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CN106018532B - The electrochemical detection device of preparation and the assembling of graphene oxide and phytic acid modified electrode - Google Patents

The electrochemical detection device of preparation and the assembling of graphene oxide and phytic acid modified electrode Download PDF

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CN106018532B
CN106018532B CN201610424736.0A CN201610424736A CN106018532B CN 106018532 B CN106018532 B CN 106018532B CN 201610424736 A CN201610424736 A CN 201610424736A CN 106018532 B CN106018532 B CN 106018532B
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electrode
nafion
graphene oxide
phytic acid
phytate
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CN106018532A (en
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刘秀玉
黄惠
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New Material Institute of Shandong Academy of Sciences
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    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon

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Abstract

The present invention provides the electrochemical detection device that novel electrode prepares graphene oxide and the preparation of phytic acid modified electrode, comprising: by graphene oxide ultrasonic disperse in the mixed solution containing phytic acid and Nafion, obtains GO-Phytate-Nafion suspension;GO-Phytate-Nafion suspension is coated uniformly on polished, cleaning, drying treated glassy carbon electrode surface to get GO-Phytate-Nafion/GCE.The graphene oxide composite material developed meets the requirement of Heavy Metals in Waters ion detection and depth removal.The electrode material of high electro-chemical activity is applied to the quick measurement of electrochemical sensor Heavy Metals in Waters, sample treatment is simple, and it is at low cost, the advantages that speed detects trace heavy metal simultaneously fastly promotes the detection of China's heavy metal water pollution and will have very big economic and social benefit after the developing industry of processing technique.

Description

The electrochemical detection device of preparation and the assembling of graphene oxide and phytic acid modified electrode
Technical field
The invention belongs to analysis detection field, in particular to novel electrode prepares graphene oxide and phytic acid modified electrode, And the electrochemical detection device assembled.
Background technique
Chemically modified electrode is to carry out MOLECULE DESIGN in electrode surface by the method for chemical modification, will have excellent chemical Molecule, ion, the polymer of property are fixed on electrode surface, cause certain micro-structure, assign the certain specific chemistry of electrode and Electrochemical properties have unique to carry out desired reaction with high selectivity in terms of improving selectivity and sensitivity Superiority.Using a variety of potential fields that can be utilized provided by the micro-structure on chemically modified electrode surface, there is determinand The separation and concentration of effect, and coordination electrode current potential is borrowed, selectivity is further increased, while the sensitivity and dressing agent of measuring method The selectivity of chemical reaction combines, and becomes the ideal system that separation, enrichment and selective three are integrated.
Anodic stripping voltammetry (ASV) becomes the main electrochemical process of detection heavy metal ion, but traditional ASV is main Using plating mercury film electrode as working electrode, since murder by poisoning of the mercury to human body is very big, therefore, it is necessary to develop novel environmental protection Electrode material pole replaces mercury.Because modified graphene oxide specific area is big, carbonaceous material mainly sends out the absorption of heavy metal ion On acidic functionality (carboxylic group and lactone acid groups), surface of graphene oxide contains a large amount of hydroxyl, carboxyl and contains for life Oxygen functional group, surface have it is stronger to heavy metal ion adsorbed power, the detection sensitivity of electrode can be promoted.
Patent CN201510518917.5 disclose it is a kind of it is synchronous detection mercury, copper, lead, cadmium ion content electrochemical sensing Graphene oxide N doping is prepared modified glassy carbon electrode using the method for electrochemical deposition by the preparation method of device, acetic acid/ Sodium acetate is to carry out Electrochemical Detection to four kinds of mercury, copper, lead, cadmium ions in the solution of supporting electrolyte.But detection limit is higher, nothing Method meets the requirement of part heavy metal element trace detection.
Phytic acid (Phytate) be also known as creatine, inositol six it is complete-dihydrogen orthophosphate, it be primarily present in plant seed, Root is dry and stem in, wherein with the seed of leguminous plant, cereal wheat bran and plumule in content highest.Phytic acid is widely used It is general, as chelating agent, antioxidant, antistaling agent, the softening agent of water, fermentation accelerant, anticorrosive metal agent etc., it is suitable for food The industry fields such as product, medicine, paint, daily-use chemical industry, intermetallic composite coating, textile industry, plastics industry and Polymeric Industry.But In electrochemistry searching field using less.
