CN106556633A - A kind of method of modifying of glass-carbon electrode - Google Patents
A kind of method of modifying of glass-carbon electrode Download PDFInfo
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- CN106556633A CN106556633A CN201610989402.8A CN201610989402A CN106556633A CN 106556633 A CN106556633 A CN 106556633A CN 201610989402 A CN201610989402 A CN 201610989402A CN 106556633 A CN106556633 A CN 106556633A
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- graphene
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Abstract
The invention discloses a kind of method of modifying of glass-carbon electrode, is obtained the composite modified glass-carbon electrode of Polymethylene blue/Graphene.The composite modified glass-carbon electrode of Polymethylene blue/Graphene that the present invention is prepared, with good stability and repeatability, sensitivity is high.On the composite modified glass-carbon electrode of Polymethylene blue/Graphene of the present invention, the oxidation peak current of dopamine is 1 × 10‑7～5 × 10‑3Good linear relationship is presented in the range of mol/L, therefore which can realize the selective determination to dopamine.
Description
Technical field
The present invention relates to be energy technology field, more particularly to a kind of method of modifying of glass-carbon electrode.
Background technology
Dopamine (DA) is the important neurotransmitter of mammalian central nervous system, is to aid in cell transfer pulse
Chemical substance, its change in concentration in vivo is directly related with nervous activity.Therefore, the research to DA assay methods has weight
Want meaning.As overpotentials of the DA on solid electrode is larger, overpotential can be reduced using modified electrode and the biography of DA can be increased
Matter speed, existing document report study the electrochemical behavior of DA with chemically modified electrode, are modified with polymer degree material with carbon element recently
The research of electrode is more.
Graphene is a kind of new nano-carbon material, since being found from 2004 by Geim etc., by numerous researchers
Attention.The unique performance of Graphene, such as quick electron transport rate, big specific surface area, high thermal conductivity, excellent machine
Tool performance and good biocompatibility etc., have application well in terms of electrochemica biological sensor.
Graphene and some conducting polymers, the chemically modified electrode of the such as compound preparation such as dyestuff, polyaniline, shitosan draw
The broad interest of researcher is played.Wherein, dyestuff occupies considerable status in the research of Electrochemical Modification electrode.To dye
Material molecule research of absorption behavior on material with carbon element electrode show, between dye molecule and graphite electrode by electron cloud it is overlap enter
Row coupling, increased adsorption strength of the graphite electrode to dye molecule, accelerates charge transfer rate.
Methylene blue (MB) is a kind of cationic phenothiazines biological dye, is also a kind of active electro transfer of comparison
Body, which has good electro-chemical activity and photochemical activity, and which on the electrode through pretreatment can aggregate into one layer of conduction and gather
Film is closed, the film has good electro-chemical activity and electrocatalysis characteristic.Ma Yanrong etc. has found using MB to prepare as dressing agent
PMB/Au electrode pair uric acid (UA) oxidation with good electrocatalysis, reduce the overpotential of UA, oxidation peak current
Significantly increase.
Contain big conjugation aromatic rings in Polymethylene blue structure, can be at material with carbon element (such as CNT and Graphene etc.)
Surface produces a certain degree of absorption by π-π noncovalent interactions, is conducive to improving the transmission efficiency of electronics.Yang Huaicheng etc. makes
Electrode is repaiied for Polymethylene blue/SWCN, electrode pair NADH (NADH) oxidation has
Good electrocatalysis.The method using electropolymerization such as Yogeswaran, is prepared for Polymethylene blue/multi-walled carbon nano-tubes
(PMB/MWCNTs) electrode modified, and have studied DA, ascorbic acid and catecholamine electrochemical behavior thereon.
The content of the invention
It is an object of the invention to propose a kind of method of modifying of glass-carbon electrode, the electrode for enabling to obtain is used for hydrochloric acid
The measure of injection sample, measurement result are accurate.
It is that, up to this purpose, the present invention is employed the following technical solutions：
A kind of method of modifying of glass-carbon electrode, including：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulfuric acid, add and account for
The sodium nitrate of graphite powder 50-80wt%, and to account for and react 30-120min under the potassium permanganate of 2-4 times of weight of graphite powder, ice bath；
(2) 30-40 DEG C of constant temperature 4-5h is heated to, deionized water and hydrogen peroxide is added, 1-3h is stirred, 5% concentration is added
HCl centrifuge washings are until sulfate radical-free ion, obtains graphene oxide；
(3) graphene oxide is put in the hydrazine hydrate solution of 10wt% concentration and is reduced, reduction temperature is 75-90
DEG C, recovery time 0.5-2h obtains Graphene；
(4) by the Graphene ultrasonic disperse in deionized water, the graphene solution of 0.8-1.5g/L is obtained；
(5) graphene solution is coated in into glass electrode surface, is dried under infrared lamp, graphene modified glass carbon electricity is obtained
Pole；
(6) the graphene modified glass-carbon electrode is immersed in the PBS (PBS) of methylene blue, adopts three
Electrode system, in the potential range of -0.8～0.8V sweeps fast scan round 15-30 circles with 90-110mV/s, polymethylene is obtained
The composite modified glass-carbon electrode of indigo plant/Graphene.
