CN105928996A - Preparation of graphene oxide and polyaniline-modified electrode and assembled electrochemical detection device - Google Patents
Preparation of graphene oxide and polyaniline-modified electrode and assembled electrochemical detection device Download PDFInfo
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Abstract
The invention provides an electrochemical detection device prepared by a graphene oxide and polyaniline-modified electrode which is prepared by a novel electrode. Preparation of the graphene oxide and polyaniline-modified electrode comprises the following steps: ultrasonically dispersing graphene oxide in a mixed solution which contains polyaniline and Nafion to obtain GO-PAN-Nafion suspension; uniformly coating the surface of a glassy carbon electrode which is polished, cleaned and subjected to blow-drying treatment with the CO-PAN-Nafion suspension to obtain GO-PAN-Nafion/GCE. The developed and prepared graphene oxide material meets the requirements on detecting and deeply removing heavy metal ions in a water body. An electrode material with high electrochemical activity is applied to quick determination of heavy metals in the water body of an electrochemical sensor, has the advantages of easiness in sample treatment, low cost, high speed and capacity of detecting trace heavy metals simultaneously and the like, and has great economic and social benefits after promoting the development and industrialization of heavy metal water pollution detection and treatment technologies of China.
Description
Technical field
The invention belongs to analyze detection field, prepare graphene oxide and polyaniline modified electrode, and group particularly to novel electrode
The electrochemical detection device of dress.
Background technology
Chemically modified electrode is to carry out MOLECULE DESIGN by the method for chemical modification at electrode surface, will have excellent chemical character
Molecule, ion, polymer are fixed on electrode surface, cause certain micro structure, give electrode certain specific chemistry and electrochemistry
Character, in order to highly selective carries out desired reaction, has the superiority of uniqueness in terms of improving selectivity and sensitivity.
Utilize the multiple potential field that can utilize that the micro structure on chemically modified electrode surface is provided, make determinand carry out efficiently separating richness
Collection, and borrow and control electrode potential, improves selectivity further, simultaneously the susceptiveness of assay method and dressing agent chemical reaction
Selectivity combines, and becomes the ideal system that separation, enrichment and selectivity three are integrated.
Anodic stripping voltammetry (ASV) becomes the main electrochemical process of detection heavy metal ion, but traditional ASV mainly uses
Plating mercury film electrode is as working electrode, owing to hydrargyrum is very big, accordingly, it would be desirable to develop the electrode of novel environmental protection to the murder by poisoning of human body
Material pole replaces hydrargyrum.Because modified graphene oxide specific area is big, the absorption of carbonaceous material heavy metal ion occurs mainly in acid
In property functional group (carboxylic group and lactonic acid group), surface of graphene oxide contains substantial amounts of hydroxyl, carboxyl and oxygen-containing functional group,
Its surface has higher heavy metal ionic adsorption power, can promote the detection sensitivity of electrode.
Patent CN201510518917.5 discloses the electrochemical sensor of a kind of synchronous detecting hydrargyrum, copper, lead, cadmium ion content
Preparation method, utilizes the method for electrochemical deposition to be prepared by graphene oxide N doping modified glassy carbon electrode, at acetic acid/sodium acetate
For the solution of supporting electrolyte carries out Electrochemical Detection to hydrargyrum, copper, lead, four kinds of ions of cadmium.But detection limit is higher, it is impossible to full
The requirement of foot portions heavy metal element trace detection.
Polyaniline (PAN), the one of macromolecular compound, there is special electricity, optical property, doped after can have and lead
Electrically and chemical property.After certain process, the various equipment with specific function and material can be prepared, as can be as biology
Or the urease sensor of chemical sensor, electronic field emission source, more traditional lithium electrode material have more excellent in charge and discharge process
Different reversible electrode material, selective membrane material, antistatic and electromagnetic shielding material, conductive fiber, anti-corrosion material, etc.
Deng.Polyaniline because of its raw material having be easy to get, synthesis technique is simple, chemistry and the feature such as environmental stability is good and obtained extensive
Research and application.
