practical value.
Developing rapidly recently as nanometer technology, especially nano metal particles have preferably nano-particle due to it
Promotion electron transport ability, higher electro catalytic activity the advantages of larger effective surface area, is typically used to repairing for electrode
Decorations.But the nano metal electrochemical sensor prepared by traditional method of modifying and technology, because of preparation process complexity or condition not
The reason such as controllable and cannot repeat, or because nano-particle thus results in sensor and exists in electrode surface original of easily reuniting or come off etc.
Reappearance and stability is not still high during practical application, and accuracy as a result is still very poor.Therefore, develop novel, functional
The nano metal particles modified electrode electrochemical sensor of (sensitivity is further lifted, and reappearance and stability are more preferable) is current
Electrochemical sensor one highly important research contents of aspect.
The content of the invention
A kind of present invention exactly pin improvements over the prior art, there is provided new recyclability nano metal particles electrochemistry
The preparation method of sensor, with sulfonated poly aryl ether ketone cation-exchange membrane as precursor and support template, nano metal particles are in electricity
Pole surface is not reunited, and repeats regeneration, and electro catalytic activity is high.The sensor of preparation is used for the electrochemistry of glucose content and examines
Survey, sensitivity is high, very well, these performances dramatically ensure that the accuracy of result, so as to advance for stability and reappearance
Application prospect of the electrochemical sensor in the real works such as clinical examination, at the same provide a low cost, it is quick and easy,
The preparation method of the high electrochemical sensor of the controllable and repeatable degree of condition.Sulfonated poly aryl ether ketone used in the present invention is organic
High molecular polymer is a kind of new amberplex, and so far also never someone is used for the preparation of electrochemical sensor
In, with it as precursor and carrier film is also to invent first the preparation method for preparing nano metal particles electrochemical sensor.
The concrete technical scheme of the present invention is as follows：
The invention discloses a kind of renewable metal nanoparticle electrochemical sensor, sensor main will be by a naked glass
Carbon electrode, one layer of sulfonated poly aryl ether ketone macromolecule cation exchange thin layer template precursor and carrier film, and one layer of nanometer nickel particles are high
Electro catalytic activity film is constituted.
The invention also discloses a kind of preparation method of renewable metal nanoparticle electrochemical sensor, using sulfonation
Sulfonic acid group on PAEK (SPAEK) thin layer precursor film has stronger mating reaction and ion with transition metal ions nickel
Exchange interaction, with nickel sulfate solution as deposition solution, using electrochemical in-situ reducing process in the film modified electricity of sulfonated poly aryl ether ketone
Extremely upper load nanometer nickel particles.
Used as further improving, preparation method of the present invention dissolves scattered sulfonated poly aryl ether ketone by solvent DMF
Solution, using micro syringe and simple ultrasound drop-coating, in glassy carbon electrode surface one layer of very thin sulfonated poly aryl ether ketone is modified
Macromolecule cation exchanges thin layer template precursor and carrier film.
As further improving, the Ni in nickel sulfate solution of the present invention2+, can be handed over by coordination and cation
Effect preenrichment is changed in sulfonated poly aryl ether ketone high molecular polymer thin layer template, then can be through electrochemical in-situ reducing process
Electrode surface is evenly distributed, the high electrocatalytic active nanometer nickel particles high electrocatalytic active film reunited does not occur.
Used as further improving, nanometer nickel particles high electrocatalytic active film of the present invention is by sulfuric acid solution
After middle immersion wash-out, the Jing preenrichments Ni in nickel sulfate solution again2+Step and electrochemical in-situ reduction step, renewable nanometer
Nickel particles high electrocatalytic active film, sulfonated poly aryl ether ketone macromolecule cation exchanges thin layer template precursor and carrier film can be multiple
Recycle, so that sensor preparation process is simple, condition is controllable, make repeatability and stability is greatly improved.
The invention also discloses a kind of renewable metal nanoparticle electrochemical sensor is applied to the electrification of glucose
Detection is learned, selects under optimal response current potential, response measure to be carried out to crossing glucose with current versus time curve method, very wide
In concentration range, described sensor has the current-responsive of stable, reproduction and rapid sensitive, described sensor system to glucose
The repeatable degree height of standby process ensure that the long-time stability of glucose electrochemical measurement.