The composite modified glass-carbon electrode of Polymethylene blue/Graphene that the present invention is prepared is used for actual sample hydrochloric acid
The measure of dopamine in injection sample.A certain amount of dopamine hydrochloride injection is pipetted in volumetric flask, is 6.9 with pH value
PBS dilutions, shake up, be subsequently placed in electrolytic cell, add Polymethylene blue/Graphene for preparing of the present invention composite modified
Glass-carbon electrode, using DPV methods parallel determination 10 times.As a result show, the rate of recovery that this method is determined to DA is 97.4-
100.3%, which is more accurate, can be used for actually detected use.
The composite modified glass-carbon electrode of Polymethylene blue/Graphene that the present invention is prepared, with good stability
And repeatability, sensitivity height.On the composite modified glass-carbon electrode of the Polymethylene blue/Graphene of the present invention, the oxygen of dopamine
Change peak current 1 × 10-7～5 × 10-3Good linear relationship is presented in the range of mol/L, therefore which can be realized to dopamine
Selective determination.
Specific embodiment
Technical scheme is further illustrated below by specific embodiment.
Embodiment 1
A kind of method of modifying of glass-carbon electrode, including：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulfuric acid, add and account for
The sodium nitrate of graphite powder 50wt%, and to account for and react 30-120min under the potassium permanganate of 2 times of weight of graphite powder, ice bath；
(2) 30 DEG C of constant temperature 4h are heated to, deionized water and hydrogen peroxide is added, 1h is stirred, the HCl centrifugations of 5% concentration are added
Washing is until sulfate radical-free ion, obtains graphene oxide；
(3) graphene oxide is put in the hydrazine hydrate solution of 10wt% concentration and is reduced, reduction temperature is 75 DEG C, also
Former time 0.5h, obtains Graphene；
(4) by the Graphene ultrasonic disperse in deionized water, the graphene solution of 0.8g/L is obtained；
(5) graphene solution is coated in into glass electrode surface, is dried under infrared lamp, graphene modified glass carbon electricity is obtained
Pole；
(6) the graphene modified glass-carbon electrode is immersed in the PBS (PBS) of methylene blue, adopts three
Electrode system, in the potential range of -0.8～0.8V sweeps fast scan round 15 with 90mV/s and encloses, and Polymethylene blue/graphite is obtained
The composite modified glass-carbon electrode of alkene.
Embodiment 2
A kind of method of modifying of glass-carbon electrode, including：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulfuric acid, add and account for
The sodium nitrate of graphite powder 80wt%, and to account for and react 120min under the potassium permanganate of 4 times of weight of graphite powder, ice bath；
(2) 40 DEG C of constant temperature 5h are heated to, deionized water and hydrogen peroxide is added, 3h is stirred, the HCl centrifugations of 5% concentration are added
Washing is until sulfate radical-free ion, obtains graphene oxide；
(3) graphene oxide is put in the hydrazine hydrate solution of 10wt% concentration and is reduced, reduction temperature is 90 DEG C, also
Former time 2h, obtains Graphene；
(4) by the Graphene ultrasonic disperse in deionized water, the graphene solution of 1.5g/L is obtained；
(5) graphene solution is coated in into glass electrode surface, is dried under infrared lamp, graphene modified glass carbon electricity is obtained
Pole；
(6) the graphene modified glass-carbon electrode is immersed in the PBS (PBS) of methylene blue, adopts three
Electrode system, in the potential range of -0.8～0.8V sweeps fast scan round 30 with 110mV/s and encloses, and Polymethylene blue/stone is obtained
The composite modified glass-carbon electrode of black alkene.
Embodiment 3
A kind of method of modifying of glass-carbon electrode, including：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulfuric acid, add and account for
The sodium nitrate of graphite powder 70wt%, and to account for and react 60min under the potassium permanganate of 3 times of weight of graphite powder, ice bath；
(2) be heated to 35 DEG C of constant temperature 4.5h, add deionized water and hydrogen peroxide, stir 2h, add the HCl of 5% concentration from
Heart washing is until sulfate radical-free ion, obtains graphene oxide；
(3) graphene oxide is put in the hydrazine hydrate solution of 10wt% concentration and is reduced, reduction temperature is 80 DEG C, also
Former time 1h, obtains Graphene；
(4) by the Graphene ultrasonic disperse in deionized water, the graphene solution of 1.0g/L is obtained；
(5) graphene solution is coated in into glass electrode surface, is dried under infrared lamp, graphene modified glass carbon electricity is obtained
Pole；
(6) the graphene modified glass-carbon electrode is immersed in the PBS (PBS) of methylene blue, adopts three
Electrode system, in the potential range of -0.8～0.8V sweeps fast scan round 20 with 100mV/s and encloses, and Polymethylene blue/stone is obtained
The composite modified glass-carbon electrode of black alkene.