Summary of the invention
In order to overcome the problems referred to above, improving the susceptiveness of detection, electrode modified material is improved by the present invention, passes through Nafion
Graphene oxide is bonded in glassy carbon electrode surface by the cementation of solution, but it was found that, when the mass fraction of Nafion is big
After 0.5%, the dissolubility of graphene oxide is deteriorated, and easily reunites, it is impossible to form uniform dispersion, the conduction of electrode
Property decline.Therefore, the present invention adds a certain amount of polyaniline in Nafion solution, due to its electron conjugated knot of non-localized P
Structure, can be uniformly deposited in the middle of graphene sheet layer after doping, can effectively prevent the accumulation between graphene nanometer sheet, and improve
The dispersion of graphene oxide, increases active surface area.It addition, the doping of polyaniline also effectively improves Nafion membrane
Electric conductivity, while not destroying Nafion membrane differential permeability, builds the structure carrier of multistage pore canal, makes full use of Graphene
The specific surface area of superelevation and excellent electric conductivity overcome the defect of Nafion membrane poorly conductive.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of graphene oxide and polyaniline modified electrode, including:
Glass-carbon electrode；
Graphene oxide-polyaniline-Nafion the layer being coated on glass-carbon electrode；
Described graphene oxide-polyaniline-Nafion layer is uniformly mixed by graphene oxide, polyaniline, Nafion.
Preferably, in described graphene oxide-polyaniline-Nafion layer, the mass ratio of graphene oxide: polyaniline: Nafion is:
4～5:1～2:1～2 × 103。
The present invention tests discovery: graphene oxide: polyaniline: in Nafion three, when Nafion proportionality coefficient is less than 1 × 103
Time film forming differential permeability poor, the accuracy and precision of electrode declines；When Nafion proportionality coefficient is more than 2 × 103Time,
The electric conductivity of electrode declines, and the dispersion of graphene oxide is uneven, easily reunites.
When the proportionality coefficient of polyaniline is more than 2, the differential permeability of film forming declines, is vulnerable to other impurity heavy metal ion
Interference, the chemical stability of film forming declines；When the proportionality coefficient of polyaniline is less than 1, it is impossible to form multistage pore canal body effectively
System, electrode conductivity declines to a great extent.
Present invention also offers a kind of graphene oxide and polyaniline modified electrode sensor, by above-mentioned arbitrary electrode as work
Electrode is prepared from.
Present invention also offers the preparation method of a kind of graphene oxide and polyaniline modified electrode, including:
By graphene oxide ultrasonic disperse in the mixed solution of polyaniline and Nafion, obtain GO-PANPAN-Nafion suspension；
GO-PAN-Nafion suspension is coated uniformly on polished, clean, dry up the glassy carbon electrode surface after process, to obtain final product
GO-PAN-Nafion/GCE。
Preferably, in described GO-PAN-Nafion suspension, graphene oxide；The mass ratio of polyaniline: Nafion is:
4～5:1～2:1～2 × 103。
Preferably, described polyaniline is 0.5～1.0mgL with the concentration of polyaniline in the mixed solution of Nafion-1, the matter of Nafion
Amount mark is 0.5～1.0%.
Present invention also offers a kind of graphene oxide and polyaniline modified electrode electrification of trace heavy metal ion in detection water body
Learn detection method, including
With above-mentioned modified graphene oxide composite modified electrode as working electrode, use anodic stripping voltammetry, measure water respectively
Heavy metal ion in body.
Preferably, described heavy metal ion includes: copper, lead, zinc, ferrum, cobalt, nickel, manganese, cadmium, hydrargyrum, tungsten, molybdenum, gold,
Silver.
It is furthermore preferred that described heavy metal ion is lead.
Preferably, the detection parameter of described anodic stripping voltammetry is:
Electro-deposition current potential-1.4V, electrodeposition time 180s；
Rest potential-1.35V, quiescent time 10s；
Sweep speed 5mV/s, sweep limits-1.4V～-1.35V.
Preferably, during the detection of described anodic stripping voltammetry, the acetate containing 0.1M and 400 μ gL in electrolyte-1
PAN.Present invention experiment finds: add 400 μ gL in the electrolytic solution-1PAN, accuracy of detection improves 1.2～about 1.7%.Can
Can be owing to the existence of polyaniline salt promotes enrichment and the dissolution efficiency of metal.
Research also shows: graphene oxide dispersion, polyaniline solutions, Nafion solution are sequentially coated at glassy carbon electrode surface,
Form corresponding graphene oxide layer, polyaniline film layer, Nafion membrane layer, the multiple modification electrode obtained and aforesaid oxidation stone
Ink alkene is roughly the same with polyaniline modified electrode testing result.
