CN103913492A - Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode as well as preparation method and application thereof - Google Patents
Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode. The preparation method comprises the following steps: selecting a glassy carbon electrode and carrying out surface treatment on the glassy carbon electrode; dropping graphene dispersion liquid on the surface of the glassy carbon electrode and putting the glassy carbon electrode under an infrared lamp to be dried to prepare a graphene modified electrode; immersing the prepared graphene modified electrode into a sulfuric acid solution containing polypyrrole and Keggin type heteropoly acid; scanning by using a cyclic voltammetry; after scanning, taking out the graphene modified electrode and eluting with water for the second time; drying at room temperature to obtain the Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode. The Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode prepared by the preparation method has a sensitive inhibition effect based on an oxidization reduction reaction of folic acid on the Keggin type heteropoly acid and can be used for determining the folic acid; compared with a common electrode, the Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode has the advantages of small over-potential, high sensitivity, good stability, high reproducibility and the like; a preparation process is simple, raw materials are easy to obtain and the cost is low.
Description
Technical field
The present invention relates to a kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode, relate to the preparation method and application of this modified electrode simultaneously.
Background technology
Folic acid (FA) is a kind of water soluble vitamin of extensive existence, is a kind of important electroactive material in human body hemopoietic system, and plays critical effect.In the time lacking FA in human body, can cause that a series of disease is as anaemia, neurasthenia, congenital malformation, and can increase the probability of heart disease and stroke.Report shows, in pregnant woman's body, the low meeting of folate content causes fetal anomaly and affects bone and the growth of brain.So sensitive and accurate detection FA has caused people's great attention.At present, the method for some traditional detection FA is in the news, for example: high performance liquid chromatography, spectrophotometric method, fluorescence etc.But there is complicated, time-consuming, high in cost of production shortcoming in these methods.Because detecting FA, electrochemical method have the advantages such as simple, high repeatability, good stability, cost are low, high sensitivity that it is developed rapidly.However, still have some shortcomings in the time using ordinary electrode Direct Electrochemistry to detect FA, as large in overpotential and electric transmission speed is crossed slowly etc.Therefore,, in order to overcome above shortcoming, development of new material modified electrode is devoted in numerous research.
Summary of the invention
Based on above-mentioned technical matters, the invention provides a kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode, preparation method and the application thereof of this modified electrode are also provided simultaneously.
The technology used in the present invention solution is:
A kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode, comprise basal electrode, at basal electrode finishing Graphene, be then placed in the sulfuric acid mixed solution electropolymerization that contains pyrroles, Keggin type heteropoly acid and obtain Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode.
Above-mentioned Keggin type heteropoly acid is preferably phosphomolybdic acid, phosphotungstic acid, silico-tungstic acid.
Above-mentioned basal electrode is preferably glass-carbon electrode.
A preparation method for Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode, comprises the following steps:
(1) preparation of graphene modified electrode
Choose glass-carbon electrode, it is carried out to surface treatment, Graphene is dispersed in aqueous solution, get graphene dispersing solution and drip and be coated in glass-carbon electrode surface, be placed under infrared lamp and dry, make graphene modified electrode;
(2) preparation of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode
Graphene modified electrode prepared by step (1) is immersed in the sulfuric acid mixed solution that contains pyrroles, Keggin type heteropoly acid, cyclic voltammetry scanning, scan rear taking-up, use second distillation water wash, dry Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode that obtains under room temperature.
Preferably, in step (1), the surface treatment process of described glass-carbon electrode is as follows: with the alumina powder of 0.3 μ m, 0.05 μ m, naked glass-carbon electrode is polished to minute surface successively, then rinse with redistilled water, use successively again nitric acid, acetone, redistilled water supersound washing, finally at room temperature dry.
Preferably, in step (1): described Graphene is Graphene body or the Graphene through functionalization, and the concentration of described graphene dispersing solution is 1mg/ml, get 6.0 μ L and drip and be coated in glass-carbon electrode surface.
Preferably, in step (2): described Keggin type heteropoly acid is phosphomolybdic acid, phosphotungstic acid or silico-tungstic acid.
Preferably, in step (2): in described mixed solution, pyrroles's concentration is 6 × 10
-3mol/L～8 × 10
-2mol/L, phosphomolybdic acid concentration is 1 × 10
-3mol/L～1 × 10
-2mol/L, sulfuric acid concentration is 0.4mol/L～0.6mol/L.
Be more preferably, in described mixed solution, pyrroles's concentration is 6 × 10
-2mol/L, phosphomolybdic acid concentration is 5 × 10
-3mol/L, sulfuric acid concentration is 0.5mol/L.
Preferably, in step (2): scanning voltage is-and 0.2v is to+0.8v, and sweep velocity is 100mV/s, and the scanning number of turns is 8 circles.