The composite modified glass-carbon electrode of Polymethylene blue/Graphene that embodiment 1-3 is prepared, stablizes with good
Property and repeatability, sensitivity is high.On the composite modified glass-carbon electrode of the Polymethylene blue/Graphene of the present invention, dopamine
Oxidation peak current is 1 × 10-7～5 × 10-3Good linear relationship is presented in the range of mol/L, therefore which can be realized to DOPA
The selective determination of amine.
Claims (1)
1. a kind of method of modifying of glass-carbon electrode, including：
(1), under condition of ice bath, under mechanical agitation, crystalline graphite powder is added in 98% concentrated sulfuric acid, add and account for graphite
The sodium nitrate of powder 50-80wt%, and to account for and react 30-120min under the potassium permanganate of 2-4 times of weight of graphite powder, ice bath；
(2) be heated to 30-40 DEG C of constant temperature 4-5h, add deionized water and hydrogen peroxide, stir 1-3h, add the HCl of 5% concentration from
Heart washing is until sulfate radical-free ion, obtains graphene oxide；
(3) graphene oxide is put in the hydrazine hydrate solution of 10wt% concentration and is reduced, reduction temperature is 75-90 DEG C, also
Former time 0.5-2h, obtains Graphene；
(4) by the Graphene ultrasonic disperse in deionized water, the graphene solution of 0.8-1.5g/L is obtained；
(5) graphene solution is coated in into glass electrode surface, is dried under infrared lamp, graphene modified glass-carbon electrode is obtained；
(6) the graphene modified glass-carbon electrode is immersed in the PBS (PBS) of methylene blue, using three electrodes
System, in the potential range of -0.8～0.8V sweeps fast scan round 15-30 with 90-110mV/s and encloses, and prepared Polymethylene blue/
The composite modified glass-carbon electrode of Graphene.
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Cited By (7)
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|---|---|---|---|---|
| CN106872544A (en) * | 2017-04-12 | 2017-06-20 | 信阳师范学院 | A kind of preparation method of poly- methyl blue/acetylene black composite modified glassy carbon electrode and its application in paracetamol is determined |
| CN109164152A (en) * | 2018-10-28 | 2019-01-08 | 桂林理工大学 | Methylene blue-gold chloride modified glassy carbon electrode preparation method and applications |
| CN109304097A (en) * | 2018-08-28 | 2019-02-05 | 天津工业大学 | Graphene oxide/methylene blue composite membrane and preparation method thereof |
| CN111398382A (en) * | 2020-04-21 | 2020-07-10 | 普洱学院 | Polymethylene blue modified glassy carbon electrode and preparation method and application thereof |
| CN111781260A (en) * | 2020-07-07 | 2020-10-16 | 常熟理工学院 | Preparation method of methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination and determination method of L-tryptophan |
| CN112194641A (en) * | 2020-09-02 | 2021-01-08 | 商丘师范学院 | Flexible electrode for simultaneously detecting hypochlorous acid and ascorbic acid and preparation method and application thereof |
| CN112730556A (en) * | 2020-12-21 | 2021-04-30 | 中南民族大学 | Trace rapid NO electrochemical sensor and preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106872544A (en) * | 2017-04-12 | 2017-06-20 | 信阳师范学院 | A kind of preparation method of poly- methyl blue/acetylene black composite modified glassy carbon electrode and its application in paracetamol is determined |
| CN109304097A (en) * | 2018-08-28 | 2019-02-05 | 天津工业大学 | Graphene oxide/methylene blue composite membrane and preparation method thereof |
| CN109304097B (en) * | 2018-08-28 | 2021-05-04 | 天津工业大学 | Graphene oxide/methylene blue composite film and preparation method thereof |
| CN109164152A (en) * | 2018-10-28 | 2019-01-08 | 桂林理工大学 | Methylene blue-gold chloride modified glassy carbon electrode preparation method and applications |
| CN111398382A (en) * | 2020-04-21 | 2020-07-10 | 普洱学院 | Polymethylene blue modified glassy carbon electrode and preparation method and application thereof |
| CN111781260A (en) * | 2020-07-07 | 2020-10-16 | 常熟理工学院 | Preparation method of methylene blue and carbon nanotube modified glassy carbon electrode for L-tryptophan determination and determination method of L-tryptophan |
| CN112194641A (en) * | 2020-09-02 | 2021-01-08 | 商丘师范学院 | Flexible electrode for simultaneously detecting hypochlorous acid and ascorbic acid and preparation method and application thereof |
| CN112730556A (en) * | 2020-12-21 | 2021-04-30 | 中南民族大学 | Trace rapid NO electrochemical sensor and preparation method and application thereof |
| CN112730556B (en) * | 2020-12-21 | 2022-05-20 | 中南民族大学 | Trace rapid NO electrochemical sensor and preparation method and application thereof |
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Application publication date: 20170405 |