Therefore, present invention also offers the multi-layered electrode of a kind of graphene oxide and Polyaniline-modified, including:
Basal electrode；
It is arranged at the graphene oxide of basal electrode outer surface；
It is arranged at the polyaniline of graphene oxide outer surface；
It is arranged at the Nafion layer of polyaniline outer surface.
Preferably, described basal electrode is glass-carbon electrode.
Present invention also offers the electrochemical sensor of a kind of graphene oxide and Polyaniline-modified, described electrode sensor is electrolysis
Pond, described electrolyzer includes: working electrode, and described working electrode is arbitrary above-mentioned multi-layered electrode, auxiliary electrode, reference electricity
Pole, it is arranged on the electrolyte of electrolyzer and bottom.
Preferably, described auxiliary electrode is platinum electrode.
Preferably, described reference electrode is calomel reference electrode
Preferably, described electrolyzer is additionally provided with magnetic stirring apparatus.
Beneficial effects of the present invention:
1) by after modified graphene oxide composite material ultrasonic disperse, composite modified electrode is prepared by adhesive in glassy carbon electrode surface,
The electro-chemical test tested for next step.The first electrolysis under suitable end liquid and applied voltage of tested heavy metal ion is enriched in
On working electrode, then make applied voltage to positive scanning direction so that it is oxidation dissolution obtains an anodic stripping peak, according to spike potential
Can be as the qualitative and quantitative analysis of heavy metal ion with peak current.
2) graphene oxide composite material developed meets Heavy Metals in Waters ion detection and the requirement of degree of depth removal.High electrochemistry
The electrode material of activity is applied to the quick mensuration of electrochemical sensor Heavy Metals in Waters, and sample treatment is simple, and low cost,
Speed detects the advantages such as trace heavy metal the most simultaneously, after promoting the developing industry of China's heavy metal water pollution detection and treatment technology
To have the biggest economic and social benefit.
3) the glass-carbon electrode detection underwater trace heavy metal ion that grapheme material is modified is used, 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 all without response), the feature such as good stability, the glass-carbon electrode that prepared grapheme material is modified can be used in environment
Measure while heavy metal ion content.
4) preparation method is simple, practical, easy to spread.
Accompanying drawing explanation
Fig. 1 is the structural representation of the Electrochemical Modification electrode of the present invention.
Wherein, 1 it is basal electrode (glass-carbon electrode), 2 is to modify graphene oxide layer in basal electrode outer surface, 3 for modifying
In graphene oxide layer outer surface polyaniline, 4 be to modify the Nafion layer in polyaniline outer surface.
Detailed description of the invention
Below by embodiment, the invention will be further described.
Embodiment 1
The aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.0ml is added the Nafion that mass fraction is 0.75% molten
In liquid (being the polyaniline solutions of 0.5mg/L containing concentration), mix homogeneously ultrasonic disperse 30min form GO-PAN-Nafion
Suspension.By glass-carbon electrode (diameter 3mm) successively at the Al containing 0.3,0.05 μm2O3It is polished to minute surface on the chamois leather of slurry,
Ultrasonic cleaning in dehydrated alcohol, dust technology and secondary water the most successively, finally rinses well with secondary water.Electrode surface nitrogen
After air-blowing is dry, drip 5 μ L GO-PAN-Nafion suspensions with the microsyringe heart in the electrodes, after solvent volatilizees, spend
Ionized water rinses electrode surface and dries in atmosphere, obtains the complex film modified glass-carbon electrode of GO-PAN-Nafion, is labeled as
GO-PAN-Nafion/GCE。
Hydrargyrum, copper, lead, the electrochemical gaging of four kinds of ions of cadmium: it is 4.5 that four metal ion species of variable concentrations are separately added into pH
(concentration of acetate is 1mol/L to acetate buffer, wherein contains the Bi that concentration is 400 μ g/L3+In), utilize
GO-PAN-Nafion/GCE combines anodic stripping voltammetry measure four kinds of ions simultaneously.
Detection parameter is:
Electro-deposition current potential-1.4V, electrodeposition time 180s；
Rest potential-1.35V, quiescent time 10s；
Sweep speed 5mV/s, sweep limits-1.4V～-1.35V.