Summary of the invention
In order to overcome the above problem, the sensitivity of detection is improved, the present invention improves electrode modified material, passes through Graphene oxide is bonded in glassy carbon electrode surface by the cementation of Nafion solution, but it was found that, works as the matter of Nafion After score is measured greater than 0.5%, the solubility of graphene oxide is deteriorated, and easily reunites, can not form uniform dispersion, The electric conductivity of electrode declines.Therefore, a certain amount of phytic acid is added in the present invention in Nafion solution, since it has 6 bands negative The phosphate groups of electricity, can uniformly be deposited among graphene sheet layer, the accumulation that can be effectively prevent between graphene nanometer sheet, And the dispersion degree of graphene oxide is improved, increase active surface area.In addition, the doping of phytic acid also effectively improves Nafion The electric conductivity of film constructs the structure carrier of multistage pore canal, makes full use of stone while not destroying Nafion membrane differential permeability The specific surface area of black alkene superelevation and excellent electric conductivity overcome the defect of Nafion membrane poorly conductive.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of graphene oxide and phytic acid modified electrode, comprising:
Glass-carbon electrode;
Coated in the graphene oxide on glass-carbon electrode-- Nafion layers of phytic acid;
The graphene oxide-- Nafion layers of phytic acid is uniformly mixed by graphene oxide, phytic acid, Nafion.
Preferably, in the graphene oxide-- Nafion layers of phytic acid, graphene oxide: phytic acid: the mass ratio of Nafion Are as follows: 4~5:1~2:1~2 × 103
The present invention tests discovery: graphene oxide: phytic acid: in Nafion three, when Nafion proportionality coefficient less than 1 × 103When the differential permeability that forms a film it is poor, the accuracy and precision decline of electrode;When Nafion proportionality coefficient is greater than 2 × 103 When, the electric conductivity decline of electrode, the dispersion of graphene oxide is uneven, easy to reunite.
In the graphene oxide-- Nafion layers of phytic acid, when the proportionality coefficient of phytic acid is greater than 2, the selected area update strategy of film forming Property decline, vulnerable to the interference of other impurities heavy metal ion, the chemical stability of film forming declines;When the proportionality coefficient of phytic acid is small When 1, effectively multistage pore canal system can not be formed, electrode conductivuty declines to a great extent.
The present invention also provides a kind of graphene oxides and phytic acid modified electrode sensor, by above-mentioned any electrode conduct Working electrode is prepared.
The present invention also provides the preparation methods of a kind of graphene oxide and phytic acid modified electrode, comprising:
By graphene oxide ultrasonic disperse in the mixed solution of phytic acid and Nafion, it is outstanding to obtain GO-Phytate-Nafion Turbid;
GO-Phytate-Nafion suspension is coated uniformly on polished, cleaning, drying treated glass-carbon electrode table Face is to get GO-Phytate-Nafion/GCE.
Preferably, in the GO-Phytate-Nafion suspension, graphene oxide;Phytic acid: the mass ratio of Nafion Are as follows: 4~5:1~2:1~2 × 103
Preferably, the concentration of phytic acid is 0.5~1.0mgL in the mixed solution of the phytic acid and Nafion-1, Nafion's Mass fraction is 0.5~1.0%.
A kind of the present invention also provides graphene oxide and phytic acid modified electrodes in detection water body trace heavy metal ion Electrochemical detection method, including
Using above-mentioned modified graphene oxide composite modified electrode as working electrode, using anodic stripping voltammetry, respectively Measure Heavy Metals in Waters ion.
Preferably, the heavy metal ion includes: copper, lead, zinc, iron, cobalt, nickel, manganese, cadmium, mercury, tungsten, molybdenum, gold, silver.
It is furthermore preferred that the heavy metal ion is lead.
Preferably, the detection parameters of the anodic stripping voltammetry are as follows:
Electro-deposition current potential -1.4V, electrodeposition time 180s;
Rest potential -1.35V, quiescent time 10s;
Sweep speed 5mV/s, scanning range -1.4V~-1.35V.
