CN106568818B - A kind of nickel complex/graphene oxide modified glassy carbon electrode and preparation method thereof - Google Patents
A kind of nickel complex/graphene oxide modified glassy carbon electrode and preparation method thereof Download PDFInfo
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- CN106568818B CN106568818B CN201610968481.4A CN201610968481A CN106568818B CN 106568818 B CN106568818 B CN 106568818B CN 201610968481 A CN201610968481 A CN 201610968481A CN 106568818 B CN106568818 B CN 106568818B
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Abstract
The invention discloses a kind of nickel complex/graphene oxide modified glassy carbon electrode production methods.Using the electro-chemical activity of terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting ethylenediamine Bis-Schiff Bases nickel complex, terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting ethylenediamine Bis-Schiff Bases nickel complex/graphene oxide modified glassy carbon electrode is prepared for using embedding inlay technique and electrodeposition process.The nickel complex/graphene oxide modified glassy carbon electrode, can be applied to concentration carmine in test sample.
Description
Technical field
The present invention relates to a kind of nickel complex/graphene oxide modified glassy carbon electrode and preparation method thereof more particularly to one
Kind can be used for quickly detecting the chemically modified electrode of carmine concentration, belong to electrochemical technology field.
Background technique
Carmine (Ponceau 4R) is widely used as the colorant of beverage, the sugar-coat capsule of drug and cosmetics etc., be
China or even whole world dosage be maximum, most popular monoazo class synthetic food color, usage amount have to comply with " in
Magnificent people's republic's national standard-food additives use standard ".The Ministry of Public Health, China provides, maximum edible in food and beverage
Amount is 0.05g/kg, this is because azo pigment can be metabolized in vivo generates aromatic amine compounds and free radical, it is further anti-
Electrophilic substance and active oxygen should be generated, thus damage dna.Therefore, in order to ensure people's health diet, research is easy, quick
The method of effective detection food additives carmine content seems particularly significant.The chemical modification of electrode refers to by from group
The methods of dress, drop coating, covalent bonding, electro-deposition or chemisorption will have specific function substance to introduce electrode surface, give electricity
The process of pole new function.Food safety is more and more taken seriously in recent years, and food analysis technology seems outstanding easily and fast for exploitation
It is important.The method of China's food safety detection mainly has chemical analysis, gas chromatography, high performance liquid chromatography at present
Deng, but these method detection times are long, selectivity is not high, serious interference, sample pre-treatments step is many and diverse, equipment price is high
It is expensive, it is not suitable for on-site measurement.Electrical analysis is since the advantages that it is easy, quick, environmentally friendly, at low cost, is as the new of food inspection
Type means.Chemically modified electrode has many advantages, such as that easy preparation, high sensitivity, chemical stability is good, response signal is big, in food point
In analysis using increasingly extensive.For example, Jing Zhang et al. uses an ion liquid modified expanded graphite electrode paste (IL-
EGPE), there is good electro-chemical activity to carmine and lemon yellow, and be successfully applied to measure containing carmine and lemon yellow soft
Beverage, it is as a result satisfactory.Nickel and cobalt complex are filled in mesopore molecular sieve modified glassy carbon electrode by Wenyang Wang et al.,
It is tested by the chemical property of cyclic voltammetry, chronoamperometry and chronocoulometry to modified electrode, as a result table
Bright, modified electrode has good catalytic effect to electro-catalysis alcohol.Contain-C=O and-NH2Substance formed by condensation reaction
The organic compound of the base containing C=N is known as schiff bases, it is strong with most of metallic ion coordination binding ability, and transition metal is matched
Closing object is ideal electronic media in chemically modified electrode.Only one layer of atomic thickness that graphene oxide is made of carbon atom
Planar nano material, have biggish specific surface area, faster electron transport rate, be good electrochemical sensing material
Material, is widely used in chemically modified electrode.The present invention is combined using glass-carbon electrode as basal electrode using embedding inlay technique and electro-deposition
Method of modifying by graphene oxide, the modification of terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting p-phenylenediamine Bis-Schiff Bases nickel complex to glass
Carbon electrodes are prepared for detecting Bis-Schiff Bases nickel complex/graphene oxide/glass-carbon electrode of carmine concentration.
Summary of the invention
The object of the present invention is to provide a kind of chemically modified electrodes and preparation method thereof that can quickly detect carmine concentration.
The method of the present invention detects the principle of carmine concentration: terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting p-phenylenediamine Bis-Schiff Bases
Chemical stability, electrochemical reversibility and the high electron transfer rate constant of nickel complex make it in electro-catalysis
Electronic media is served as in, electronics is shifted in carmine and basal electrode (glass-carbon electrode), and carmine oxidation performance is gone out
Efficient electrocatalysis characteristic, electrochemical response signal and carmine concentration are in a linear relationship, thus terephthalaldehydic acid Buddha's warrior attendant
Alkyl ester contracting p-phenylenediamine Bis-Schiff Bases nickel complex modified electrode, has and is measured carmine content using cyclic voltammetry
Condition.
