CN205749393U - Graphene oxide and phytic acid modified electrode and electrochemical sensor thereof - Google Patents
Graphene oxide and phytic acid modified electrode and electrochemical sensor thereof Download PDFInfo
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- CN205749393U CN205749393U CN201620571459.1U CN201620571459U CN205749393U CN 205749393 U CN205749393 U CN 205749393U CN 201620571459 U CN201620571459 U CN 201620571459U CN 205749393 U CN205749393 U CN 205749393U
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Abstract
This utility model provides a kind of graphene oxide and phytic acid modified electrode and electrochemical sensor thereof, including: basal electrode；It is arranged at the graphene oxide of basal electrode outer surface；It is arranged at the phytic acid layer of graphene oxide outer surface；It is arranged at the Nafion layer of phytic acid layer outer surface.Described electrode sensor is electrolyzer, and described electrolyzer includes: working electrode, and described working electrode is above-mentioned modified electrode, auxiliary electrode, reference electrode, is arranged on the electrolyte of electrolyzer and bottom.The graphene oxide composite material developed meets Heavy Metals in Waters ion detection and the requirement of degree of depth removal.The electrode material of high electro-chemical activity is applied to the quick mensuration of electrochemical sensor Heavy Metals in Waters, sample treatment is simple, and low cost, speed detects the advantages such as trace heavy metal the most simultaneously, promotes that China's heavy metal water pollution detection will have the biggest economic and social benefit after the developing industry for the treatment of technology.
Description
Technical field
This utility model belongs to analysis detection field, particularly to preparing graphene oxide and the assembling of phytic acid modified electrode
Electrochemical detection device.
Background technology
Chemically modified electrode is to carry out MOLECULE DESIGN by the method for chemical modification at electrode surface, will have excellent chemical
The molecule of character, ion, polymer are fixed on electrode surface, cause certain micro structure, give certain specific chemistry of electrode and
Electrochemical properties, in order to highly selective carries out desired reaction, has uniqueness in terms of improving selectivity and sensitivity
Superiority.Utilize the multiple potential field that can utilize that the micro structure on chemically modified electrode surface is provided, make determinand have
The separation and concentration of effect, and borrow control electrode potential, improve selectivity further, simultaneously susceptiveness and the dressing agent of assay method
The selectivity of chemical reaction 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 is main
Employing plating mercury film electrode is as working electrode, owing to hydrargyrum is very big to the murder by poisoning of human body, accordingly, it would be desirable to develop novel environmental protection
Electrode material pole replaces hydrargyrum.Because modified graphene oxide specific area is big, the absorption of carbonaceous material heavy metal ion is mainly sent out
Raw on acidic functionality (carboxylic group and lactonic acid group), surface of graphene oxide contains substantial amounts of hydroxyl, carboxyl and contains
Oxygen functional group, its surface has higher heavy metal ionic adsorption power, can promote the detection sensitivity of electrode.
Patent CN201510518917.5 discloses a kind of synchronous detecting hydrargyrum, copper, lead, the electrochemical sensing of cadmium ion content
The preparation method of device, utilizes the method for electrochemical deposition that prepared by graphene oxide N doping modified glassy carbon electrode, acetic acid/
Sodium acetate be supporting electrolyte solution in hydrargyrum, copper, lead, four kinds of ions of cadmium are carried out Electrochemical Detection.But detection limit is relatively low, nothing
Method meets the requirement of part heavy metal element trace detection.
Phytic acid (Phytate) also known as creatine, cyclohexanhexanol six complete-dihydrogen orthophosphate, it be primarily present in plant seed,
Root is done and in stem, wherein the highest with content in fabaceous seed, the wheat bran of corn and plumule.The application of phytic acid is the widest
General, as chelating agen, antioxidant, antistaling agent, water correction agent, fermentation accelerant, anticorrosive metal agent etc., it is adaptable to food
The industry fields such as product, medicine, paint, daily-use chemical industry, intermetallic composite coating, textile industry, plastics industry and Polymeric Industry.But
Less in the use of electrochemistry searching field.
Utility model content
In order to overcome the problems referred to above, improving the susceptiveness of detection, electrode modified material is improved by this utility model, logical
Graphene oxide is bonded in glassy carbon electrode surface by the cementation crossing Nafion solution, but it was found that, when Nafion's
After mass fraction is more than 0.5%, the dissolubility of graphene oxide is deteriorated, and easily reunites, it is impossible to form uniform dispersion
System, the electric conductivity of electrode declines, and therefore, this utility model adds a certain amount of phytic acid in Nafion solution, owing to it has 6
Individual electronegative phosphate groups, it is possible to be deposited on uniformly in the middle of graphene sheet layer, can effectively prevent between graphene nanometer sheet
Accumulation, and improve the dispersion of graphene oxide, increase active surface area.It addition, the doping of phytic acid is also effectively improved
The electric conductivity of Nafion membrane, while do not destroy Nafion membrane differential permeability, builds the structure carrier of multistage pore canal, fills
The specific surface area of Graphene superelevation and excellent electric conductivity point is utilized to overcome the defect of Nafion membrane poorly conductive.
