CN104655699A - 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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- CN104655699A CN104655699A CN201510081228.2A CN201510081228A CN104655699A CN 104655699 A CN104655699 A CN 104655699A CN 201510081228 A CN201510081228 A CN 201510081228A CN 104655699 A CN104655699 A CN 104655699A
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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
The invention belongs to Electroanalytical Chemistry technical field, specifically, be a kind of with the preparation of sulfonated poly aryl ether ketone cation-exchange membrane (SPAEK) the renewable nano metal particles modified electrode electrochemical sensor that is precursor and carrier film and sensitive, the stable and accurate electrochemical gaging being applied to concentration of glucose thereof.
Background technology
Determine sensitivity for analysis in electrochemical analysis, the key of reappearance and accuracy is working electrode, i.e. electrochemical sensor, and it is electrochemical analysis system " heart ".Conventional glass carbon, the solid electrodes such as gold and platinum are after analytical test, pollution and the passivation of electrode surface is caused because electrochemical reaction product is adsorbed on electrode surface, or because of the physical and chemical changes occurred in Long-Time Service rear electrode surface own, through troublesome operation steps such as artificial mechanism polishings after measuring even if each, also cannot obtain the electrode surface completely, effectively upgraded, cause the reappearance of testing result, stability and degree of accuracy greatly to reduce, thus do not possess practical value.
Developing rapidly in recent years along with nanometer technology, nano particle especially nano metal particles promotes electron transport ability preferably because it has, higher electro catalytic activity, and the advantages such as larger effective surface area are usually used to the modification of electrode.But the nano metal electrochemical sensor prepared by traditional method of modifying and technology, cannot repeat because of reasons such as preparation process are complicated or condition is uncontrollable, because of nano particle electrode surface very easily reunite or to come off etc. reason and cause sensor in practical application time reappearance and stability still not high, the accuracy of result is still very poor.Therefore, exploitation novel, functional (sensitivity promotes further, reappearance and stability better) nano metal particles modified electrode electrochemical sensor be the very important research contents in one, current electrochemical sensor aspect.
Summary of the invention
The present invention is pin improvements over the prior art just, a kind of preparation method of novel recyclability nano metal particles electrochemical sensor is provided, with sulfonated poly aryl ether ketone cation-exchange membrane for precursor and support template, nano metal particles is not reunited at electrode surface, can repeat regeneration, electro catalytic activity is high.The sensor of preparation is used for the Electrochemical Detection of glucose content, highly sensitive, stability and reappearance fine, these performances ensure that the accuracy of result dramatically, thus advance the application prospect of electrochemical sensor in the real works such as clinical examination, provide simultaneously a low cost, fast simple, condition is controlled and can repeat the preparation method of the high electrochemical sensor of degree.Sulfonated poly aryl ether ketone organic high molecular polymer used by the present invention is a kind of novel amberplex, also never have people up to now in the preparation of electrochemical sensor, with the preparation method preparing nano metal particles electrochemical sensor for precursor and carrier film invent first.
Concrete technical scheme of the present invention is as follows:
The invention discloses a kind of renewable metal nanoparticle electrochemical sensor, sensor exchanges thin layer template precursor and carrier film primarily of a naked glass-carbon electrode, one deck sulfonated poly aryl ether ketone macromolecule cation, and one deck nano nickel particle high electrocatalytic active film forms.
The invention also discloses a kind of preparation method of renewable metal nanoparticle electrochemical sensor, the sulfonic acid group on sulfonated poly aryl ether ketone (SPAEK) thin layer precursor film and transition metal ion nickel is utilized to have stronger mating reaction and ion exchange, take nickel sulfate solution as deposit solution, adopt electrochemical in-situ reducing process loaded with nano nickel particles on sulfonated poly aryl ether ketone film modified electrod.
As improving further, preparation method of the present invention dissolves the sulfonated poly aryl ether ketone solution of dispersion by solvent DMF, adopt micro syringe and simple ultrasonic drop-coating, modify the very thin sulfonated poly aryl ether ketone macromolecule cation of one deck in glassy carbon electrode surface and exchange thin layer template precursor and carrier film.
As improving further, the Ni in nickel sulfate solution of the present invention
2+can by coordination and cation exchange effect preenrichment in sulfonated poly aryl ether ketone high molecular polymer thin layer template, then can obtain at electrode surface through electrochemical in-situ reducing process and be evenly distributed, the high electrocatalytic active nano nickel particle high electrocatalytic active film of reuniting does not occur.