Preferably, acetate and 400 μ in the detection process of the anodic stripping voltammetry, in electrolyte containing 0.1M gL-1Phytate.It is found in present invention experiment: 400 μ gL being added in the electrolytic solution-1Phytate, detection accuracy raising 1.1~ 1.67% or so.This may be since the presence of phytate promotes enrichment and the dissolution efficiency of metal.
Research also shows: graphene oxide dispersion, plant acid solution, Nafion solution are sequentially coated at glass-carbon electrode table Face forms corresponding graphene oxide layer, phytic acid film layer, Nafion membrane layer, obtained multiple modification electrode and oxidation above-mentioned Graphene and phytic acid modified electrode testing result are roughly the same.
Therefore, the present invention also provides the multi-layered electrodes of a kind of graphene oxide and phytic acid modification, comprising:
Basal electrode;
It is set to the graphene oxide of basal electrode outer surface;
It is set to the phytic acid layer of graphene oxide outer surface;
It is set to the Nafion layer of phytic acid layer outer surface.
Preferably, the basal electrode is glass-carbon electrode.
The present invention also provides the electrochemical sensor of a kind of graphene oxide and phytic acid modification, the electrode sensor is Electrolytic cell, the electrolytic cell include: working electrode, and the working electrode is any above-mentioned multi-layered electrode, auxiliary electrode, reference Electrode, the electrolyte that electrolytic cell and bottom are set.
Preferably, the auxiliary electrode is platinum electrode.
Preferably, the reference electrode is calomel reference electrode
Preferably, magnetic stirring apparatus is additionally provided in the electrolytic cell.
Beneficial effects of the present invention:
1) by after modified graphene oxide composite material ultrasonic disperse, compound repair is prepared in glassy carbon electrode surface by adhesive Electrode is adornd, the electro-chemical test tested for next step.Under bottom liquid appropriate and applied voltage first by tested heavy metal ion Electrolysis is enriched on working electrode, scans applied voltage to positive direction, its oxidation is made to dissolve out to obtain an Anodic Stripping peak, It can be used as the qualitative and quantitative analysis of heavy metal ion according to spike potential and peak current.
2) graphene oxide composite material developed meets the requirement of Heavy Metals in Waters ion detection and depth removal.High The electrode material of electro-chemical activity is applied to the quick measurement of electrochemical sensor Heavy Metals in Waters, and sample treatment is simple, and It is at low cost, speed the advantages that detecting trace heavy metal simultaneously fastly, promote the hair of China's heavy metal water pollution detection and processing technique To there is very big economic and social benefit after opening up industrialization.
3) underwater trace heavy metal ion is detected using the glass-carbon electrode of grapheme material modification, wherein to lead ion (Pb2 +) and cadmium ion (Cd2+) detection limit respectively reach 0.2ug/L and 0.1ug/L.Good (the Na of selectivity+、Ca2+、K+、Al3+、Li+、 Cr3+Plasma is without response), the features such as stability is good, the glass-carbon electrode of prepared grapheme material modification can be used for environment It is measured while middle heavy metal ion content.
4) preparation method is simple, practical, easy to spread.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of Electrochemical Modification electrode of the invention.
Wherein, 1 be basal electrode (glass-carbon electrode), 2 be modification in basal electrode outer surface graphene oxide layer, 3 be Modify the phytic acid layer in graphene oxide layer outer surface, 4 be modification in the Nafion layer of phytic acid layer outer surface.
Specific embodiment
Below by embodiment, the invention will be further described.
Embodiment 1
It is 0.75% that mass fraction, which is added, in the aqueous solution (concentration 2.3mg/mL) of the graphene oxide of 1.0ml In Nafion solution (plant acid solution for being 0.5mg/L containing concentration), it is uniformly mixed and ultrasonic disperse 30min forms GO- Phytate-Nafion suspension.Glass-carbon electrode (diameter 3mm) is successively being contained into 0.3,0.05 μm of Al2O3The chamois leather upthrow of slurry Light is successively cleaned by ultrasonic in dehydrated alcohol, dust technology and secondary water later, is finally rinsed well with secondary water to mirror surface.Electricity Pole surface is with after being dried with nitrogen, and with micro syringe, 5 μ L GO-Phytate-Nafion suspensions are added dropwise in the heart in the electrodes, to molten After agent volatilization, electrode surface is rinsed with deionized water and is dried in air, it is complex film modified to obtain GO-Phytate-Nafion Glass-carbon electrode is labeled as GO-Phytate-Nafion/GCE.