Result shows: linearly increasing four metal ion species showing that this sensing electrode can successfully detect unknown concentration of peak current, should
Modified electrode is respectively provided with good linear dependence, the wider range of linearity to these four metal ion, and higher sensitivity is low and low
Detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-PAN-Nafion/GCE to hydrargyrum, copper,
Lead, four kinds of ions of cadmium have the strongest selectivity, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma has relatively
Strong capacity of resisting disturbance.Even if at various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. simultaneous complexity
In environment, GO-PAN-Nafion/GCE does not has significant change to hydrargyrum, copper, lead, the electrochemical response of four kinds of ions of cadmium yet, from
And get rid of the interference of some common zwitterions.
Wherein, to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit be respectively 0.211ug/L and 0.111ug/L.
Embodiment 2
The aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.25ml is added the Nafion that mass fraction is 1.0% molten
In liquid (being the polyaniline salt of 1.0mg/L containing concentration), mix homogeneously ultrasonic disperse 30min form GO-PAN-Nafion
Suspension.By glass-carbon electrode (diameter 3mm) successively at the Al containing 0.3,0.05 μm2O3It is polished to minute surface on the chamois leather of slurry,
Ultrasonic cleaning in dehydrated alcohol, dust technology and secondary water the most successively, finally rinses well with secondary water.Electrode surface nitrogen
After air-blowing is dry, drip 5 μ LGO-PAN-Nafion suspensions with the microsyringe heart in the electrodes, after solvent volatilizees, spend
Ionized water rinses electrode surface and dries in atmosphere, obtains the complex film modified glass-carbon electrode of GO-PAN-Nafion, is labeled as
GO-PAN-Nafion/GCE。
Hydrargyrum, copper, lead, the electrochemical gaging of four kinds of ions of cadmium: it is 4.5 that four metal ion species of variable concentrations are separately added into pH
In acetate buffer (concentration of acetate is 1mol/L, wherein contains the PAN that concentration is 400 μ g/L), utilize GO-PAN
-Nafion/GCE combines anodic stripping voltammetry measure four kinds of ions simultaneously,
Detection parameter is:
Electro-deposition current potential-1.4V, electrodeposition time 180s；
Rest potential-1.35V, quiescent time 10s；
Sweep speed 5mV/s, sweep limits-1.4V～-1.35V.
Result shows: linearly increasing four metal ion species showing that this sensing electrode can successfully detect unknown concentration of peak current, should
Modified electrode is respectively provided with good linear dependence, the wider range of linearity to these four metal ion, and higher sensitivity is low and low
Detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-PAN-Nafion/GCE to hydrargyrum,
Copper, lead, four kinds of ions of cadmium have the strongest selectivity, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma has
There is stronger capacity of resisting disturbance.Even if at various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. simultaneous
In complex environment, GO-PAN-Nafion/GCE does not has significant change to hydrargyrum, copper, lead, the electrochemical response of four kinds of ions of cadmium yet,
Thus get rid of the interference of some common zwitterions.
Wherein, to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit respectively reach 0.216ug/L and 0.113ug/L.
Embodiment 3
The aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.2ml is added the Nafion that mass fraction is 0.8% molten
In liquid (being the polyaniline solutions of 0.75mg/L containing concentration), mix homogeneously ultrasonic disperse 30min form GO-PAN-Nafion
Suspension.By glass-carbon electrode (diameter 3mm) successively at the Al containing 0.3,0.05 μm2O3It is polished to minute surface on the chamois leather of slurry,
Ultrasonic cleaning in dehydrated alcohol, dust technology and secondary water the most successively, finally rinses well with secondary water.Electrode surface nitrogen
After air-blowing is dry, drip 5 μ L GO-PAN-Nafion suspensions with the microsyringe heart in the electrodes, after solvent volatilizees, spend
Ionized water rinses electrode surface and dries in atmosphere, obtains the complex film modified glass-carbon electrode of GO-PAN-Nafion, is labeled as
GO-PAN-Nafion/GCE。
Hydrargyrum, copper, lead, the electrochemical gaging of four kinds of ions of cadmium: it is 4.5 that four metal ion species of variable concentrations are separately added into pH
In acetate buffer (concentration of acetate is 1mol/L, wherein contains the PAN that concentration is 400 μ g/L), utilize
GO-PAN-Nafion/GCE combines anodic stripping voltammetry measure four kinds of ions simultaneously,
Detection parameter is:
Electro-deposition current potential-1.4V, electrodeposition time 180s；
Rest potential-1.35V, quiescent time 10s；
Sweep speed 5mV/s, sweep limits-1.4V～-1.35V.
