CN106568818A - Nickel complex/graphene oxide modified glass-carbon electrode and manufacturing method thereof - Google Patents
Nickel complex/graphene oxide modified glass-carbon electrode and manufacturing method thereof Download PDFInfo
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- CN106568818A CN106568818A CN201610968481.4A CN201610968481A CN106568818A CN 106568818 A CN106568818 A CN 106568818A CN 201610968481 A CN201610968481 A CN 201610968481A CN 106568818 A CN106568818 A CN 106568818A
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Abstract
The invention discloses manufacturing method of a nickel complex/graphene oxide modified glass-carbon electrode. By utilizing the electrochemical activity of adamantane p-aldehyde benzoate ethylene diamine bis(Schiff base) nickel complex, an embedding method and an electro-deposition method are adopted to prepare the adamantane p-aldehyde benzoate ethylene diamine bis(Schiff base) nickel complex/graphene oxide modified glass-carbon electrode. The nickel complex/graphene oxide modified glass-carbon electrode can be used to measure the concentration of carmine in a 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
The chemically modified electrode that can be used for quick detection carmine concentration is planted, belongs to technical field of electrochemistry.
Background technology
Carmine (Ponceau 4R) is widely used as the coloring agent of beverage, the sugar-coat capsule of medicine and cosmetics etc., be
China or even whole world consumption is maximum, most popular monoazo class synthetic food color, usage amount has to comply with《In
Magnificent people's republic's national standard-food additive uses standard》.China's Ministry of Public Health regulation, it is maximum edible in food and beverage
Measure as 0.05g/kg, this is because azo pigment metabolism can generate aromatic amine compounds and free radical in vivo, it is further anti-
Electrophilic material and active oxygen should be generated, so as to damage dna.Therefore, in order to ensure the health diet of people, research is easy, quick
Effectively the method for detection food additive carmine content seems particularly significant.The chemical modification of electrode is referred to by from group
The methods such as dress, drop coating, covalent bonding, electro-deposition or chemisorbed will introduce electrode surface with specific function material, give electricity
The process of pole New function.Food safety in recent years is more and more taken seriously, and easily and fast food analyses technology seems outstanding for exploitation
For important.At present the method for China's food safety detection mainly has chemical analysis, gas chromatography, high performance liquid chromatography
Deng, but these method detection time length, not high selectivity, serious interference, sample pre-treatments step be numerous and diverse, equipment price is held high
It is expensive, it is not suitable for on-site measurement.Electrical analysis becomes the new of food inspection due to its easy, quick, environmental protection, low cost and other advantages
Type means.Chemically modified electrode has the advantages that easily preparation, sensitivity are high, chemical stability is good, response signal is big, in food point
Application in analysis is increasingly extensive.For example, Jing Zhang et al. use 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 determine soft containing carmine and lemon yellow
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.,
The chemical property of modified electrode is tested by cyclic voltammetry, chronoamperometry and chronocoulometry, as a result table
Bright, modified electrode has good catalytic effect to electro-catalysis alcohol.Containing-C=O and-NH2Material formed by condensation reaction
Organic compound containing C=N bases is referred to as Schiff's base, and it is strong with most of metallic ion coordination binding ability, and its transition metal is matched somebody with somebody
Compound is preferable electronic media in chemically modified electrode.Only one layer of atomic thickness that graphene oxide is made up of carbon atom
Planar nano material, be good electrochemical sensing material with larger specific surface area, faster electron transport rate
Material, in being widely used in chemically modified electrode.The present invention is combined with glass-carbon electrode as basal electrode using imbedding method 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 the Bis-Schiff Bases nickel complex/graphene oxide/glass-carbon electrode of carmine concentration.
The content of the invention
It is an object of the invention to provide a kind of chemically modified electrode of energy quick detection carmine concentration and preparation method thereof.
The inventive method detects the principle of carmine concentration：Terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting p-phenylenediamine Bis-Schiff Bases
The chemical stability of nickel complex, electrochemical reversibility and high electron transfer rate constant so that it can make in electro-catalysis
Serve as electronic media with, transfer electronics, goes out to the oxidation performance of carmine in carmine and basal electrode (glass-carbon electrode)
Efficient electrocatalysis characteristic, its electrochemical response signal is linear with carmine concentration, thus terephthalaldehydic acid Buddha's warrior attendant
Alkyl ester contracting p-phenylenediamine Bis-Schiff Bases nickel complex modified electrode, possesses and is measured carmine content using cyclic voltammetry
Condition.
What chemically modified electrode made concretely comprises the following steps：
(1) first successively with 0.5 μm of Al2O3A diameter of 2mm glass-carbon electrodes are polished to minute surface by powder on chamois leather, super
Successively in ultra-pure water, dehydrated alcohol under sound wave auxiliary, each ultrasonic 3 minutes in redistilled water, afterwards, in being put into 50 DEG C of baking oven
It is dried 5 minutes, it is standby.
(2) 2 milligrams of graphene oxide is taken with filter paper, the graphene oxide is then ground always until being inhaled by electrode
It is attached, it is to be ground it is good after, take out dried glass-carbon electrode from baking oven at once, electrode surface is being placed with into ground oxidation
Rub back and forth on the qualitative filter paper of Graphene 1 minute, then cleaned with dehydrated alcohol and distilled water, graphene oxide modification is obtained
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 electrodes are reference electrode, and platinum electrode is auxiliary electrode, by step (2)
The graphene oxide modified glassy carbon electrode for preparing be working electrode, with (3) as electrolyte, control voltage scope be -1.5～
1.5V, sweep speed is 100mV/s, and scanning 20 is enclosed, and terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting ethylenediamine Bis-Schiff Bases nickel is coordinated
Thing is electrodeposited into glassy carbon electrode surface, and nickel complex/graphene oxide modified glassy carbon electrode is obtained after drying at room temperature.