Mercury, copper, lead, four kinds of ions of cadmium electrochemical gaging: four metal ion species of various concentration be separately added into pH be 4.5 Acetate buffer (concentration of acetate be 1mol/L, wherein containing concentration be 400 μ g/L Bi3+) in, utilize GO- Phytate-Nafion/GCE combination anodic stripping voltammetry is carried out while being measured to four kinds of ions.
Detection parameters are as follows:
Electro-deposition current potential -1.4V, electrodeposition time 180s;
Rest potential -1.35V, quiescent time 10s;
Sweep speed 5mV/s, scanning range -1.4V~-1.35V.
The result shows that: peak current is linearly increasing show the sensing electrode can successfully detect four kinds of metals of unknown concentration from Son, the modified electrode all have good linear dependence, the wider range of linearity, higher sensitivity to these four metal ions Low and low detection limit.
Electrochemical sensor detect mercury, copper, lead, four kinds of ions of cadmium Performance Evaluation: GO-Phytate-Nafion/GCE pairs Four kinds of mercury, copper, lead, cadmium ions have very strong selectivity, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma have compared with Strong anti-interference ability.Even if in various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. simultaneous complicated ring In border, GO-Phytate-Nafion/GCE to mercury, copper, lead, four kinds of ions of cadmium electrochemical response also without significant change, from And exclude the interference of some common zwitterions.
Wherein, to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit be respectively 0.201ug/L and 0.101ug/L.
Embodiment 2
It is 1.0% that mass fraction, which is added, in the aqueous solution (concentration 2.3mg/mL) of the graphene oxide of 1.25ml In Nafion solution (phytate for being 1.0mg/L containing concentration), it is uniformly mixed and ultrasonic disperse 30min forms GO- Phytate-Nafion suspension.Glass-carbon electrode (diameter 3mm) is successively being contained into 0.3,0.05 μm of Al2O3The chamois leather upthrow of slurry Light is successively cleaned by ultrasonic in dehydrated alcohol, dust technology and secondary water later, is finally rinsed well with secondary water to mirror surface.Electricity Pole surface is with after being dried with nitrogen, and with micro syringe, 5 μ LGO-Phytate-Nafion suspensions are added dropwise in the heart in the electrodes, to molten After agent volatilization, electrode surface is rinsed with deionized water and is dried in air, it is complex film modified to obtain GO-Phytate-Nafion Glass-carbon electrode is labeled as GO-Phytate-Nafion/GCE.
Mercury, copper, lead, four kinds of ions of cadmium electrochemical gaging: four metal ion species of various concentration be separately added into pH be 4.5 Acetate buffer (concentration of acetate be 1mol/L, wherein containing concentration be 400 μ g/L Phytate) in, utilize GO- Phytate-Nafion/GCE combination anodic stripping voltammetry is carried out while being measured to four kinds of ions,
Detection parameters are as follows:
Electro-deposition current potential -1.4V, electrodeposition time 180s;
Rest potential -1.35V, quiescent time 10s;
Sweep speed 5mV/s, scanning range -1.4V~-1.35V.
The result shows that: peak current is linearly increasing show the sensing electrode can successfully detect four kinds of metals of unknown concentration from Son, the modified electrode all have good linear dependence, the wider range of linearity, higher sensitivity to these four metal ions Low and low detection limit.
Electrochemical sensor detect mercury, copper, lead, four kinds of ions of cadmium Performance Evaluation: GO-Phytate-Nafion/GCE pairs Four kinds of mercury, copper, lead, cadmium ions have very strong selectivity, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma have compared with Strong anti-interference ability.Even if in various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. simultaneous complicated ring In border, GO-Phytate-Nafion/GCE to mercury, copper, lead, four kinds of ions of cadmium electrochemical response also without significant change, from And exclude the interference of some common zwitterions.
Wherein, to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit respectively reach 0.206ug/L and 0.103ug/L.