To achieve these goals, this utility model adopts the following technical scheme that
A kind of graphene oxide and phytic acid modified electrode, including:
Basal electrode；
It is arranged at the graphene oxide of basal electrode outer surface；
It is arranged at the phytic acid layer of graphene oxide outer surface；
It is arranged at the Nafion layer of phytic acid layer outer surface.
Preferably, described basal electrode is glass-carbon electrode.
Preferably, the thickness of described phytic acid layer and Nafion layer is than for 0.9:0102.
The painting method of the phytic acid layer during this is novel may is that deposition is having the electrode of graphene oxide be immersed in phytic acid
In solution, process after 30-60min, static, clean, dry, to obtain final product.
This utility model additionally provides the electrochemical sensor that a kind of graphene oxide is modified with phytic acid, and described electrochemistry passes
Sensor is electrolyzer, and described electrolyzer includes: working electrode, and described working electrode is arbitrary above-mentioned modified electrode, auxiliary electricity
Pole, reference electrode, 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.
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, the multiple modification electrode obtained and aforesaid oxidation
Graphene is roughly the same with phytic acid modified electrode testing result.
Therefore, this utility model additionally provides a kind of graphene oxide and phytic acid modified electrode, including:
Glass-carbon electrode；
The graphene oxide being coated on glass-carbon electrode-phytic acid-Nafion layer；
Described graphene oxide-phytic acid-Nafion layer is uniformly mixed by graphene oxide, phytic acid, Nafion.
Preferably, in described graphene oxide-phytic acid-Nafion layer, the mass ratio of graphene oxide: phytic acid: Nafion
For: 4～5:1～2:1～2 × 103。
This utility model experiment finds: graphene oxide: phytic acid: in Nafion three, when Nafion proportionality coefficient is less than 1
×103Time film forming differential permeability poor, the accuracy and precision of electrode declines；When Nafion proportionality coefficient more than 2 ×
103Time, the electric conductivity of electrode declines, and the dispersion of graphene oxide is uneven, easily reunites.
In described graphene oxide-phytic acid-Nafion layer, when the proportionality coefficient of phytic acid is more than 2, the selected area update strategy of film forming
Property decline, be vulnerable to the interference of other impurity heavy metal ion, the chemical stability of film forming declines；When the proportionality coefficient of phytic acid is little
In 1 time, it is impossible to form multistage pore canal system effectively, electrode conductivity declines to a great extent.
This utility model additionally provides a kind of graphene oxide and modifies electrochemical sensor with phytic acid, by above-mentioned arbitrary electricity
Pole is prepared from as working electrode.
This utility model additionally provides the preparation method of a kind of graphene oxide and phytic acid modified electrode, including:
By graphene oxide ultrasonic disperse in the mixed solution of phytic acid and Nafion, obtain GO-Phytate-Nafion and hang
Turbid liquid；
GO-Phytate-Nafion suspension is coated uniformly on polished, clean, dry up the glass-carbon electrode table after process
Face, obtains GO-Phytate-Nafion/GCE.
Preferably, in described GO-Phytate-Nafion suspension, graphene oxide；The mass ratio of phytic acid: Nafion
For: 4～5:1～2:1～2 × 103。
Preferably, described phytic acid is 0.5～1.0mg L with the concentration of phytic acid in the mixed solution of Nafion-1, Nafion's
Mass fraction is 0.5～1.0%.
This utility model additionally provides a kind of graphene oxide and phytic acid modified electrode trace heavy metal in detection water body
The electrochemical detection method of ion, including:
With above-mentioned modified graphene oxide composite modified electrode as working electrode, use anodic stripping voltammetry, respectively
Measure Heavy Metals in Waters ion.
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 g in electrolyte
L-1Phytate.This utility model experiment finds: add 400 μ g L in the electrolytic solution-1Phytate, accuracy of detection improves 1.1
～about 1.67%.The existence being likely due to phytate promotes enrichment and the dissolution efficiency of metal.