Advantage for present invention and effect：
1. the present invention be with cation exchange high molecular polymer sulfonated poly aryl ether ketone as metal ion enrichment precursor film and
The metal nanoparticle modified electrode electrochemical sensor of metal nanoparticle carrier film, using ultrasonic drop-coating, in glass carbon electricity
The cation exchange polymer precursor of pole surface modification and support template, with good film-forming property, thickness of thin, the template is anti-in electrode
Should in electric transmission resistance it is little, stability and homogeneity many with the avtive spot of metallic nickel ions coordination and ion exchange
The features such as good.
2. the method that the nanometer nickel particles decorative layer that prepared by the present invention is adopted is Jing metal ion preconcentrations to electrode
Electrochemical in-situ reduction sedimentation behind surface, the method is simple to operate, and condition is fully controllable, repeats degree height, obtained
Electroactive nickel particles are in nanostructured, are evenly distributed in electrode surface, are not reunited, and are firmly combined with electrode surface.
3. the macromolecule cation in the present invention exchanges thin layer precursor template and repeats before the regeneration as nanometer nickel particles
Body film and carrier film, and regenerative process is repeatable high.
4. the advantage each above and effect that the present invention has causes prepared nanometer nickel particles modified electrode electrochemistry
Sensor has the electrocatalytic oxidation effect that significantly increases to glucose, and sensor production is repeatable high, when being applied to Portugal
Response sensitivity is high during grape sugar electrochemical analysis, determines stability and favorable reproducibility, can be used for the standard of low concentration glucose content
Really quick analysis.
Description of the drawings
Fig. 1 is sulfonated poly aryl ether ketone (SPAEK) molecular structural formula figure；
Fig. 2 is the making of sensor nano nickel particles/sulfonated poly aryl ether ketone/glass-carbon electrode (NiNPs/SPAEK/GCE)
Journey mechanism figure；
Fig. 3 sweeps for sensor nano nickel particles/sulfonated poly aryl ether ketone/glass-carbon electrode (NiNPs/SPAEK/GCE) surface
Retouch electron microscope；
Fig. 4 is sensor nano nickel particles/sulfonated poly aryl ether ketone/glass-carbon electrode (NiNPs/SPAEK/GCE) in 0.1M
Current-vs-time (i-t) response curve of different glucose is continuously added in NaOH solution；Operating potential：0.55V.
Specific embodiment
The invention discloses a kind of new renewable nano metal particles electrochemical sensor, mainly by a naked glass
Carbon electrode, one layer of sulfonated poly aryl ether ketone macromolecule cation exchange precursor and carrier thin film, the high electro-catalysis of one layer of nanometer nickel particles
Active film is constituted.
(1), scattered SPAEK solution is dissolved by DMF, using micro syringe and simple ultrasound drop-coating, in glass carbon electricity
The very thin SPAEK macromolecule cations of one layer of pole surface modification exchange precursor and support template.
(2), the Ni in nickel sulfate solution2+, preenrichment can be acted on to SPAEK macromolecules by coordination and cation exchange
In polymer foil template, can be evenly distributed in electrode surface through simple electrochemical in-situ reducing process, stable height
Electro catalytic activity nanometer nickel particles.
(3), nanometer nickel particles decorative layer can completely effectively update glass carbon electricity after the immersion wash-out in sulfuric acid solution
The SPAEK macromolecule cations on pole surface exchange precursor and support template, then Jing steps (2) again, and regeneration nanometer nickel particles are lived
Sex modification layer.So circulation, SPAEK macromolecule cations exchange thin layer template precursor and carrier film can Reusability.
(4), the invention also discloses a kind of new recyclability nanometer nickel particles electrochemical sensor is applied to
The electrochemical determination method of glucose.
Technical scheme is made more specifically with reference to Figure of description and by specific embodiment
It is bright：
Bare glassy carbon electrode (GCE) is polished successively with the alumina powder of 0.3 μm and 0.5 μm on deerskin, mirror is polished to
Face.It is cleaned by ultrasonic 5min with absolute ethyl alcohol, distilled water.Dry, in 0.1mol/L H2SO4In sweep stably obtain final product cleaning naked electricity
Pole.
(1) preparation of sulfonated poly aryl ether ketone preenrichment precursor and carrier film modified electrode takes 0.01g sulfonated poly aryl ether ketones, molten
In 4mLDMF, ultrasonic 30min, thing to be polymerized dissolves to form sulfonated poly aryl ether ketone solution.The solution for taking 3 μ L is dripped in dry
In bare glassy carbon electrode, after ultrasonic vibration, dry naturally, dry again after being cleaned with redistilled water, in 1mol/L H2SO4Middle immersion
After obtain final product the preenrichment of sulfonated poly aryl ether ketone precursor and carrier film modified electrode (SPAEK/GCE).
