CN106018532A - Preparation of graphene oxide and phytate modified electrode and electrochemical detection device assembled by graphene oxide and phytate modified electrode - Google Patents
Preparation of graphene oxide and phytate modified electrode and electrochemical detection device assembled by graphene oxide and phytate modified electrode Download PDFInfo
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Abstract
The invention provides novel electrode preparation, and discloses an electrochemical detection device prepared from a graphene oxide and phytate modified electrode. A preparation method includes the steps that graphene oxide is dispersed into a mixed solution containing phytate and Nafion under ultrasound, and GO-Phytate-Nafion suspension is obtained; the polished, cleaned and blow-dried surface of a glassy carbon electrode is uniformly coated with the GO-Phytate-Nafion suspension, and a GO-Phytate-Nafion-GCE is obtained. The prepared graphene oxide material meets the requirements for detection and deep removal of heavy metal ions in water. The electrode material with high electrochemical activity has the advantages of being simple in sample treatment, low in cost, high in speed, capable of detecting trace heavy metal and the like when applied to rapid determination of heavy metal in water through electrochemical transducers, and can bring great economic and social benefits after promoting the development and industrialization of the heavy metal water pollution detection and treatment technology in China.
Description
Technical field
The invention belongs to analyze detection field, prepare graphene oxide and phytic acid modified electrode, and the electrochemical detection device assembled particularly to novel electrode.
Background technology
Chemically modified electrode is to carry out MOLECULE DESIGN by the method for chemical modification at electrode surface, by having the molecule of excellent chemical character, ion, polymer are fixed on electrode surface, cause certain micro structure, give electrode certain specific chemistry and electrochemical properties, so that highly selective carries out desired reaction, there is in terms of improving selectivity and sensitivity the superiority of uniqueness.Utilize the multiple potential field that can utilize that the micro structure on chemically modified electrode surface is provided, determinand is made to carry out efficiently separating enrichment, and borrow control electrode potential, improve selectivity further, the susceptiveness of assay method and the selectivity of dressing agent chemical reaction are combined simultaneously, become 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 as working electrode, owing to hydrargyrum is very big to the murder by poisoning of human body, accordingly, it would be desirable to the electrode material pole developing novel environmental protection replaces hydrargyrum.Because modified graphene oxide specific area is big, the absorption of carbonaceous material heavy metal ion occurs mainly in (carboxylic group and lactonic acid group) on acidic functionality, 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 preparation method of the electrochemical sensor of a kind of synchronous detecting hydrargyrum, copper, lead, cadmium ion content, graphene oxide N doping is prepared modified glassy carbon electrode by the method utilizing electrochemical deposition, in the solution that acetic acid/sodium acetate is supporting electrolyte, hydrargyrum, copper, lead, four kinds of ions of cadmium is carried out Electrochemical Detection.But detection limit is higher, it is impossible to meet the requirement of part heavy metal element trace detection.
Phytic acid (Phytate) also known as creatine, cyclohexanhexanol six complete-dihydrogen orthophosphate, it is primarily present in that the seed of plant, root be dry and in stem, wherein the highest with content in fabaceous seed, the wheat bran of corn and plumule.The application of phytic acid is widely, as chelating agen, antioxidant, antistaling agent, water correction agent, fermentation accelerant, anticorrosive metal agent etc., it is adaptable to industry fields such as food, medicine, paint, daily-use chemical industry, intermetallic composite coating, textile industry, plastics industry and Polymeric Industries.But it is less in the use of electrochemistry searching field.