The beneficial effects of the utility model:
1) by after modified graphene oxide composite material ultrasonic disperse, compound repairing is prepared by adhesive in glassy carbon electrode surface
Decorations electrode, the electro-chemical test tested for next step.By tested heavy metal ion elder generation under suitable end liquid and applied voltage
Electrolysis is enriched on working electrode, then makes applied voltage to positive scanning direction so that it is oxidation dissolution obtains an anodic stripping peak,
Can be as the qualitative and quantitative analysis of heavy metal ion according to spike potential and peak current.
2) graphene oxide composite material developed meets Heavy Metals in Waters ion detection and the requirement of degree of depth removal.High
The electrode material of electro-chemical 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, and the heavy metal water pollution detection of promotion China is sent out with treatment technology
The biggest economic and social benefit will be had after exhibition industrialization.
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 0.202ug/L and 0.098ug/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 for
Environment measures while heavy metal ion content.
4) preparation method is simple, practical, easy to spread.
Accompanying drawing explanation
Fig. 1 is the structural representation of Electrochemical Modification electrode of the present utility model.Wherein: 1 is basal electrode (glass carbon electricity
Pole), 2 is to modify the graphene oxide layer in basal electrode outer surface, and 3 is to modify in the phytic acid of graphene oxide layer outer surface
Layer.4 for modify in the Nafion layer of phytic acid layer outer surface.
Detailed description of the invention
Below by embodiment, the utility model is described in further detail.
Embodiment 1
A kind of graphene oxide and phytic acid modified electrode, including:
Basal electrode 1；
It is arranged at the graphene oxide 2 of basal electrode outer surface；
It is arranged at the phytic acid layer 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of phytic acid layer 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: peak current is linearly increasing show this sensing electrode can successfully detect four kinds of metals of unknown concentration from
Son, this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity to these four metal ion
Low and low detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE pair
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 complicated ring
In border, GO-Phytate-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 0.201ug/L and 0.101ug/L.
Embodiment 2
A kind of graphene oxide and phytic acid 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 phytic acid layer 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of phytic acid layer outer surface.
Embodiment 3
A kind of graphene oxide and phytic acid modified electrode, including:
Basal electrode 1；
It is arranged at the graphene oxide 2 of basal electrode outer surface；
It is arranged at the phytic acid layer 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of phytic acid layer outer surface.
The thickness of described phytic acid layer and Nafion layer is than for 0.9:0102.
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: peak current is linearly increasing show this sensing electrode can successfully detect four kinds of metals of unknown concentration from
Son, this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity to these four metal ion
Low and low detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE pair
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 complicated ring
In border, GO-Phytate-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 0.191ug/L and 0.991ug/L.
Embodiment 4
The electrochemical sensor that a kind of graphene oxide is modified with phytic acid, described electrochemical sensor is electrolyzer, described
Electrolyzer includes: working electrode, auxiliary electrode, reference electrode, be arranged on the electrolyte of electrolyzer and bottom.
Described working electrode is graphene oxide and phytic acid 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 phytic acid layer 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of phytic acid layer outer surface.
Embodiment 5
The electrochemical sensor that a kind of graphene oxide is modified with phytic acid, described electrochemical sensor is electrolyzer, described
Electrolyzer includes: working electrode, auxiliary electrode, reference electrode, be arranged on the electrolyte of electrolyzer and bottom.
Described working electrode is graphene oxide and phytic acid 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 phytic acid layer 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of phytic acid layer outer surface.
Described auxiliary electrode is platinum electrode.
Embodiment 6
The electrochemical sensor that a kind of graphene oxide is modified with phytic acid, described electrochemical sensor is electrolyzer, described
Electrolyzer includes: working electrode, auxiliary electrode, reference electrode, be arranged on the electrolyte of electrolyzer and bottom.
Described working electrode is graphene oxide and phytic acid 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 phytic acid layer 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of phytic acid layer outer surface.
Described reference electrode is calomel reference electrode
Embodiment 7
The electrochemical sensor that a kind of graphene oxide is modified with phytic acid, described electrochemical sensor is electrolyzer, described
Electrolyzer includes: working electrode, auxiliary electrode, reference electrode, be arranged on the electrolyte of electrolyzer and bottom.
Described working electrode is graphene oxide and phytic acid 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 phytic acid layer 3 of graphene oxide outer surface；
It is arranged at the Nafion layer 4 of phytic acid layer outer surface.
Described electrolyzer is additionally provided with magnetic stirring apparatus.
Embodiment 8
A kind of graphene oxide and phytic acid modified electrode, including:
Indium-tin oxide electrode；
It is arranged at the graphene oxide of indium-tin oxide electrode outer surface；
It is arranged at the zinc oxide of surface of graphene oxide
It is arranged at the Nafion layer 4 of graphene oxide 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: peak current is linearly increasing show this sensing electrode can successfully detect four kinds of metals of unknown concentration from
Son, this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity to these four metal ion
Low and low detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE pair
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 complicated ring
In border, GO-Phytate-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 0.101ug/L and 0.157ug/L.