The application of above-mentioned Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode aspect folic acid.
Useful technique effect of the present invention is:
Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode prepared by the present invention can be used for the mensuration of folic acid, than ordinary electrode, there is the little and fast advantage of electric transmission speed of overpotential, and there is highly sensitive, good stability, repeatability advantages of higher.And the preparation process of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode of the present invention is simple, raw material is easy to get, and cost is low.
Brief description of the drawings
Fig. 1 is that cyclic voltammetry electropolymerization is prepared Py-PMo12, and polymerizing condition is 6 × 10
-3mol/L Py+1 × 10
-2mol/LPMo
12at 0.5mol/L H
2sO
4, voltage :+0.8to-0.2V, sweeps speed: 100mV/s;
Fig. 2 illustrates TEM and the PMo of GR
12-PPy, PMo
12the SEM of-PPy/GR, the TEM figure that wherein Fig. 2 a is GR, Fig. 2 b is PMo
12the SEM figure of-PPy, Fig. 2 c is PMo
12the SEM figure of-PPy/GR;
Fig. 3 is depicted as PMo
12-PPy/GR/GCE is at 0.01mol/L H
2sO
4(a), containing 1 × 10
-6the 0.01mol/L H of mol/L FA
2sO
4(b), process the electrode again obtaining afterwards at 0.01mol/L H
2sO
4(c) differential pulse voltammetry figure;
Fig. 4 illustrates different modified electrode (A) PMo
12-PPy/GR/GCE, (B) PMo
12-PPy/GCE, (C) PMo
12/ GCE and (D) GCE are containing 1.0 × 10
-6mol/L FA and not containing the 0.01mol/L H of FA
2sO
4the ratio that middle electric current reduces;
Fig. 5 illustrates PMo
12-PPy/GR/GCE is at variable concentrations 0,0.1 × 10
-8, 0.5 × 10
-8, 1.0 × 10
-8, 5.0 × 10
-8, 10 × 10
-8, 20 × 10
-8differential pulse voltammetry figure (a) in the FA of mol/L, the linear relationship chart (b) of electric current and concentration.
Embodiment
A kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode, comprise basal electrode, basal electrode is selected glass-carbon electrode, first, at glass-carbon electrode finishing Graphene, be then placed in the sulfuric acid mixed solution electropolymerization that contains pyrroles, Keggin type heteropoly acid and obtain Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode.Described Keggin type heteropoly acid is preferably phosphomolybdic acid, phosphotungstic acid or silico-tungstic acid.
The preparation process of a kind of phosphomolybdic acid-polypyrrole-graphene composite material modified electrode is specific as follows:
(1) preparation of graphene modified electrode (GR/GCE)
Choose naked glass-carbon electrode as basal electrode, first with the alumina powder of 0.3 μ m, 0.05 μ m, naked glass-carbon electrode is polished to minute surface successively, then rinse with redistilled water, use successively again nitric acid, acetone, redistilled water supersound washing, the supersound washing time is 20～40s, finally drying for standby at room temperature.Get graphene dispersing solution that 6.0 μ L concentration are 1mg/ml and drip and be coated in glass-carbon electrode after treatment surface, be then placed under infrared lamp and dry, make graphene modified electrode (GR/GCE).Graphene dispersing solution is that Graphene or ultrasonic being dispersed in water of functionalization graphene obtain, and concrete amount ratio is: in the ultrasonic water that is dispersed in 1ml of 1mg Graphene or functionalization graphene.
(2) PMo
12the preparation of-PPy/GR/GCE
Graphene modified electrode (GR/GCE) prepared by step (1) is immersed in and contains pyrroles (Py), Keggin type phosphomolybdic acid H
7pMo
12o
42xH
2o(can be abbreviated as PMo
12) sulfuric acid mixed solution in, in mixed solution, pyrroles's concentration is 6 × 10
-2mol/L, phosphomolybdic acid concentration is 5 × 10
-3mol/L, sulfuric acid concentration is 0.5mol/L.Employing cyclic voltammetry scanning, scanning voltage be-and 0.2v is to+0.8v, and sweep velocity is 100mV/s, and scanning the number of turns is 8 circles.Scan rear taking-up, used second distillation water wash, dry phosphomolybdic acid-polypyrrole-graphene composite material modified electrode (PMo that obtains under room temperature
12-PPy/GR/GCE).
Above-mentioned phosphomolybdic acid also can be replaced with phosphotungstic acid or silico-tungstic acid, with corresponding phosphotungstic acid-polypyrrole-graphene composite material modified electrode or the silico-tungstic acid-polypyrrole-graphene composite material modified electrode prepared.