Embodiment 3
It is 0.8% that mass fraction, which is added, in the aqueous solution (concentration 2.3mg/mL) of the graphene oxide of 1.2ml In Nafion solution (plant acid solution for being 0.75mg/L containing concentration), it is uniformly mixed and ultrasonic disperse 30min forms GO- Phytate-Nafion suspension.Glass-carbon electrode (diameter 3mm) is successively being contained into 0.3,0.05 μm of Al2O3The chamois leather upthrow of slurry Light is successively cleaned by ultrasonic in dehydrated alcohol, dust technology and secondary water later, is finally rinsed well with secondary water to mirror surface.Electricity Pole surface is with after being dried with nitrogen, and with micro syringe, 5 μ L GO-Phytate-Nafion suspensions are added dropwise in the heart in the electrodes, to molten After agent volatilization, electrode surface is rinsed with deionized water and is dried in air, it is complex film modified to obtain GO-Phytate-Nafion Glass-carbon electrode is labeled as GO-Phytate-Nafion/GCE.
Mercury, copper, lead, four kinds of ions of cadmium electrochemical gaging: four metal ion species of various concentration be separately added into pH be 4.5 Acetate buffer (concentration of acetate be 1mol/L, wherein containing concentration be 400 μ g/L Phytate) in, utilize GO- Phytate-Nafion/GCE combination anodic stripping voltammetry is carried out while being measured to four kinds of ions,
Detection parameters are as follows:
Electro-deposition current potential -1.4V, electrodeposition time 180s;
Rest potential -1.35V, quiescent time 10s;
Sweep speed 5mV/s, scanning range -1.4V~-1.35V.
The result shows that: peak current is linearly increasing show the sensing electrode can successfully detect four kinds of metals of unknown concentration from Son, the modified electrode all have good linear dependence, the wider range of linearity, higher sensitivity to these four metal ions Low and low detection limit.
Electrochemical sensor detect mercury, copper, lead, four kinds of ions of cadmium Performance Evaluation: GO-Phytate-Nafion/GCE pairs Four kinds of mercury, copper, lead, cadmium ions have very strong selectivity, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma have compared with Strong anti-interference ability.Even if in various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. simultaneous complicated ring In border, GO-Phytate-Nafion/GCE to mercury, copper, lead, four kinds of ions of cadmium electrochemical response also without significant change, from And exclude the interference of some common zwitterions.
Wherein, to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit respectively reach 0.198ug/L and 0.099ug/L.
Embodiment 4
It is 0.8% that mass fraction, which is added, in the aqueous solution (concentration 2.3mg/mL) of the graphene oxide of 1.0ml In Nafion solution (plant acid solution for being 0.75mg/L containing concentration), it is uniformly mixed and ultrasonic disperse 30min forms GO- Phytate-Nafion suspension.Glass-carbon electrode (diameter 3mm) is successively being contained into 0.3,0.05 μm of Al2O3The chamois leather upthrow of slurry Light is successively cleaned by ultrasonic in dehydrated alcohol, dust technology and secondary water later, is finally rinsed well with secondary water to mirror surface.Electricity Pole surface is with after being dried with nitrogen, and with micro syringe, 5 μ LGO-Phytate-Nafion suspensions are added dropwise in the heart in the electrodes, to molten After agent volatilization, electrode surface is rinsed with deionized water and is dried in air, it is complex film modified to obtain GO-Phytate-Nafion Glass-carbon electrode is labeled as GO-Phytate-Nafion/GCE.
Mercury, copper, lead, four kinds of ions of cadmium electrochemical gaging: four metal ion species of various concentration be separately added into pH be 4.5 Acetate buffer (concentration of acetate be 1mol/L, wherein containing concentration be 400 μ g/L Phytate) in, utilize GO- Phytate-Nafion/GCE combination anodic stripping voltammetry is carried out while being measured to four kinds of ions,
Detection parameters are as follows:
Electro-deposition current potential -1.4V, electrodeposition time 180s;
Rest potential -1.35V, quiescent time 10s;
Sweep speed 5mV/s, scanning range -1.4V~-1.35V.
The result shows that: peak current is linearly increasing show the sensing electrode can successfully detect four kinds of metals of unknown concentration from Son, the modified electrode all have good linear dependence, the wider range of linearity, higher sensitivity to these four metal ions Low and low detection limit.