Summary of the invention
In order to overcome the problems referred to above, improve the susceptiveness of detection, electrode modified material is improved by the present invention, by the cementation of Nafion solution graphene oxide is bonded in glassy carbon electrode surface, but it was found that, after the mass fraction of Nafion is more than 0.5%, the dissolubility of graphene oxide is deteriorated, easily reuniting, it is impossible to form uniform dispersion, the electric conductivity of electrode declines.Therefore, the present invention adds a certain amount of phytic acid in Nafion solution, owing to it has 6 electronegative phosphate groups, can be deposited in the middle of graphene sheet layer uniformly, can effectively prevent the accumulation between graphene nanometer sheet, and improve the dispersion of graphene oxide, increase active surface area.Additionally, the doping of phytic acid also effectively improves the electric conductivity of Nafion membrane, while not destroying Nafion membrane differential permeability, build the structure carrier of multistage pore canal, make full use of the specific surface area of Graphene superelevation and excellent electric conductivity overcomes 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 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 is: 4～5:1～2:1～2 × 103。
The present invention tests discovery: 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 is 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 differential permeability of film forming declines, is vulnerable to the interference of other impurity heavy metal ion, and the chemical stability of film forming declines；When the proportionality coefficient of phytic acid is less than 1, it is impossible to forming multistage pore canal system effectively, electrode conductivity declines to a great extent.
Present invention also offers a kind of graphene oxide and phytic acid modified electrode sensor, above-mentioned arbitrary electrode be prepared from as working electrode.
Present invention also offers 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 suspension；
GO-Phytate-Nafion suspension is coated uniformly on polished, clean, dry up the glassy carbon electrode surface after process, obtain GO-Phytate-Nafion/GCE.
Preferably, in described GO-Phytate-Nafion suspension, graphene oxide；The mass ratio of phytic acid: Nafion is: 4～5:1～2:1～2 × 103。
Preferably, described phytic acid is 0.5～1.0mgL with the concentration of phytic acid in the mixed solution of Nafion-1, the mass fraction of Nafion is 0.5～1.0%.
Present invention also offers a kind of graphene oxide and phytic acid modified electrode electrochemical detection method of trace heavy metal ion in detection water body, including
With above-mentioned modified graphene oxide composite modified electrode as working electrode, use anodic stripping voltammetry, measure Heavy Metals in Waters ion respectively.
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-1Phytate.Present invention experiment finds: add 400 μ gL in the electrolytic solution-1Phytate, accuracy of detection improves 1.1～about 1.67%.This existence being likely due to phytate promotes enrichment and the dissolution efficiency of metal.
Research also shows: graphene oxide dispersion, plant acid solution, Nafion solution are sequentially coated at glassy carbon electrode surface, forming corresponding graphene oxide layer, phytic acid film layer, Nafion membrane layer, the multiple modification electrode obtained is roughly the same with phytic acid modified electrode testing result with aforesaid graphene oxide.
Therefore, present invention also offers the multi-layered electrode that a kind of graphene oxide is modified with phytic acid, 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.
Present invention also offers the electrochemical sensor that a kind of graphene oxide is modified with phytic acid, described electrode sensor is electrolyzer, described electrolyzer includes: working electrode, and described working electrode is arbitrary above-mentioned multi-layered electrode, auxiliary electrode, reference electrode, 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 on working electrode, then make applied voltage to positive scanning direction, make it aoxidize dissolution and obtain 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.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.
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 for measuring while heavy metal ion content in environment.
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 be basal electrode (glass-carbon electrode), 2 be modify graphene oxide layer in basal electrode outer surface, 3 be modify phytic acid layer in graphene oxide layer outer surface, 4 be to modify in the Nafion layer of phytic acid layer outer surface.
Detailed description of the invention
Below by embodiment, the invention will be further described.
Embodiment 1
Being added by the aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.0ml in the Nafion solution (being the plant acid solution of 0.5mg/L containing concentration) that mass fraction is 0.75%, 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 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 rinse well with secondary water.After electrode surface nitrogen dries up, 5 μ L GO-Phytate-Nafion suspensions are dripped with the microsyringe heart in the electrodes, after solvent volatilizees, with deionized water rinsing electrode surface and dry in atmosphere, obtain the complex film modified glass-carbon electrode of GO-Phytate-Nafion, be labeled as GO-Phytate-Nafion/GCE.