Phosphomolybdic acid-polypyrrole-graphene composite material modified electrode, phosphotungstic acid-polypyrrole-graphene composite material modified electrode or silico-tungstic acid-polypyrrole-graphene composite material modified electrode of above-mentioned preparation all can be used for the mensuration of folic acid.
Below in conjunction with accompanying drawing, the invention will be further described:
Galvanochemistry is synthesized PMo
12-PPy/GR modified electrode, is immersed in graphene modified electrode the 0.5mol/L H that contains pyrroles and phosphomolybdic acid
2sO
4in solution, enclose to+0.8v scan round 8 at-0.2v, as shown in Figure 1.CV figure can find out three pairs of redox peaks, and this is the character of phosphomolybdic acid itself.From the inside to surface, along with the increase of the scanning number of turns, redox peak current constantly increases, and shows that phosphomolybdic acid is successfully embedded in pyrroles's film, forms PMo at graphene modified electrode surface
12-PPy.But film is too thick can be hindered the transmission of electronics and be easy to come off, therefore preferably electropolymerization 8 encloses the film modified electrod that obtains character the best.
Fig. 2 illustrates TEM and the PMo of GR
12-PPy, PMo
12the SEM of-PPy/GR.The pattern of GR, from TEM, presents the paper structure of accordion, and this is the distinctive structure of Graphene, as shown in Figure 2 a.Fig. 2 b and Fig. 2 c are PMo
12-PPy and PMo
12the stereoscan photograph of-PPy/GR, by seeing in Fig. 2 b, the PMo that particle is larger
12what-Ppy was inhomogeneous is dispersed in glass-carbon electrode surface, and graphene modified electrode surface form be tiny uniform PMo
12(Fig. 2 c), can see the three-dimensional structure of a porous simultaneously to-Ppy particle.This is mainly easily to form a three-dimensional structure because Graphene can provide large specific surface area, coarse skeleton, and this three-dimensional structure is conducive to the electric transmission in electrochemical reaction.
Fig. 3 is that folic acid (FA) exists (a) and do not have under the condition of (b) differential pulse voltammogram.As can be seen from Figure 3, after adding FA, PMo
12reduction peak current reduce, this result shows that FA has inhibiting effect to the redox reaction of PMo12, and strong adsorption is at electrode surface.After electrode is shifted out to FA solution, modified electrode is at 0.5mol/L H
2sO
4continuous circulation volt-ampere can be removed the FA that is adsorbed on electrode surface after scanning several circles, obtains a new electrode, can find out PMo from Fig. 3 (c)
12reduction peak current almost reached initial value.The steady-state response value (RSD) of this modified electrode is 8.0%.From experiment, can find, at PMo
12-PPy/GR/GCE surface FA is to PMo
12redox reaction have inhibiting effect.
The DPVs of the electrochemical behavior to different modifying electrode is studied.Different modifying electrode is at 0.01mol/L H
2sO
4the 0.01mol/L H that middle ratio is containing FA
2sO
4the ratio that electric current reduces as shown in Figure 4.At PMo
12it is 53.8% that the upper electric current of-PPy/GR/GCE reduces ratio, and at PMo
12-PPy/GCE and PMo
12the upper electric current of/GCE reduces ratio and is respectively 24.3% and 8.36%.Result shows, PMo
12-PPy/GR/GCE has the strongest suction-operated to FA, simultaneously at this modified electrode surface FA to PMo
12redox peak inhibiting effect the strongest, this derives from is the synergy of PPy and GR.On the one hand, PPy provides the stephanoporate framework can the more PMo of embedding
12and increase its stability.On the other hand, GR provides large specific surface area and two-dimensional structure, is PMo
12-PPy provides more avtive spot, and adsorbable more FA strengthens FA and PMo
12between-PPy, electrically contact ability.GR can accelerate PMo simultaneously
12electronic conduction speed in-PPy film.
The DPVs of variable concentrations FA is at PMo
12the research of-PPy/GR/GCE as shown in Figure 5.Along with the increase of FA concentration, PMo
12voltammetric current reduces, and the concentration of peak current and FA is 1.0 × 10
-9-2.0 × 10
-7linear within the scope of mol/L, linear equation is I
p(mA)=0.545-0.0149n (c=n × 10
-8m, r=0.999).Therefore the Sensitive Detection FA that the method can be quantitative, and detectability can reach 3.3 × 10
-11mol/L (S/N=3).
Also carry out in addition interference experiment, prove FA to exist the material of potential interference, as the uric acid of 100 times (UA), ascorbic acid (AA), dopamine (DA), glucose, L-TYR, the Ca of 300 times
2+, Mg
2+, Al
3+, Fe
2+, Fe
3+, NH
4 +, SO
4 2-, under optimal conditions, FA electrochemical behavior is not all produced to interference.