As improving further, nano nickel particle high electrocatalytic active film of the present invention by after soak wash-out in sulfuric acid solution, again in nickel sulfate solution through preenrichment Ni
2+step and electrochemical in-situ reduction step, renewable nano nickel particle high electrocatalytic active film, sulfonated poly aryl ether ketone macromolecule cation exchanges thin layer template precursor and carrier film can repeatedly recycle, thus make sensor preparation process simple, condition is controlled, and making repeatability and stability improve greatly.
The invention also discloses the Electrochemical Detection that a kind of renewable metal nanoparticle electrochemical sensor is applied to glucose, select under optimal response current potential, response mensuration is carried out to crossing glucose by current versus time curve method, in very wide concentration range, described sensor to glucose have stable, reappear and the current-responsive of rapid sensitive, the high long-time stability that ensure that glucose electrochemical measurement of repeated degree of described sensor preparation process.
The advantage that the present invention has and effect:
1. the metal nanoparticle modified electrode electrochemical sensor that the present invention is is metallic ion enrichment precursor film and metal nanoparticle carrier film with cation exchange high molecular polymer sulfonated poly aryl ether ketone, adopt ultrasonic drop-coating, in cation exchange polymer precursor and the support template of glassy carbon electrode surface modification, there is good film-forming property, thickness is thin, this template electric transmission resistance in electrode reaction is little, many with the avtive spot of metallic nickel ions coordination and ion exchange, stability and the feature such as homogeneity is good.
2. the method that the nano nickel particle decorative layer that prepared by the present invention adopts is the electrochemical in-situ reduction sedimentation after metallic ion preconcentration to electrode surface, the method is simple to operate, condition is completely controlled, degree can be repeated high, obtained electroactive nickel particles is nanostructured, be evenly distributed at electrode surface, do not reunite, and be combined firmly with electrode surface.
3. the macromolecule cation in the present invention exchanges regeneration precursor film and the carrier film that thin layer precursor template can be reused as nano nickel particle, and regenerative process repeatability is high.
4. above each advantage of having of the present invention and effect cause prepared nano nickel particle modified electrode electrochemical sensor glucose to be had to the catalytic oxidation effect significantly strengthened, sensor production repeatability is high, when being applied to glucose electrochemical analysis, response sensitivity is high, measure stability and favorable reproducibility, can be used for the accurate express-analysis of low concentration glucose content.
Accompanying drawing explanation
Fig. 1 is sulfonated poly aryl ether ketone (SPAEK) molecular structural formula figure;
Fig. 2 is the manufacturing process mechanism figure of sensor nano nickel particles/sulfonated poly aryl ether ketone/glass-carbon electrode (NiNPs/SPAEK/GCE);
Fig. 3 is the scanning electron microscope (SEM) photograph on sensor nano nickel particles/sulfonated poly aryl ether ketone/glass-carbon electrode (NiNPs/SPAEK/GCE) surface;
Fig. 4 is current-vs-time (i-t) response curve that sensor nano nickel particles/sulfonated poly aryl ether ketone/glass-carbon electrode (NiNPs/SPAEK/GCE) adds different glucose continuously in 0.1MNaOH solution; Operating potential: 0.55V.
Embodiment
The invention discloses a kind of novel renewable nano metal particles electrochemical sensor, exchange precursor and carrier thin film primarily of a naked glass-carbon electrode, one deck sulfonated poly aryl ether ketone macromolecule cation, one deck nano nickel particle high electrocatalytic active film forms.
(1), dissolved the SPAEK solution disperseed by DMF, adopt micro syringe and simple ultrasonic drop-coating, modify the very thin SPAEK macromolecule cation of one deck in glassy carbon electrode surface and exchange precursor and support template.
(2) Ni, in nickel sulfate solution
2+, can by coordination and cation exchange effect preenrichment in SPAEK high molecular polymer thin layer template, can obtain at electrode surface through simple electrochemical in-situ reducing process be evenly distributed, stable high electrocatalytic active nano nickel particle.
(3) after, nano nickel particle decorative layer passes through to soak wash-out in sulfuric acid solution, the SPAEK macromolecule cation that can upgrade glassy carbon electrode surface completely effectively exchanges precursor and support template, and then through step (2), regeneration nano nickel particle activity modifying layer.Circulation like this, SPAEK macromolecule cation exchanges thin layer template precursor and carrier film can Reusability.
(4), the invention also discloses the electrochemical determination method that a kind of novel recyclability nano nickel particle electrochemical sensor is applied to glucose.
Technical scheme of the present invention to be described in further detail by specific embodiment below in conjunction with Figure of description:
Naked glass-carbon electrode (GCE) is polished with the alumina powder of 0.3 μm and 0.5 μm successively on deerskin, is polished to minute surface.With absolute ethyl alcohol, distilled water ultrasonic cleaning 5min.Dry, at 0.1mol/L H
2sO
4in sweep and stablize and obtain clean bare electrode.