Hydrargyrum, copper, lead, the electrochemical gaging of four kinds of ions of cadmium: four metal ion species of variable concentrations are separately added into the acetate buffer that pH is 4.5, and (concentration of acetate is 1mol/L, wherein contains the Bi that concentration is 400 μ g/L3+In), utilize GO-Phytate-Nafion/GCE to combine anodic stripping voltammetry and four kinds of ions are measured 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, and this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity low and low detection limit to these four metal ion.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE have the strongest selectivity to hydrargyrum, copper, lead, four kinds of ions of cadmium, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma has stronger capacity of resisting disturbance.Even if at various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. in simultaneous complex environment, GO-Phytate-Nafion/GCE does not has significant change to hydrargyrum, copper, lead, the electrochemical response of four kinds of ions of cadmium yet, thus gets 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
Being added by the aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.25ml in the Nafion solution (being the phytate of 1.0mg/L containing concentration) that mass fraction is 1.0%, 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 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 rinse well with secondary water.After electrode surface nitrogen dries up, 5 μ LGO-Phytate-Nafion suspensions are dripped with the microsyringe heart in the electrodes, after solvent volatilizees, with deionized water rinsing electrode surface and dry in atmosphere, obtain the complex film modified glass-carbon electrode of GO-Phytate-Nafion, be labeled as GO-Phytate-Nafion/GCE.
Hydrargyrum, copper, lead, the electrochemical gaging of four kinds of ions of cadmium: four metal ion species of variable concentrations are separately added into the acetate buffer that pH is 4.5, and (concentration of acetate is 1mol/L, wherein contain the Phytate that concentration is 400 μ g/L) in, utilize GO-Phytate-Nafion/GCE to combine anodic stripping voltammetry four kinds of ions are measured 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, and this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity low and low detection limit to these four metal ion.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE have the strongest selectivity to hydrargyrum, copper, lead, four kinds of ions of cadmium, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma has stronger capacity of resisting disturbance.Even if at various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. in simultaneous complex environment, GO-Phytate-Nafion/GCE does not has significant change to hydrargyrum, copper, lead, the electrochemical response of four kinds of ions of cadmium yet, thus gets 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 3
Being added by the aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.2ml in the Nafion solution (being the plant acid solution of 0.75mg/L containing concentration) that mass fraction is 0.8%, 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 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 rinse well with secondary water.After electrode surface nitrogen dries up, 5 μ L GO-Phytate-Nafion suspensions are dripped with the microsyringe heart in the electrodes, after solvent volatilizees, with deionized water rinsing electrode surface and dry in atmosphere, obtain the complex film modified glass-carbon electrode of GO-Phytate-Nafion, be labeled as GO-Phytate-Nafion/GCE.
Hydrargyrum, copper, lead, the electrochemical gaging of four kinds of ions of cadmium: four metal ion species of variable concentrations are separately added into the acetate buffer that pH is 4.5, and (concentration of acetate is 1mol/L, wherein contain the Phytate that concentration is 400 μ g/L) in, utilize GO-Phytate-Nafion/GCE to combine anodic stripping voltammetry four kinds of ions are measured 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, and this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity low and low detection limit to these four metal ion.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE have the strongest selectivity to hydrargyrum, copper, lead, four kinds of ions of cadmium, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma has stronger capacity of resisting disturbance.Even if at various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. in simultaneous complex environment, GO-Phytate-Nafion/GCE does not has significant change to hydrargyrum, copper, lead, the electrochemical response of four kinds of ions of cadmium yet, thus gets 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 4
Being added by the aqueous solution (concentration is 2.3mg/mL) of the graphene oxide of 1.0ml in the Nafion solution (being the plant acid solution of 0.75mg/L containing concentration) that mass fraction is 0.8%, 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 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 rinse well with secondary water.After electrode surface nitrogen dries up, 5 μ LGO-Phytate-Nafion suspensions are dripped with the microsyringe heart in the electrodes, after solvent volatilizees, with deionized water rinsing electrode surface and dry in atmosphere, obtain the complex film modified glass-carbon electrode of GO-Phytate-Nafion, be labeled as GO-Phytate-Nafion/GCE.