(2) preparation of nano nickel modified electrode electrochemical sensor is with obtained SPAEK/GCE as working electrode, and platinum filament is electric
Extremely auxiliary electrode, saturated calomel electrode is reference electrode, containing 100mmol/LNiSO4Preenrichment Ni in solution2+After 3 hours,
0.1mol/LNa is placed in again2SO4In solution, fast cyclic voltammetry scan 4 is swept with 0.02V/s in -1.4～-0.6V potential regions
Circle, takes out and dries after being cleaned with redistilled water, then sweeps in 0.1mol/LNaOH stable, obtain final product a nanometer nickel particles/
Sulfonated poly aryl ether ketone modified glassy carbon electrode (NiNPs/SPAEK/GCE).
(3) by the NiNPs/SPAEK/GCE after use in 1mol/L H2SO4In middle immersion a few hours, realize the poly- virtue of sulfonation
The renewal of ether ketone preenrichment precursor and carrier film.Repeat step (2) regenerates nanometer nickel particles, and regeneration prepares the modification of nanometer nickel particles
Electrode electrochemical sensor.
Fig. 1 is sulfonated poly aryl ether ketone (SPAEK) molecular structural formula figure；It has preferable chemical stability, good machine
Tool intensity, higher electrical conductivity, in being commonly used for the electrochemical process such as fuel cell.The microcellular structure that the film has can increase
The contact site of electrode surface, the sulfonic acid group connected on side chain can be with metallic nickel ions by coordination and electrostatic interaction
Firmly combine very much, so as to receive so as to be lifted as the preenrichment precursor film and carrier film that build nano nickel electrochemical sensor
The performance of rice metallic sensor.
Fig. 2 is the making of sensor nano nickel particles/sulfonated poly aryl ether ketone/glass-carbon electrode (NiNPs/SPAEK/GCE)
Journey mechanism figure；Sulfonic acid group and metal ion of the ultrasonic drop coating in the sulfonated poly aryl ether ketone precursor film of glassy carbon electrode surface
Ni2+With stronger mating reaction and ion exchange, the preenrichment Ni in nickel sulfate solution2+(step1)；In Na2SO4It is molten
Jing electrochemical in-situs reduction deposition process (step2) in liquid, load nanometer nickel particles on sulfonated poly aryl ether ketone film；Jing acidleach
Bubble dissolving nanometer nickel particles, the SPAEK precursors for being updated completely and carrier film (step3).It is sonicated using drop-coating
After being dispersed in the sulfonated poly aryl ether ketone solution film forming of glassy carbon electrode surface afterwards, electrode surface is stably and firmly attached to, and
With microcellular structure, this increases the specific surface area of film and and Ni significantly2+Effective binding site.Step1 represents film surface
Many sulfonic acid groups are connected to, Jing after acid soak process upper proton H is combined+, when with NiSO4When solution is contacted, the H on film+With
Ni2+Generation ion exchange, so as to reach in glassy carbon electrode surface preenrichment Ni2+Purpose；Step2 represents that preenrichment exists
The Ni of electrode surface2+Electrochemical in-situ is reduced to the process of nanometer nickel particles；Step3 represents that acid soak elutes nanometer nickel particles reality
The process for now regenerating.The electroactive nanometer nickel particles Jing electrochemical oxidations in the basic conditions of sensor surface prepared by the present invention
Afterwards in the form of NiOOH, when sensor surface is contacted with glucose solution, glucose is produced by NiOOH catalysis oxidations
Catalysis oxidation electric current is linearly related to concentration of glucose based on the electric current, it is possible to achieve the measure of glucose content.
Fig. 3 is the pattern of the sensor surface seen by SEM (SEM).Nanometer nickel particles are extremely uniform
Be dispersed in electrode surface, particle diameter about 60nm.
Fig. 4 is the linear relationship chart of current method response current and glucose in solutions concentration, linear equation be i (μ A)=
41.2898C (mM)+1.7394, the range of linearity is 1 μm of ol/L～4mmol/L, and coefficient correlation is up to 0.9998.Counted according to S/N=3
Calculation obtains the detection of this method and is limited to 200nmol/L, and this method is wider than the range of linearity of many document reports, and test limit is low.It is right
20 μM of glucose METHOD FOR CONTINUOUS DETERMINATIONs 10 times, current-responsive relative standard deviation (RSD) is only 0.23%.Modified electrode is placed in pH7.0
Glucose is redeterminated after preserving 1 month in 4 DEG C of refrigerators in phosphate buffer, current-responsive only declines 3%.Repeat to prepare and pass
Sensor 6 times, is only 1.5% to the current-responsive relative standard deviation (RSD) of 20 μM of glucose.