(1) 0.01g sulfonated poly aryl ether ketone is got in the preparation of sulfonated poly aryl ether ketone preenrichment precursor and carrier film modified electrode, is dissolved in 4mLDMF, ultrasonic 30min, and thing to be polymerized dissolves and forms sulfonated poly aryl ether ketone solution.This solution getting 3 μ L drips on the naked glass-carbon electrode of drying, after ultrasonic vibration, naturally dries, and dries, at 1mol/L H after cleaning with redistilled water again
2sO
4namely the preenrichment of sulfonated poly aryl ether ketone precursor and carrier film modified electrode (SPAEK/GCE) is obtained after middle immersion.
(2) preparation of nano nickel modified electrode electrochemical sensor is with obtained SPAEK/GCE for working electrode, and platinum electrode is auxiliary electrode, and saturated calomel electrode is contrast electrode, is containing 100mmol/LNiSO
4preenrichment Ni in solution
2+after 3 hours, then be placed in 0.1mol/LNa
2sO
4in solution, fast cyclic voltammetry scan 4 of sweeping with 0.02V/s in-1.4 ~-0.6V potential region encloses, taking-up is also dried after cleaning with redistilled water, and then sweep stable in 0.1mol/LNaOH, obtain nano nickel particle/sulfonated poly aryl ether ketone modified glassy carbon electrode (NiNPs/SPAEK/GCE).
(3) by use after NiNPs/SPAEK/GCE in 1mol/L H
2sO
4in in soak a few hours, realize the renewal of sulfonated poly aryl ether ketone preenrichment precursor and carrier film.Repeat step (2) regeneration nano nickel particle, nano nickel particle modified electrode electrochemical sensor is prepared in regeneration.
Fig. 1 is sulfonated poly aryl ether ketone (SPAEK) molecular structural formula figure; It has good chemical stability, good physical strength, and higher conductivity is often used in the electrochemical process such as fuel cell.The microcellular structure that this film has can increase the contact site of electrode surface, the sulfonic acid group that side chain connects very firmly can be combined by coordination and electrostatic interaction with metallic nickel ions, thus can be used as the preenrichment precursor film and carrier film thus the performance of lifting nano metal particles sensor that build nano nickel electrochemical sensor.
Fig. 2 is the manufacturing process mechanism figure of sensor nano nickel particles/sulfonated poly aryl ether ketone/glass-carbon electrode (NiNPs/SPAEK/GCE); Ultrasonic is applied to sulfonic acid group in the sulfonated poly aryl ether ketone precursor film of glassy carbon electrode surface and metallic ion Ni
2+there is stronger mating reaction and ion exchange, preenrichment Ni in nickel sulfate solution
2+(step1); At Na
2sO
4through electrochemical in-situ reduction deposition process (step2) in solution, loaded with nano nickel particles on sulfonated poly aryl ether ketone film; Dissolve nano nickel particle through acid soak, obtain the SPAEK precursor and carrier film (step3) that upgrade completely.After adopting drop-coating to be dispersed in the sulfonated poly aryl ether ketone solution film forming of glassy carbon electrode surface after ultrasonic process, stablize and be firmly bonded to electrode surface, and have microcellular structure, this increases specific surface area and and the Ni of film greatly
2+effective binding site.Step1 represents that film surface is connected to many sulfonic acid groups, combines upper proton H after acid soak process
+, when with NiSO
4during solution contact, the H on film
+with Ni
2+there is ion exchange, thus reach at glassy carbon electrode surface preenrichment Ni
2+object; Step2 represents the Ni of preenrichment at electrode surface
2+electrochemical in-situ is reduced to the process of nano nickel particle; Step3 represents that acid soak wash-out nano nickel particle realizes the process of regeneration.The electroactive nano nickel particle of sensor surface prepared by the present invention exists with the form of NiOOH in the basic conditions after electrochemical oxidation, when sensor surface contacts with glucose solution, glucose is by NiOOH catalytic oxidation, produce catalytic oxidation electric current, linearly relevant to concentration of glucose based on this electric current, the mensuration of glucose content can be realized.
Fig. 3 is the pattern of the sensor surface seen by scanning electron microscope (SEM).Nano nickel particle is extremely evenly dispersed in electrode surface, and particle diameter is about 60nm.