The specific steps of chemically modified electrode production are as follows:
(1) first successively with 0.5 μm of Al2O3Diameter is that 2mm glass-carbon electrode is polished to mirror surface on chamois leather by powder, super
It successively later, is put into 50 DEG C of baking oven each ultrasonic 3 minutes in ultrapure water, dehydrated alcohol, secondary distilled water under sound wave auxiliary
It is 5 minutes dry, it is spare.
(2) 2 milligrams of graphene oxide is taken with filter paper, then grinds the graphene oxide always until that can be inhaled by electrode
It is attached, it is to be ground it is good after, dried glass-carbon electrode is taken out from baking oven at once, electrode surface is being placed with ground oxidation
It rubs on the qualitative filter paper of graphene 1 minute, is then cleaned with dehydrated alcohol and distilled water back and forth, graphene oxide modification is made
Glass-carbon electrode.
(3) terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting ethylenediamine Bis-Schiff Bases nickel complex is dissolved in dichloromethane solvent,
It is configured to 0.002mol/L solution.
(4) three-electrode system is used, Ag/AgCl electrode is reference electrode, and platinum electrode is auxiliary electrode, by step (2)
The graphene oxide modified glassy carbon electrode prepared be working electrode, with (3) be electrolyte, control voltage range be -1.5~
1.5V, sweep speed 100mV/s, 20 circle of scanning, terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting ethylenediamine Bis-Schiff Bases nickel is cooperated
Object is electrodeposited into glassy carbon electrode surface, obtains nickel complex/graphene oxide modified glassy carbon electrode after drying at room temperature.
Detailed description of the invention
Fig. 1 is in the embodiment of the present invention using the red concentration of rouge rouge as slogan banner and the work drawn by ordinate of oxidation peak current
Curve graph.
Specific embodiment
Embodiment:
(1) first successively with 0.5 μm of Al2O3Diameter is that 2mm glass-carbon electrode is polished to mirror surface on chamois leather by powder, super
It successively later, is put into 50 DEG C of baking oven each ultrasonic 3 minutes in ultrapure water, dehydrated alcohol, secondary distilled water under sound wave auxiliary
It is 5 minutes dry, it is spare.
(2) 2 milligrams of graphene oxide is taken with filter paper, then grinds the graphene oxide always until that can be inhaled by electrode
It is attached, it is to be ground it is good after, dried glass-carbon electrode is taken out from baking oven at once, electrode surface is being placed with ground oxidation
It rubs on the qualitative filter paper of graphene 1 minute, is then cleaned with dehydrated alcohol and distilled water back and forth, graphene oxide modification is made
Glass-carbon electrode.
(3) terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting ethylenediamine Bis-Schiff Bases nickel complex is dissolved in dichloromethane solvent,
It is configured to 0.002mol/L solution.
(4) three-electrode system is used, Ag/AgCl electrode is reference electrode, and platinum electrode is auxiliary electrode, by step (2)
The graphene oxide modified glassy carbon electrode prepared be working electrode, with (3) be electrolyte, control voltage range be -1.5~
1.5V, sweep speed 100mV/s, 20 circle of scanning, terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting ethylenediamine Bis-Schiff Bases nickel is cooperated
Object is electrodeposited into glassy carbon electrode surface, obtains nickel complex/graphene oxide modified glassy carbon electrode after drying at room temperature.
(5) it is repaired respectively with nickel complex/graphene oxide made from above-mentioned steps (4) at room temperature using three-electrode system
Decorations glass-carbon electrode is working electrode, and the Ag/AgCl electrode of saturated sodium chloride solution is reference electrode, and platinum electrode is auxiliary electricity
Pole, measurement (pH=7.0) all in the PBS buffer solution of the 30mL famille rose containing various concentration carry out, and cyclic voltammetry is swept
It retouches, scanning speed 50mV/s, scanning range -0.85~+0.4V.Record oxidation peak (anode peak) electricity of various concentration famille rose
Stream, Fig. 1 the result shows that, carmine concentration is in 0.0333~3.33g/L (or 0.001g-0.1g) range, concentration and corresponding
Good linear relationship is presented in oxidation peak peak point current, and linear equation is y=3.984 × 10-6+1.469×10-4χ, phase relation
Number is 0.99523.