Hydrargyrum, copper, lead, the electrochemical gaging of four kinds of ions of cadmium: four metal ion species of variable concentrations are separately added into the acetate buffer that pH is 4.5, and (concentration of acetate is 1mol/L, wherein contain the Phytate that concentration is 400 μ g/L) in, utilize GO-Phytate-Nafion/GCE to combine anodic stripping voltammetry four kinds of ions are measured 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, and this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity low and low detection limit to these four metal ion.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE have the strongest selectivity to hydrargyrum, copper, lead, four kinds of ions of cadmium, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma has stronger capacity of resisting disturbance.Even if at various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. in simultaneous complex environment, GO-Phytate-Nafion/GCE does not has significant change to hydrargyrum, copper, lead, the electrochemical response of four kinds of ions of cadmium yet, thus gets 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.
Embodiment 5
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: linearly increasing four metal ion species showing that this sensing electrode can successfully detect unknown concentration of peak current, and this modified electrode is respectively provided with good linear dependence, the wider range of linearity, higher sensitivity low and low detection limit to these four metal ion.
Electrochemical sensor detection hydrargyrum, copper, lead, the Performance Evaluation of four kinds of ions of cadmium: GO-Phytate-Nafion/GCE have the strongest selectivity to hydrargyrum, copper, lead, four kinds of ions of cadmium, and to Na+、Ca2+、K+、Al3+、Li+、Cr3+Plasma has stronger capacity of resisting disturbance.Even if at various zwitterions, such as Br-、Cl-、NO3-、H2PO4-、SO4 2-Etc. in simultaneous complex environment, GO-Phytate-Nafion/GCE does not has significant change to hydrargyrum, copper, lead, the electrochemical response of four kinds of ions of cadmium yet, thus gets 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 6
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 7
The electrochemical sensor that a kind of graphene oxide and phytic acid are modified, described electrode sensor is electrolyzer, and 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 8
The electrochemical sensor that a kind of graphene oxide and phytic acid are modified, described electrode sensor is electrolyzer, and 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 9
The electrochemical sensor that a kind of graphene oxide and phytic acid are modified, described electrode sensor is electrolyzer, and 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 10
The electrochemical sensor that a kind of graphene oxide and phytic acid are modified, described electrode sensor is electrolyzer, and 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.
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 makees 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 graphene oxide (GO) solution of this buffer 0.25mg/mL；Carrying out electrochemical reduction in above-mentioned mixed solution 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, the foregoing is only the preferred embodiments of the present invention, it is not limited to the present invention, although the present invention being described in detail with reference to previous embodiment, for a person skilled in the art, technical scheme described in previous embodiment still can be modified by it, or wherein part is carried out equivalent.All within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.Although the detailed description of the invention of the present invention is described by above-mentioned combination; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme, those skilled in the art need not to pay various amendments or deformation that creative work can make still within protection scope of the present invention.
Claims (10)
1. a graphene oxide and phytic acid modified electrode, it is characterised in that 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, phytate, Nafion.
2. graphene oxide as claimed in claim 1 and phytic acid modified electrode, it is characterised in that described graphene oxide-phytic acid
In-Nafion layer, the mass ratio of graphene oxide: phytic acid: Nafion is: 4～5:1～2:1～2 × 103。
3. a graphene oxide and phytic acid modified electrode sensor, it is characterised in that include the arbitrary described electricity of claim 1 or 2
Pole.
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 phytic acid and Nafion, obtain GO-Phytate-Nafion suspension；
GO-Phytate-Nafion suspension is coated uniformly on polished, clean, dry up the glassy carbon electrode surface after process, i.e.
Obtain GO-Phytate-Nafion/GCE.
5. method as claimed in claim 4, it is characterised in that in described GO-Phytate-Nafion suspension, graphite oxide
Alkene；The mass ratio of phytic acid: Nafion is: 4～5:1～2:1～2 × 103；
Or described phytic acid is 0.5～1.0mgL with the concentration of phytic acid in Nafion mixed solution-1, the mass fraction of Nafion is
0.5～1.0%.