Result shows: linearly increasing four metal ion species showing that this sensing electrode can successfully detect unknown concentration of peak current, should
Modified electrode is respectively provided with good linear dependence, the wider range of linearity to these four metal ion, and higher sensitivity is low and low
Detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-PAN-Nafion/GCE to hydrargyrum, copper,
Lead, four kinds of ions of cadmium have the strongest selectivity, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma has relatively
Strong capacity of resisting disturbance.Even if at various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. simultaneous complexity
In environment, GO-PAN-Nafion/GCE does not has significant change to hydrargyrum, copper, lead, the electrochemical response of four kinds of ions of cadmium yet, from
And get rid of the interference of some common zwitterions.
Wherein, to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit respectively reach 0.208ug/L and 0.109ug/L.
Embodiment 4
The aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.0ml is added the Nafion that mass fraction is 0.8% molten
In liquid (being the polyaniline solutions of 0.75mg/L containing concentration), mix homogeneously ultrasonic disperse 30min form GO-PAN-Nafion
Suspension.By glass-carbon electrode (diameter 3mm) successively at the Al containing 0.3,0.05 μm2O3It is polished to minute surface on the chamois leather of slurry,
Ultrasonic cleaning in dehydrated alcohol, dust technology and secondary water the most successively, finally rinses well with secondary water.Electrode surface nitrogen
After air-blowing is dry, drip 5 μ LGO-PAN-Nafion suspensions with the microsyringe heart in the electrodes, after solvent volatilizees, spend
Ionized water rinses electrode surface and dries in atmosphere, obtains the complex film modified glass-carbon electrode of GO-PAN-Nafion, is labeled as
GO-PAN-Nafion/GCE。
Hydrargyrum, copper, lead, the electrochemical gaging of four kinds of ions of cadmium: it is 4.5 that four metal ion species of variable concentrations are separately added into pH
In acetate buffer (concentration of acetate is 1mol/L, wherein contains the PAN that concentration is 400 μ g/L), utilize
GO-PAN-Nafion/GCE combines anodic stripping voltammetry measure four kinds of ions simultaneously,
Detection parameter is:
Electro-deposition current potential-1.4V, electrodeposition time 180s；
Rest potential-1.35V, quiescent time 10s；
Sweep speed 5mV/s, sweep limits-1.4V～-1.35V.
Result shows: linearly increasing four metal ion species showing that this sensing electrode can successfully detect unknown concentration of peak current, should
Modified electrode is respectively provided with good linear dependence, the wider range of linearity to these four metal ion, and higher sensitivity is low and low
Detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-PAN-Nafion/GCE to hydrargyrum, copper,
Lead, four kinds of ions of cadmium have the strongest selectivity, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma has relatively
Strong capacity of resisting disturbance.Even if at various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. simultaneous complexity
In environment, GO-PAN-Nafion/GCE does not has significant change to hydrargyrum, copper, lead, the electrochemical response of four kinds of ions of cadmium yet, from
And get rid of the interference of some common zwitterions.
Wherein, to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit respectively reach 0.211ug/L and 0.108ug/L.
Embodiment 5
A kind of graphene oxide and polyaniline modified electrode, including:
Basal electrode 1；
It is arranged at the graphene oxide 2 of basal electrode outer surface；
It is arranged at the polyaniline 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of polyaniline outer surface.
Detection parameter is:
Electro-deposition current potential-1.4V, electrodeposition time 180s；
Rest potential-1.35V, quiescent time 10s；
Sweep speed 5mV/s, sweep limits-1.4V～-1.35V.
Result shows: linearly increasing four metal ion species showing that this sensing electrode can successfully detect unknown concentration of peak current, should
Modified electrode is respectively provided with good linear dependence, the wider range of linearity to these four metal ion, and higher sensitivity is low and low
Detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-PAN-Nafion/GCE to hydrargyrum, copper,
Lead, four kinds of ions of cadmium have the strongest selectivity, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma has relatively
Strong capacity of resisting disturbance.Even if at various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. simultaneous complexity
In environment, GO-PAN-Nafion/GCE does not has significant change to hydrargyrum, copper, lead, the electrochemical response of four kinds of ions of cadmium yet, from
And get rid of the interference of some common zwitterions.
Wherein, to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit be respectively 0.211ug/L and 0.111ug/L.