Electrochemical sensor detect mercury, copper, lead, four kinds of ions of cadmium Performance Evaluation: GO-Phytate-Nafion/GCE pairs Four kinds of mercury, copper, lead, cadmium ions have very strong selectivity, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma have compared with Strong anti-interference ability.Even if in various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. simultaneous complicated ring In border, GO-Phytate-Nafion/GCE to mercury, copper, lead, four kinds of ions of cadmium electrochemical response also without significant change, from And exclude the interference of some common zwitterions.
Wherein, to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit respectively reach 0.201ug/L and 0.098ug/L.
Embodiment 5
A kind of graphene oxide and phytic acid modified electrode, comprising:
Basal electrode 1;
It is set to the graphene oxide 2 of basal electrode outer surface;
It is set to the phytic acid layer 3 of graphene oxide outer surface;
It is set to the Nafion layer 4 of phytic acid layer outer surface.
Detection parameters are as follows:
Electro-deposition current potential -1.4V, electrodeposition time 180s;
Rest potential -1.35V, quiescent time 10s;
Sweep speed 5mV/s, scanning range -1.4V~-1.35V.
The result shows that: peak current is linearly increasing show the sensing electrode can successfully detect four kinds of metals of unknown concentration from Son, the modified electrode all have good linear dependence, the wider range of linearity, higher sensitivity to these four metal ions Low and low detection limit.
Electrochemical sensor detect mercury, copper, lead, four kinds of ions of cadmium Performance Evaluation: GO-Phytate-Nafion/GCE pairs Four kinds of mercury, copper, lead, cadmium ions have very strong selectivity, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma have compared with Strong anti-interference ability.Even if in various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. simultaneous complicated ring In border, GO-Phytate-Nafion/GCE to mercury, copper, lead, four kinds of ions of cadmium electrochemical response also without significant change, from And exclude the interference of some common zwitterions.
Wherein, to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit be respectively 0.201ug/L and 0.101ug/L.
Embodiment 6
A kind of graphene oxide and phytic acid modified electrode, comprising:
Glass-carbon electrode 1;
It is set to the graphene oxide 2 of glass-carbon electrode outer surface;
It is set to the phytic acid layer 3 of graphene oxide outer surface;
It is set to the Nafion layer 4 of phytic acid layer outer surface.
Embodiment 7
A kind of electrochemical sensor of graphene oxide and phytic acid modification, the electrode sensor is electrolytic cell, the electricity Xie Chi includes: working electrode, auxiliary electrode, reference electrode, the electrolyte that electrolytic cell and bottom is arranged in.
The working electrode is graphene oxide and phytic acid modified electrode, comprising:
Glass-carbon electrode 1;
It is set to the graphene oxide 2 of glass-carbon electrode outer surface;
It is set to the phytic acid layer 3 of graphene oxide outer surface;
It is set to the Nafion layer 4 of phytic acid layer outer surface.
Embodiment 8
A kind of electrochemical sensor of graphene oxide and phytic acid modification, the electrode sensor is electrolytic cell, the electricity Xie Chi includes: working electrode, auxiliary electrode, reference electrode, the electrolyte that electrolytic cell and bottom is arranged in.
The working electrode is graphene oxide and phytic acid modified electrode, comprising:
Glass-carbon electrode 1;
It is set to the graphene oxide 2 of glass-carbon electrode outer surface;
It is set to the phytic acid layer 3 of graphene oxide outer surface;
It is set to the Nafion layer 4 of phytic acid layer outer surface.
The auxiliary electrode is platinum electrode.
Embodiment 9
A kind of electrochemical sensor of graphene oxide and phytic acid modification, the electrode sensor is electrolytic cell, the electricity Xie Chi includes: working electrode, auxiliary electrode, reference electrode, the electrolyte that electrolytic cell and bottom is arranged in.
The working electrode is graphene oxide and phytic acid modified electrode, comprising:
Glass-carbon electrode 1;
It is set to the graphene oxide 2 of glass-carbon electrode outer surface;
It is set to the phytic acid layer 3 of graphene oxide outer surface;
It is set to the Nafion layer 4 of phytic acid layer outer surface.