6. a graphene oxide and phytic acid modified electrode electrochemical detection method for trace heavy metal ion in detection water body, it is special
Levy and be, 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-1Phytate。
9. 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.
10. the electrochemical sensor that a graphene oxide is modified with phytic acid, 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109374707A (en) * | 2018-11-16 | 2019-02-22 | 肇庆学院 | A method of with carboxylated carbon nanosheet@carboxylated graphene composite film electrochemical sensor trace fluoride worm nitrile |
| CN110371964A (en) * | 2019-07-17 | 2019-10-25 | 中国科学院金属研究所 | A kind of preparation method of the graphene oxide composite material of nanoscale piece diameter size |
| CN110724424A (en) * | 2019-10-14 | 2020-01-24 | 浙江海洋大学 | Antifouling coating for marine mesh wire and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008154452A1 (en) * | 2007-06-07 | 2008-12-18 | Anne Schwartz | Systems and methods of removing and managing heavy metals |
| CN101915790A (en) * | 2010-07-09 | 2010-12-15 | 上海师范大学 | Method for preparing phytic acid micelle modified hydrogen peroxide sensor |
| CN103399063A (en) * | 2013-08-07 | 2013-11-20 | 上海师范大学 | Graphene nano material-modified glassy carbon electrode based on phytic acid dispersion, preparation method and application |
| CN103940882A (en) * | 2014-04-18 | 2014-07-23 | 上海师范大学 | Sensor for detecting trace copper ions in water sample and construction method thereof |
| CN104391030A (en) * | 2014-12-17 | 2015-03-04 | 济南大学 | Preparation method and application of sensor for heavy metal ions Cd2+, Pb2+ and Cu2+ built based on alginic acid functionalized graphene |
| CN205749393U (en) * | 2016-06-13 | 2016-11-30 | 山东省科学院新材料研究所 | Graphene oxide and phytic acid modified electrode and electrochemical sensor thereof |
-
2016
- 2016-06-13 CN CN201610424736.0A patent/CN106018532B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008154452A1 (en) * | 2007-06-07 | 2008-12-18 | Anne Schwartz | Systems and methods of removing and managing heavy metals |
| CN101915790A (en) * | 2010-07-09 | 2010-12-15 | 上海师范大学 | Method for preparing phytic acid micelle modified hydrogen peroxide sensor |
| CN103399063A (en) * | 2013-08-07 | 2013-11-20 | 上海师范大学 | Graphene nano material-modified glassy carbon electrode based on phytic acid dispersion, preparation method and application |
| CN103940882A (en) * | 2014-04-18 | 2014-07-23 | 上海师范大学 | Sensor for detecting trace copper ions in water sample and construction method thereof |
| CN104391030A (en) * | 2014-12-17 | 2015-03-04 | 济南大学 | Preparation method and application of sensor for heavy metal ions Cd2+, Pb2+ and Cu2+ built based on alginic acid functionalized graphene |
| CN205749393U (en) * | 2016-06-13 | 2016-11-30 | 山东省科学院新材料研究所 | Graphene oxide and phytic acid modified electrode and electrochemical sensor thereof |
Non-Patent Citations (1)
| Title |
|---|
| HONGXIU DAI等: "An electrochemical sensor based on phytic acid functionalized polypyrrole/graphene oxide nanocomposites for simultaneous determination of Cd(II) and Pb(II)", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109374707A (en) * | 2018-11-16 | 2019-02-22 | 肇庆学院 | A method of with carboxylated carbon nanosheet@carboxylated graphene composite film electrochemical sensor trace fluoride worm nitrile |
| CN110371964A (en) * | 2019-07-17 | 2019-10-25 | 中国科学院金属研究所 | A kind of preparation method of the graphene oxide composite material of nanoscale piece diameter size |
| CN110724424A (en) * | 2019-10-14 | 2020-01-24 | 浙江海洋大学 | Antifouling coating for marine mesh wire and preparation method thereof |
| CN110724424B (en) * | 2019-10-14 | 2022-03-25 | 浙江海洋大学 | Antifouling coating for marine mesh wire and preparation method thereof |
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