Embodiment 9
The aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.0ml is added mass fraction is 0.75%
In Nafion solution (being the plant acid solution of 0.5mg/L containing concentration), mix homogeneously ultrasonic disperse 30min form GO-
Phytate-Nafion suspension.By glass-carbon electrode (diameter 3mm) successively at the Al containing 0.3,0.05 μm2O3The chamois leather upthrow of slurry
Light to minute surface, ultrasonic cleaning in dehydrated alcohol, dust technology and secondary water the most successively, finally rinse well with secondary water.Electricity
After surface, pole nitrogen dries up, drip 5 μ L GO-Phytate-Nafion suspensions with the microsyringe heart in the electrodes, treat molten
After agent volatilization, with deionized water rinsing electrode surface and dry in atmosphere, obtain GO-Phytate-Nafion complex film modified
Glass-carbon electrode, is labeled as GO-Phytate-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
Acetate buffer (concentration of acetate is 1mol/L, wherein contains the Bi that concentration is 400 μ g/L3+In), utilize GO-
Phytate-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: peak current is linearly increasing show this sensing electrode can successfully detect four kinds of metals of unknown concentration from
Son, this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity to these four metal ion
Low and low detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE pair
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 complicated ring
In border, GO-Phytate-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 0.201ug/L and 0.101ug/L.
Embodiment 10
The aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.25ml is added mass fraction is 1.0%
In Nafion solution (being the phytate of 1.0mg/L containing concentration), mix homogeneously ultrasonic disperse 30min form GO-
Phytate-Nafion suspension.By glass-carbon electrode (diameter 3mm) successively at the Al containing 0.3,0.05 μm2O3The chamois leather upthrow of slurry
Light to minute surface, ultrasonic cleaning in dehydrated alcohol, dust technology and secondary water the most successively, finally rinse well with secondary water.Electricity
After surface, pole nitrogen dries up, drip 5 μ LGO-Phytate-Nafion suspensions with the microsyringe heart in the electrodes, treat molten
After agent volatilization, with deionized water rinsing electrode surface and dry in atmosphere, obtain GO-Phytate-Nafion complex film modified
Glass-carbon electrode, is labeled as GO-Phytate-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
Acetate buffer (concentration of acetate is 1mol/L, wherein contains the Phytate that concentration is 400 μ g/L) in, utilize GO-
Phytate-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: peak current is linearly increasing show this sensing electrode can successfully detect four kinds of metals of unknown concentration from
Son, this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity to these four metal ion
Low and low detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE pair
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 complicated ring
In border, GO-Phytate-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 0.206ug/L and 0.103ug/L.
Embodiment 11
The aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.2ml is added mass fraction is 0.8%
In Nafion solution (being the plant acid solution of 0.75mg/L containing concentration), mix homogeneously ultrasonic disperse 30min form GO-
Phytate-Nafion suspension.By glass-carbon electrode (diameter 3mm) successively at the Al containing 0.3,0.05 μm2O3The chamois leather upthrow of slurry
Light to minute surface, ultrasonic cleaning in dehydrated alcohol, dust technology and secondary water the most successively, finally rinse well with secondary water.Electricity
After surface, pole nitrogen dries up, drip 5 μ L GO-Phytate-Nafion suspensions with the microsyringe heart in the electrodes, treat molten
After agent volatilization, with deionized water rinsing electrode surface and dry in atmosphere, obtain GO-Phytate-Nafion complex film modified
Glass-carbon electrode, is labeled as GO-Phytate-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
Acetate buffer (concentration of acetate is 1mol/L, wherein contains the Phytate that concentration is 400 μ g/L) in, utilize GO-
Phytate-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: peak current is linearly increasing show this sensing electrode can successfully detect four kinds of metals of unknown concentration from
Son, this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity to these four metal ion
Low and low detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE pair
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 complicated ring
In border, GO-Phytate-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 0.198ug/L and 0.099ug/L.