(6) beverage for choosing certain brand carries out sample analysis.The sample of certain volume is heated, to drive away CO2、O2, cooling
Afterwards, accurate respectively to measure 10.0mL beverage, it is settled to 100mL with the buffer solution of PBS=8, correct amount drinks material dilution
30.0mL is placed in 50mL beaker, to the sample solution, carries out cyclic voltammetry scan, is oxidized peak current and is substituted into work song
Line linear equation calculates the carmine content in dilute sample, and parallel to carry out 5 experiments, carmine average content is in sample
3.891mg/L, relative standard deviation RSD are 0.28%.It is then 38.91mg/L through carmine content in conversion beverage.To 30mL
Add 600 μ L 10mg/L carmine red standard solution in sample solution, carries out recovery testu.Recovery of standard addition 97.91%~
Between 100.39%, RSD=0.99% shows that this method accuracy is good, can be used for the measurement of carmine content in beverage.
Carmine content measurement result in 1 beverage of table
Claims (1)
1. a kind of nickel complex/graphene oxide modified glassy carbon electrode production method, it is characterised in that specific steps are as follows:
(1) first with 0.5 μm of Al2O3Diameter is that 2mm glass-carbon electrode is polished to mirror surface on chamois leather by powder, is assisted in ultrasonic wave
Under successively each ultrasonic 3 minutes in ultrapure water, dehydrated alcohol, secondary distilled water, later, be put into 50 DEG C of baking oven 5 points dry
Clock, it is spare；
(2) 2 milligrams of graphene oxide is taken with filter paper, then grind always the graphene oxide until can by electrode adsorption,
It is to be ground it is good after, dried glass-carbon electrode is taken out from baking oven at once, electrode surface is being placed with ground oxidation stone
It rubs on the qualitative filter paper of black alkene 1 minute, is then cleaned with dehydrated alcohol and distilled water back and forth, graphene oxide is made and modifies glass
Carbon electrode；
(3) terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting ethylenediamine Bis-Schiff Bases nickel complex is dissolved in dichloromethane solvent, is configured
At 0.002mol/L solution；
(4) three-electrode system is used, Ag/AgCl electrode is reference electrode, and platinum electrode is auxiliary electrode, prepared by step (2)
Good graphene oxide modified glassy carbon electrode is working electrode, using the solution of step (3) configuration as electrolyte, controls voltage range
For -1.5~1.5V, sweep speed 100mV/s, 20 circle of scanning, by the double Schiffs of terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting ethylenediamine
Alkali nickel complex is electrodeposited into glassy carbon electrode surface, and nickel complex/graphene oxide modification glass carbon electricity is obtained after drying at room temperature
Pole；
Above-mentioned obtained nickel complex/graphene oxide modified glassy carbon electrode is applied to concentration carmine in test sample.
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| CN104280435A (en) * | 2014-09-28 | 2015-01-14 | 上海应用技术学院 | Graphene-modified glassy carbon electrode and preparation method and application of graphene-modified glassy carbon electrode |
| CN105175297A (en) * | 2015-10-18 | 2015-12-23 | 桂林理工大学 | Synthesis and application of 4-formyl benzoic acid adamantine ester condensed o-aminobenzene thiophenol schiff base nickel complex |
| CN105294489A (en) * | 2015-10-18 | 2016-02-03 | 桂林理工大学 | 4-formyl benzoic adamantanol ester condensation bromoaniline Schiff base nickel complex synthesis and application |
| CN105388203A (en) * | 2015-10-18 | 2016-03-09 | 桂林理工大学 | Method for detecting carmine concentration |
| CN105403611A (en) * | 2015-10-18 | 2016-03-16 | 桂林理工大学 | Method for detecting concentration of L-cysteine |
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| CN104280435A (en) * | 2014-09-28 | 2015-01-14 | 上海应用技术学院 | Graphene-modified glassy carbon electrode and preparation method and application of graphene-modified glassy carbon electrode |
| CN105175297A (en) * | 2015-10-18 | 2015-12-23 | 桂林理工大学 | Synthesis and application of 4-formyl benzoic acid adamantine ester condensed o-aminobenzene thiophenol schiff base nickel complex |
| CN105294489A (en) * | 2015-10-18 | 2016-02-03 | 桂林理工大学 | 4-formyl benzoic adamantanol ester condensation bromoaniline Schiff base nickel complex synthesis and application |
| CN105388203A (en) * | 2015-10-18 | 2016-03-09 | 桂林理工大学 | Method for detecting carmine concentration |
| CN105403611A (en) * | 2015-10-18 | 2016-03-16 | 桂林理工大学 | Method for detecting concentration of L-cysteine |
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Application publication date: 20170419 Assignee: GUANGXI JISHUN ENERGY TECHNOLOGY Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000495 Denomination of invention: A nickel complex/graphene oxide modified glassy carbon electrode and its preparation method Granted publication date: 20191011 License type: Common License Record date: 20221229 |
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Application publication date: 20170419 Assignee: Guangxi pinri Electronic Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000634 Denomination of invention: A nickel complex/graphene oxide modified glassy carbon electrode and its preparation method Granted publication date: 20191011 License type: Common License Record date: 20221230 |