In sum, the present invention utilizes the method for electropolymerization by PMo
12, PPy and GR combine and constructed a novel modified electrode is PMo
12-PPy/GR/GCE.On this modified electrode surface, FA is to PMo
12redox reaction have strong inhibiting effect, utilize this unique advantage can Sensitive Detection FA.Adding of Graphene given modified electrode more avtive spot, is conducive to sensitive determination folic acid.At modified electrode surface, PMo
12redox reaction be one surface control process, at 0.01mol/L H
2sO
4middle PMo
12be better than and H with the binding ability of FA
+binding ability.PMo
12peak current and the concentration of FA 1.0 × 10
-9-2.0 × 10
-7within the scope of mol/L, be good linear relationship, detection limit reaches 3.3 × 10
-11mol/L.
Above reagent and instrument: folic acid (FA), pyrroles (Py), Keggin type phosphomolybdic acid H
7pMo
12o
42xH
2o(is abbreviated as PMo
12), Graphene.It is pure that all reagent is analysis, and water is redistilled water.Cyclic voltammetric and differential pulse volt-ampere curve are operated by the Shanghai CHI660C of Chen Hua instrument company electrochemical workstation, glass-carbon electrode (GCE) is working electrode, saturated calomel electrode (SCE) is contrast electrode, and platinum electrode is to electrode, and all electrochemistry experiments carry out at normal temperatures.The sign SEM (JSM-7001F) of material, TEM (JEOL JEM-2100 is at 90KV).The configuration of folic acid titer is be dissolved in 0.1mol/L NaOH and be diluted to 100mL with intermediate water by 4.4mg FA.Damping fluid is H
2sO
4and Na
2sO
4mixed liquor.The configuration water of all solution is redistilled water.
Claims (10)
1. Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode, it is characterized in that: comprise basal electrode, at basal electrode finishing Graphene, be then placed in the sulfuric acid mixed solution electropolymerization that contains pyrroles, Keggin type heteropoly acid and obtain Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode.
2. a kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode according to claim 1, is characterized in that: described Keggin type heteropoly acid is phosphomolybdic acid, phosphotungstic acid, silico-tungstic acid.
3. a preparation method for Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode, is characterized in that comprising the following steps:
(1) preparation of graphene modified electrode
Choose glass-carbon electrode, it is carried out to surface treatment, Graphene is dispersed in aqueous solution, get graphene dispersing solution and drip and be coated in glass-carbon electrode surface, be placed under infrared lamp and dry, make graphene modified electrode;
(2) preparation of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode
Graphene modified electrode prepared by step (1) is immersed in the sulfuric acid mixed solution that contains pyrroles, Keggin type heteropoly acid, cyclic voltammetry scanning, scan rear taking-up, use second distillation water wash, dry Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode that obtains under room temperature.
4. the preparation method of a kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode according to claim 3, it is characterized in that, in step (1), the surface treatment process of described glass-carbon electrode is as follows: with the alumina powder of 0.3 μ m, 0.05 μ m, naked glass-carbon electrode is polished to minute surface successively, then rinse with redistilled water, use successively again nitric acid, acetone, redistilled water supersound washing, finally at room temperature dry.
5. the preparation method of a kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode according to claim 3, it is characterized in that, in step (1): described Graphene is Graphene body or the Graphene through functionalization, the concentration of described graphene dispersing solution is 1mg/ml, gets 6.0 μ L and drips and be coated in glass-carbon electrode surface.
6. the preparation method of a kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode according to claim 3, is characterized in that, in step (2): described Keggin type heteropoly acid is phosphomolybdic acid, phosphotungstic acid or silico-tungstic acid.
7. the preparation method of a kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode according to claim 3, is characterized in that, in step (2): in described mixed solution, pyrroles's concentration is 6 × 10
-3mol/L～8 × 10
-2mol/L, phosphomolybdic acid concentration is 1 × 10
-3mol/L～1 × 10
-2mol/L, sulfuric acid concentration is 0.4mol/L～0.6mol/L.
8. the preparation method of a kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode according to claim 7, is characterized in that: in described mixed solution, pyrroles's concentration is 6 × 10
-2mol/L, phosphomolybdic acid concentration is 5 × 10
-3mol/L, sulfuric acid concentration is 0.5mol/L.
9. the preparation method of a kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode according to claim 3, it is characterized in that, in step (2): scanning voltage is-and 0.2v is to+0.8v, and sweep velocity is 100mV/s, and the scanning number of turns is 8 circles.
10. the application of a kind of Keggin type heteropoly acid-polypyrrole-graphene composite material modified electrode as claimed in claim 1 aspect folic acid.
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