Embodiment 12
The aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.0ml is added mass fraction is 0.8%
In Nafion solution (being the plant acid solution of 0.75mg/L containing concentration), mix homogeneously ultrasonic disperse 30min form GO-
Phytate-Nafion suspension.By glass-carbon electrode (diameter 3mm) successively at the Al containing 0.3,0.05 μm2O3The chamois leather upthrow of slurry
Light to minute surface, ultrasonic cleaning in dehydrated alcohol, dust technology and secondary water the most successively, finally rinse well with secondary water.Electricity
After surface, pole nitrogen dries up, drip 5 μ LGO-Phytate-Nafion suspensions with the microsyringe heart in the electrodes, treat molten
After agent volatilization, with deionized water rinsing electrode surface and dry in atmosphere, obtain GO-Phytate-Nafion complex film modified
Glass-carbon electrode, is labeled as GO-Phytate-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
Acetate buffer (concentration of acetate is 1mol/L, wherein contains the Phytate that concentration is 400 μ g/L) in, utilize
GO-Phytate-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: peak current is linearly increasing show this sensing electrode can successfully detect four kinds of metals of unknown concentration from
Son, this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity to these four metal ion
Low and low detection limit.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE pair
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 complicated ring
In border, GO-Phytate-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 0.201ug/L and 0.098ug/L.
Comparative example 1
Preparation method and detection method are with embodiment 1, and difference is, do not contain phytic acid in described Nafion solution.
Result shows: 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 is made
Electrolyte.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 this buffer 0.25mg/mL's
Graphene oxide (GO) solution；In above-mentioned mixed solution, carry out electrochemical reduction by current-time curvel method and deposit, deposition
Current 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 μ
mol/L。
Finally should be noted that and the foregoing is only preferred embodiment of the present utility model, be not limited to
This utility model, although being described in detail this utility model with reference to previous embodiment, for those skilled in the art
For Yuan, the technical scheme described in previous embodiment still can be modified by it, or is equal to wherein part
Replace.All within spirit of the present utility model and principle, any modification, equivalent substitution and improvement etc. made, should be included in
Within protection domain of the present utility model.Although detailed description of the invention of the present utility model is described by above-mentioned combination, but
The not restriction to this utility model protection domain, one of ordinary skill in the art should be understood that technical side of the present utility model
On the basis of case, those skilled in the art need not to pay various amendments or deformation that creative work can make still in this reality
Within novel protection domain.
Claims (7)
1. a graphene oxide and phytic acid 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 phytic acid layer of graphene oxide outer surface；
It is arranged at the Nafion layer of phytic acid layer outer surface.
2. graphene oxide as claimed in claim 1 and phytic acid modified electrode, it is characterised in that described basal electrode is glass carbon
Electrode.
3. graphene oxide as claimed in claim 1 and phytic acid modified electrode, it is characterised in that described phytic acid layer and Nafion
The thickness of layer ratio is for 0.9:0102.
4. the electrochemical sensor that a graphene oxide is modified with phytic acid, it is characterised in that
Described electrochemical sensor is electrolyzer, and described electrolyzer includes: working electrode, and described working electrode is such as claim
Modified electrode described in any one of 1-3, auxiliary electrode, reference electrode, it is arranged on the electrolyte of electrolyzer and bottom.
5. electrochemical sensor as claimed in claim 4, it is characterised in that described auxiliary electrode is platinum electrode.
6. electrochemical sensor as claimed in claim 4, it is characterised in that described reference electrode is calomel reference electrode.
7. electrochemical sensor as claimed in claim 4, its feature exists, and is additionally provided with magnetic stirring apparatus in described electrolyzer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106018532A (en) * | 2016-06-13 | 2016-10-12 | 山东省科学院新材料研究所 | Preparation of graphene oxide and phytate modified electrode and electrochemical detection device assembled by graphene oxide and phytate modified electrode |
| CN108467033A (en) * | 2018-03-13 | 2018-08-31 | 镇江致达新材料科技有限公司 | A kind of preparation method of bionic laminar nano composite film |
| CN111650259A (en) * | 2020-06-24 | 2020-09-11 | 南京大学 | Electrochemical sensor for simultaneously detecting multiple ions in trace manner |
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2016
- 2016-06-13 CN CN201620571459.1U patent/CN205749393U/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106018532A (en) * | 2016-06-13 | 2016-10-12 | 山东省科学院新材料研究所 | Preparation of graphene oxide and phytate modified electrode and electrochemical detection device assembled by graphene oxide and phytate modified electrode |
| CN106018532B (en) * | 2016-06-13 | 2019-01-22 | 山东省科学院新材料研究所 | The electrochemical detection device of preparation and the assembling of graphene oxide and phytic acid modified electrode |
| CN108467033A (en) * | 2018-03-13 | 2018-08-31 | 镇江致达新材料科技有限公司 | A kind of preparation method of bionic laminar nano composite film |
| CN111650259A (en) * | 2020-06-24 | 2020-09-11 | 南京大学 | Electrochemical sensor for simultaneously detecting multiple ions in trace manner |
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