Embodiment 6
A kind of graphene oxide and polyaniline modified electrode, including:
Glass-carbon electrode 1；
It is arranged at the graphene oxide 2 of glass-carbon electrode outer surface；
It is arranged at the polyaniline 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of polyaniline outer surface.
Embodiment 7
A kind of graphene oxide and the electrochemical sensor of Polyaniline-modified, described electrode sensor is electrolyzer, described electrolyzer
Including: working electrode, auxiliary electrode, reference electrode, it is arranged on the electrolyte of electrolyzer and bottom.
Described working electrode is graphene oxide and polyaniline modified electrode, including:
Glass-carbon electrode 1；
It is arranged at the graphene oxide 2 of glass-carbon electrode outer surface；
It is arranged at the polyaniline 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of polyaniline outer surface.
Embodiment 8
A kind of graphene oxide and the electrochemical sensor of Polyaniline-modified, described electrode sensor is electrolyzer, described electrolyzer
Including: working electrode, auxiliary electrode, reference electrode, it is arranged on the electrolyte of electrolyzer and bottom.
Described working electrode is graphene oxide and polyaniline modified electrode, including:
Glass-carbon electrode 1；
It is arranged at the graphene oxide 2 of glass-carbon electrode outer surface；
It is arranged at the polyaniline 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of polyaniline outer surface.
Described auxiliary electrode is platinum electrode.
Embodiment 9
A kind of graphene oxide and the electrochemical sensor of Polyaniline-modified, described electrode sensor is electrolyzer, described electrolyzer
Including: working electrode, auxiliary electrode, reference electrode, it is arranged on the electrolyte of electrolyzer and bottom.
Described working electrode is graphene oxide and polyaniline modified electrode, including:
Glass-carbon electrode 1；
It is arranged at the graphene oxide 2 of glass-carbon electrode outer surface；
It is arranged at the polyaniline 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of polyaniline outer surface.
Described reference electrode is calomel reference electrode
Embodiment 10
A kind of graphene oxide and the electrochemical sensor of Polyaniline-modified, described electrode sensor is electrolyzer, described electrolyzer
Including: working electrode, auxiliary electrode, reference electrode, it is arranged on the electrolyte of electrolyzer and bottom.
Described working electrode is graphene oxide and polyaniline modified electrode, including:
Glass-carbon electrode 1；
It is arranged at the graphene oxide 2 of glass-carbon electrode outer surface；
It is arranged at the polyaniline 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of polyaniline outer surface.
Described electrolyzer is additionally provided with magnetic stirring apparatus.
Comparative example 1
Preparation method and detection method are with embodiment 1, and difference is, do not contain polyaniline in described Nafion solution.Knot
Fruit display: catalysis jitter.
Comparative example 2
Preparation method is with embodiment 1, and difference is, during detection, the acetate buffer using pH to be 4.5 makees electricity
Solve liquid.Result shows: to lead ion (Pb2+) and cadmium ion (Cd2+) detection limit respectively reach 0.198ug/L and 0.98ug/L.
Comparative example 3
Ammonium chloride-ammonia (the NH of preparation 0.05M4Cl-NH3) buffer solution, then with the oxidation stone of this buffer 0.25mg/mL
Ink alkene (GO) solution；In above-mentioned mixed solution, carry out electrochemical reduction by current-time curvel method and deposit, sedimentation potential-1.3V,
Sedimentation time 400s, such nitrogen-doped graphene (NG) thin film directly becomes glass-carbon electrode (GCE) surface.
Detection method is with embodiment 1.
Result shows: Monitoring lower-cut: Hg2+It is 0.1 μm ol/L, Cu2+It is 0.007 μm ol/L, Pb2+And Cd2+It is 0.008 μm ol/L.
Finally should be noted that and the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, to the greatest extent
The present invention has been described in detail by pipe with reference to previous embodiment, and for a person skilled in the art, it still can be right
Technical scheme described in previous embodiment is modified, or wherein part is carried out equivalent.All spirit in the present invention
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.On
Although state combination the detailed description of the invention of the present invention is described, but not limiting the scope of the invention, affiliated neck
Field technique personnel should be understood that on the basis of technical scheme, and those skilled in the art need not pay creative labor
The dynamic various amendments that can make or deformation are still within protection scope of the present invention.