Description of the drawings
Fig. 1 is the work drawn as vertical coordinate with the red concentration of fat fat as slogan banner and with oxidation peak current in the embodiment of the present invention
Curve chart.
Specific embodiment
Embodiment:
(1) first successively with 0.5 μm of Al2O3A diameter of 2mm glass-carbon electrodes are polished to minute surface by powder on chamois leather, super
Successively in ultra-pure water, dehydrated alcohol under sound wave auxiliary, each ultrasonic 3 minutes in redistilled water, afterwards, in being put into 50 DEG C of baking oven
It is dried 5 minutes, it is standby.
(2) 2 milligrams of graphene oxide is taken with filter paper, the graphene oxide is then ground always until being inhaled by electrode
It is attached, it is to be ground it is good after, take out dried glass-carbon electrode from baking oven at once, electrode surface is being placed with into ground oxidation
Rub back and forth on the qualitative filter paper of Graphene 1 minute, then cleaned with dehydrated alcohol and distilled water, graphene oxide modification is obtained
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 electrodes are reference electrode, and platinum electrode is auxiliary electrode, by step (2)
The graphene oxide modified glassy carbon electrode for preparing be working electrode, with (3) as electrolyte, control voltage scope be -1.5～
1.5V, sweep speed is 100mV/s, and scanning 20 is enclosed, and terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting ethylenediamine Bis-Schiff Bases nickel is coordinated
Thing is electrodeposited into glassy carbon electrode surface, and nickel complex/graphene oxide modified glassy carbon electrode is obtained after drying at room temperature.
(5) three-electrode system is adopted, under room temperature, is repaiied with nickel complex/graphene oxide obtained in above-mentioned steps (4) respectively
Decorations glass-carbon electrode is working electrode, and the Ag/AgCl electrodes of saturated nacl aqueous solution are reference electrode, and platinum electrode is auxiliary electricity
Pole, (pH=7.0) is carried out all in the PBS buffer solution of the 30mL carmine containing variable concentrations for measurement, and cyclic voltammetry is swept
Retouch, scanning speed 50mV/s, sweep limitss -0.85～+0.4V.Oxidation peak (anode peak) electricity of record variable concentrations carmine
Stream, Fig. 1 results show, carmine concentration in the range of 0.0333～3.33g/L (or 0.001g-0.1g), its concentration with it is corresponding
Oxidation peak peak point current is presented good linear relationship, and linear equation is y=3.984 × 10-6+1.469×10-4χ, phase relation
Number is 0.99523.
(6) choosing the beverage of certain brand carries out sample analysis.The sample of heating certain volume, to drive away CO2、O2, cooling
Afterwards, 10.0mL beverages accurately being measured respectively, with the buffer solution of PBS=8 100mL being settled to, correct amount drinks material diluent
30.0mL, in being placed in 50mL beakers, to the sample solution, is circulated voltammetric scan, is oxidized peak current substitution work bent
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 is 0.28%.Carmine content is then 38.91mg/L in Jing conversion beverages.To 30mL
Add 600 μ L 10mg/L carmine red standard solution in sample solution, carry out recovery testu.Recovery of standard addition 97.91%～
Between 100.39%, RSD=0.99% shows that the method accuracy is good, can be used for the measure of carmine content in beverage.
Carmine content measurement result in the beverage of table 1
Claims (2)
1. the manufacture method of a kind of nickel complex/graphene oxide modified glassy carbon electrode, it is characterised in that concretely comprise the following steps：
(1) first with 0.5 μm of Al2O3A diameter of 2mm glass-carbon electrodes are polished to minute surface by powder on chamois leather, in ultrasonic assistant
Under successively in ultra-pure water, dehydrated alcohol, each ultrasonic 3 minutes in redistilled water, afterwards, be put in 50 DEG C of baking oven be dried 5 points
Clock, it is standby；
(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, take out dried glass-carbon electrode from baking oven at once, electrode surface is being placed with into ground oxidation stone
Rub back and forth on the qualitative filter paper of black alkene 1 minute, then cleaned with dehydrated alcohol and distilled water, graphene oxide modification glass is obtained
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
Into 0.002mol/L solution；
(4) three-electrode system is used, Ag/AgCl electrodes are reference electrode, and platinum electrode is auxiliary electrode, prepared by step (2)
Good graphene oxide modified glassy carbon electrode is working electrode, and with (3) as electrolyte, control voltage scope is -1.5～1.5V,
Sweep speed is 100mV/s, and scanning 20 is enclosed, and terephthalaldehydic acid Buddha's warrior attendant alkyl ester contracting ethylenediamine Bis-Schiff Bases nickel complex electricity is heavy
Product obtains nickel complex/graphene oxide modified glassy carbon electrode to glassy carbon electrode surface after drying at room temperature.
2. the manufacture method of nickel complex according to claim 1/graphene oxide modified glassy carbon electrode, it is characterised in that
Obtained nickel complex/graphene oxide modified glassy carbon electrode is applied to the concentration of carmine in detection sample.
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Cited By (1)
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|---|---|---|---|---|
| CN107576715A (en) * | 2017-09-17 | 2018-01-12 | 桂林理工大学 | A kind of method that concentration of benzoic acid is detected using modified glassy carbon electrode |
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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 |
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| 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 |
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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 |
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| CN107576715A (en) * | 2017-09-17 | 2018-01-12 | 桂林理工大学 | A kind of method that concentration of benzoic acid is detected using modified glassy carbon electrode |
| CN107576715B (en) * | 2017-09-17 | 2019-11-26 | 桂林理工大学 | A method of concentration of benzoic acid is detected using modified glassy carbon electrode |
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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 |