Fig. 4 is the linear relationship chart of current method response current and glucose in solutions concentration, and linear equation is i (μ A)=41.2898C (mM)+1.7394, and the range of linearity is 1 μm of ol/L ~ 4mmol/L, and related coefficient reaches 0.9998.The detection calculating this method according to S/N=3 is limited to 200nmol/L, and this method is wider than the range of linearity of many bibliographical informations, and detectability is low.To 20 μMs of glucose METHOD FOR CONTINUOUS DETERMINATION 10 times, current-responsive relative standard deviation (RSD) is only 0.23%.Modified electrode is placed in pH7.0 phosphate buffer and redeterminates glucose after 4 DEG C of refrigerators preserves 1 month, and current-responsive only declines 3%.Repeat to prepare sensor 6 times, 1.5% is only to the current-responsive relative standard deviation (RSD) of 20 μMs of glucose.
NiNPs/SPAEK/GCE is to glucose in 0.1M NaOH medium, and dopamine (DA), ascorbic acid (AA), NaCl carries out i-t method mensuration.Under 0.55V measures current potential, relative to the glucose solution of 20 μMs, 1 μM of DA of low concentration, 100 μMs of NaCl (the suitable concentration in actual biological sample) of 1 μM of AA and high concentration, do not produce interference, this proves that the antijamming capability of NiNPs-SPAEK/GCE is very strong, can be used for the mensuration of actual biological sample completely.
What more than enumerate is only some embodiments of the present invention; obviously, the invention is not restricted to above embodiment, many distortion can also be had; all distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (6)
1. a renewable metal nanoparticle electrochemical sensor, it is characterized in that, described sensor exchanges thin layer template precursor and carrier film primarily of a naked glass-carbon electrode, one deck sulfonated poly aryl ether ketone macromolecule cation, and one deck nano nickel particle high electrocatalytic active film forms.
2. the preparation method of a renewable metal nanoparticle electrochemical sensor as claimed in claim 1, it is characterized in that, the sulfonic acid group on sulfonated poly aryl ether ketone (SPAEK) thin layer precursor film and transition metal ion nickel is utilized to have stronger mating reaction and ion exchange, take nickel sulfate solution as deposit solution, adopt electrochemical in-situ reducing process loaded with nano nickel particles on sulfonated poly aryl ether ketone film modified electrod.
3. the preparation method of renewable metal nanoparticle electrochemical sensor according to claim 2, it is characterized in that, the sulfonated poly aryl ether ketone solution of dispersion is dissolved by solvent DMF, adopt micro syringe and simple ultrasonic drop-coating, modify the very thin sulfonated poly aryl ether ketone macromolecule cation of one deck in glassy carbon electrode surface and exchange thin layer template precursor and carrier film.
4. the preparation method of the renewable metal nanoparticle electrochemical sensor according to Claims 2 or 3, is characterized in that, the Ni in described nickel sulfate solution
2+can by coordination and cation exchange effect preenrichment in sulfonated poly aryl ether ketone high molecular polymer thin layer template, then can obtain at electrode surface through electrochemical in-situ reducing process and be evenly distributed, the high electrocatalytic active nano nickel particle high electrocatalytic active film of reuniting does not occur.
5. the preparation method of renewable metal nanoparticle electrochemical sensor according to claim 4, it is characterized in that, described nano nickel particle high electrocatalytic active film by after soak wash-out in sulfuric acid solution, again in nickel sulfate solution through preenrichment Ni
2+step and electrochemical in-situ reduction step, renewable nano nickel particle high electrocatalytic active film, described sulfonated poly aryl ether ketone macromolecule cation exchanges thin layer template precursor and carrier film can repeatedly recycle.
6. a renewable metal nanoparticle electrochemical sensor as claimed in claim 1 is applied to the Electrochemical Detection of glucose, it is characterized in that, select under optimal response current potential, response mensuration is carried out to crossing glucose by current versus time curve method, in very wide concentration range, described sensor to glucose have stable, reappear and the current-responsive of rapid sensitive, the high long-time stability that ensure that glucose electrochemical measurement of repeated degree of described sensor preparation process.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105891291A (en) * | 2016-04-11 | 2016-08-24 | 浙江大学 | Copper nanoparticle cluster loaded electrochemical sensor and preparation method thereof |
| CN109142478A (en) * | 2018-08-30 | 2019-01-04 | 浙江大学 | A kind of novel high molecular polymer film functionalization graphene modified electrode electrochemical sensor and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105891291A (en) * | 2016-04-11 | 2016-08-24 | 浙江大学 | Copper nanoparticle cluster loaded electrochemical sensor and preparation method thereof |
| CN109142478A (en) * | 2018-08-30 | 2019-01-04 | 浙江大学 | A kind of novel high molecular polymer film functionalization graphene modified electrode electrochemical sensor and preparation method and application |
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