Claims (10)
1. a graphene oxide and polyaniline modified electrode, it is characterised in that including:
Glass-carbon electrode；
Graphene oxide-polyaniline-Nafion the layer being coated on glass-carbon electrode；
Described graphene oxide-polyaniline-Nafion layer is uniformly mixed by graphene oxide, polyaniline salt, Nafion.
2. graphene oxide as claimed in claim 1 and polyaniline modified electrode, it is characterised in that described graphene oxide-poly-
In aniline-Nafion layer, the mass ratio of graphene oxide: polyaniline: Nafion is: 4～5:1～2:1～2 × 103。
3. a graphene oxide and polyaniline modified electrode sensor, it is characterised in that include that claim 1 or 2 is arbitrary described
Electrode.
4. the preparation method of the electrode described in a claim 1 or 2, it is characterised in that including:
By graphene oxide ultrasonic disperse in the mixed solution of polyaniline and Nafion, obtain GO-PAN-Nafion suspension；
GO-PAN-Nafion suspension is coated uniformly on polished, clean, dry up the glassy carbon electrode surface after process, to obtain final product
GO-PAN-Nafion/GCE。
5. method as claimed in claim 4, it is characterised in that in described GO-PAN-Nafion suspension, graphene oxide；
The mass ratio of polyaniline: Nafion is: 4～5:1～2:1～2 × 103；
Or described polyaniline is 0.5～1.0mgL with the concentration of polyaniline in Nafion mixed solution-1, the mass fraction of Nafion is
0.5～1.0%.
6. a graphene oxide and polyaniline modified electrode electrochemical detection method for trace heavy metal ion in detection water body, its
It is characterised by, including:
With the electrode described in claim 1 or 2 as working electrode, use anodic stripping voltammetry, measure a huge sum of money in water body respectively
Belong to ion.
7. method as claimed in claim 6, it is characterised in that described heavy metal ion includes: copper, lead, zinc, ferrum, cobalt,
Nickel, manganese, cadmium, hydrargyrum, tungsten, molybdenum, gold, silver.
8. method as claimed in claim 6, it is characterised in that the detection parameter of described anodic stripping voltammetry is:
Electro-deposition current potential-1.4V, electrodeposition time 180s；
Rest potential-1.35V, quiescent time 10s；
Sweep speed 5mV/s, sweep limits-1.4V～-1.35V；
During the detection of described anodic stripping voltammetry, the acetate containing 0.1M and 500 μ gL in electrolyte-1PAN。
9. a graphene oxide and polyaniline modified electrode, it is characterised in that including:
Basal electrode；
It is arranged at the graphene oxide of basal electrode outer surface；
It is arranged at the polyaniline of graphene oxide outer surface；
It is arranged at the Nafion layer of polyaniline outer surface.
10. a graphene oxide and the electrochemical sensor of Polyaniline-modified, it is characterised in that
Described electrode sensor is electrolyzer, and described electrolyzer includes: working electrode, and described working electrode is such as claim 9
Described modified electrode, auxiliary electrode, reference electrode, it is arranged on the electrolyte of electrolyzer and bottom.
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| CN107115850B (en) * | 2017-06-14 | 2019-08-27 | 山东省科学院新材料研究所 | The sodium alginate gel ball of graphene oxide-polyaniline compound synthesis removes the adsorptivity of lead in water body and cadmium heavy metal ion |
| CN108823594A (en) * | 2018-05-30 | 2018-11-16 | 中氧科技（广州）有限公司 | A kind of preparation method of the modified membrane electrode of the graphene being used to prepare ozone |
| CN108823594B (en) * | 2018-05-30 | 2020-10-09 | 中氧科技（广州）有限公司 | Preparation method of graphene modified membrane electrode for preparing ozone |
| CN110514726A (en) * | 2019-07-29 | 2019-11-29 | 宁德师范学院 | For dopamine, the Fe-PANI/Au modified electrode of uric acid Sensitive Detection and its preparation |
| CN110514726B (en) * | 2019-07-29 | 2021-08-13 | 宁德师范学院 | Fe-PANI/Au modified electrode for sensitive detection of dopamine and uric acid and preparation thereof |
| CN112067680A (en) * | 2020-09-17 | 2020-12-11 | 吉林化工学院 | Graphene oxide/enzyme/polyaniline LB modified electrode and preparation method and application thereof |
| CN112067680B (en) * | 2020-09-17 | 2022-09-23 | 吉林化工学院 | Graphene oxide/enzyme/polyaniline LB modified electrode and preparation method and application thereof |
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