NiNPs/SPAEK/GCE is in 0.1M NaOH media to glucose, dopamine (DA), ascorbic acid (AA), NaCl
Carry out i-t method measure.Determine under current potential in 0.55V, relative to 20 μM of glucose solution, 1 μM of DA of low concentration, 1 μM of AA and
100 μM of NaCl (the suitable concentration in actual biological sample) of high concentration, do not produce interference, and this proves NiNPs-SPAEK/
The antijamming capability of GCE is very strong, is fully available for the measure of actual biological sample.
Listed above is only some embodiments of the present invention, it is clear that the invention is not restricted to above example, may be used also
To have many deformations, all changes that one of ordinary skill in the art can directly derive from present disclosure or associate
Shape, is considered as protection scope of the present invention.
Claims (6)
1. a kind of renewable metal nanoparticle electrochemical sensor, it is characterised in that described sensor main will be by
Bare glassy carbon electrode, one layer of sulfonated poly aryl ether ketone macromolecule cation exchange thin layer template precursor and carrier film, one layer of nanometer nickel shot
Sub- high electrocatalytic active film composition.
2. a kind of preparation method of renewable metal nanoparticle electrochemical sensor as claimed in claim 1, its feature
It is have using the sulfonic acid group on sulfonated poly aryl ether ketone (SPAEK) thin layer precursor film and transition metal ions nickel stronger
Mating reaction and ion exchange, with nickel sulfate solution as deposition solution, using electrochemical in-situ reducing process in the poly- virtue of sulfonation
Nanometer nickel particles are loaded on ether ketone film modified electrod.
3. the preparation method of renewable metal nanoparticle electrochemical sensor according to claim 2, its feature exists
In scattered sulfonated poly aryl ether ketone solution being dissolved by solvent DMF, using micro syringe and simple ultrasound drop-coating, in glass carbon
The very thin sulfonated poly aryl ether ketone macromolecule cation of one layer of electrode face finish exchanges thin layer template precursor and carrier film.
4. the preparation method of the renewable metal nanoparticle electrochemical sensor according to Claims 2 or 3, its feature
It is, the Ni in described nickel sulfate solution2+, preenrichment can be acted on to sulfonated poly aryl ether ketone by coordination and cation exchange
In high molecular polymer thin layer template, then can be evenly distributed in electrode surface, not sent out through electrochemical in-situ reducing process
The raw high electrocatalytic active nanometer nickel particles high electrocatalytic active film reunited.
5. the preparation method of renewable metal nanoparticle electrochemical sensor according to claim 4, its feature exists
In described nanometer nickel particles high electrocatalytic active film is again molten in nickel sulfate after the immersion wash-out in sulfuric acid solution
Jing preenrichments Ni in liquid2+Step and electrochemical in-situ reduction step, renewable nanometer nickel particles high electrocatalytic active film is described
Sulfonated poly aryl ether ketone macromolecule cation exchange thin layer template precursor and carrier film and can be recycled for multiple times.
6. a kind of renewable metal nanoparticle electrochemical sensor as claimed in claim 1 is applied to the electrification of glucose
Learn detection, it is characterised in that select under optimal response current potential, response survey to be carried out to crossing glucose with current versus time curve method
Fixed, in very wide concentration range, described sensor has the current-responsive of stable, reproduction and rapid sensitive, institute to glucose
The repeatable degree height of the sensor preparation process stated ensure that the long-time stability of glucose electrochemical measurement.
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| CN102881925A (en) * | 2012-09-28 | 2013-01-16 | 孙公权 | Novel ordering membrane electrode and preparation method and application thereof |
| CN103983680A (en) * | 2014-04-29 | 2014-08-13 | 浙江大学 | Novel hydrogen peroxide electrochemical sensor |
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| CN102881925A (en) * | 2012-09-28 | 2013-01-16 | 孙公权 | Novel ordering membrane electrode and preparation method and application thereof |
| CN103983680A (en) * | 2014-04-29 | 2014-08-13 | 浙江大学 | Novel hydrogen peroxide electrochemical sensor |
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