The reference electrode is calomel reference electrode
Embodiment 10
A kind of electrochemical sensor of graphene oxide and phytic acid modification, the electrode sensor is electrolytic cell, the electricity Xie Chi includes: working electrode, auxiliary electrode, reference electrode, the electrolyte that electrolytic cell and bottom is arranged in.
The working electrode is graphene oxide and phytic acid modified electrode, comprising:
Glass-carbon electrode 1;
It is set to the graphene oxide 2 of glass-carbon electrode outer surface;
It is set to the phytic acid layer 3 of graphene oxide outer surface;
It is set to the Nafion layer 4 of phytic acid layer outer surface.
Magnetic stirring apparatus is additionally provided in the electrolytic cell.
Comparative example 1
Preparation method and detection method with embodiment 1, the difference is that, in the Nafion solution do not contain phytic acid. As the result is shown: catalysis jitter.
Comparative example 2
The preparation method is the same as that of Example 1, the difference is that, in detection process, pH is used to make for 4.5 acetate buffer Electrolyte.As the result is shown: to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit respectively reach 0.198ug/L and 0.98ug/ L.Comparative example 3
Prepare ammonium chloride-ammonia (NH of 0.05M4Cl-NH3) buffer solution, then with buffer 0.25mg/mL's Graphene oxide (GO) solution;Electrochemical reduction is carried out in above-mentioned mixed solution with current-time curvel method and is deposited, is deposited Current potential -1.3V, sedimentation time 400s, such nitrogen-doped graphene (NG) film is directly in the surface glass-carbon electrode (GCE).
Detection method is the same as embodiment 1.
The result shows that: Monitoring lower-cut: Hg2+For 0.1 μm of ol/L, Cu2+For 0.007 μm of ol/L, Pb2+And Cd2+It is 0.008 μ mol/L。
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still It can modify to technical solution documented by previous embodiment, or part is equivalently replaced.It is all in this hair Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention Within.Although above-mentioned in conjunction with specific embodiments of the present invention have been described, not to the limit of the scope of the present invention System, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art do not need to pay The various modifications or changes that creative work can be made out are still within protection scope of the present invention.

Claims (6)

1. a kind of detection Pb2+Graphene oxide and phytic acid modified electrode preparation method characterized by comprising
By graphene oxide ultrasonic disperse in the mixed solution of phytic acid and Nafion, GO-Phytate-Nafion suspension is obtained;
GO-Phytate-Nafion suspension is coated uniformly on polished, cleaning, drying treated glassy carbon electrode surface, Up to GO-Phytate-Nafion/GCE;In the GO-Phytate-Nafion suspension, graphene oxide;Phytic acid:
The mass ratio of Nafion are as follows: 4~5:1~2:1 × 103~2 × 103
The concentration of phytic acid is 0.5~1.0mgL in the phytic acid and Nafion mixed solution-1, the mass fraction of Nafion is 0.5 ~1.0%.
2. the modified electrode of method preparation described in claim 1.
3. modified electrode as claimed in claim 2, which is characterized in that the electrode can also be used in detect copper, zinc, iron, cobalt, nickel, Manganese, cadmium, mercury, tungsten, molybdenum, gold, silver.
4. a kind of graphene oxide described in claim 2 or 3 and phytic acid modified electrode in detection water body trace heavy metal from The electrochemical detection method of son characterized by comprising
Using graphene oxide described in claim 2 or 3 and phytic acid modified electrode as working electrode, using anodic stripping voltammetry Method measures Heavy Metals in Waters ion respectively.
5. method as claimed in claim 4, which is characterized in that the detection parameters of the anodic stripping voltammetry are as follows:
Electro-deposition current potential -1.4V, electrodeposition time 180s;
Rest potential -1.35V, quiescent time 10s;
Sweep speed 5mV/s, scanning range -1.4V~-1.35V;
Acetate and 500 μ gL in the detection process of the anodic stripping voltammetry, in electrolyte containing 0.1M-1Phytate。
6. the electrochemical sensor of a kind of graphene oxide and phytic acid modification, which is characterized in that
The electrochemical sensor is electrolytic cell, and the electrolytic cell includes: working electrode, auxiliary electrode, reference electrode and electrolysis Liquid;The working electrode is modified electrode as claimed in claim 2 or claim 3.
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