CN103913492B - A kind of Keggin-type heteropoly acid-polypyrrole-graphene composite material modified electrode and its preparation method and application - Google Patents
A kind of Keggin-type heteropoly acid-polypyrrole-graphene composite material modified electrode and its preparation method and application Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of Keggin-type heteropoly acid-polypyrrole-graphene composite material modified electrode, it comprises the following steps: choose glass-carbon electrode, surface treatment is carried out to it, then get graphene dispersion drop and be coated in glassy carbon electrode surface, dry under being placed in infrared lamp, obtained graphene modified electrode; Then the graphene modified electrode of preparation is immersed in the sulfuric acid solution containing pyrroles, Keggin-type heteropoly acid, cyclic voltammetry scans, scanned rear taking-up, used intermediate water drip washing, under room temperature, drying obtains Keggin-type heteropoly acid-polypyrrole-graphene composite material modified electrode.Keggin-type heteropoly acid-polypyrrole-graphene composite material modified electrode prepared by the present invention has sensitive inhibiting effect based on the redox reaction of folic acid to Keggin-type heteropoly acid, can be used for the mensuration of folic acid, compared to ordinary electrode, have that overpotential is little, highly sensitive, good stability, repeatability advantages of higher, and preparation process is simple, raw material is easy to get, and 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.When lacking FA in human body, a series of disease can be caused as anaemia, neurasthenia, congenital malformation, and the probability that can increase heart disease and stroke.Report shows, in pregnant woman's body, the low meeting of folate content causes fetal anomaly and affects the growth of bone and brain.So sensitive and accurate detection FA causes the great attention of people.At present, the method for some traditional detection FA is in the news, such as: high performance liquid chromatography, spectrophotometric method, fluorescence etc.But there is complicated, time-consuming, high in cost of production shortcoming in these methods.The advantages such as simple, high repeatability, good stability, cost are low, high sensitivity are had to make it be developed rapidly because electrochemical method detects FA.However, still there are some shortcomings when using ordinary electrode Direct Electrochemistry to detect FA, as large in overpotential and electron transfer rate 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, the sulfuric acid mixed solution electropolymerization be then placed in containing pyrroles, Keggin-type heteropoly acid obtains 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, surface treatment is carried out to it, by graphene dispersion in aqueous, get graphene dispersion drop and be coated in glassy carbon electrode surface, dry under being placed in infrared lamp, obtained 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 containing pyrroles, Keggin-type heteropoly acid, cyclic voltammetry scans, scan rear taking-up, use second distillation water wash, under room temperature, drying obtains Keggin-type heteropoly acid-polypyrrole-graphene composite material modified electrode.
Preferably, in step (1), the surface treatment process of described glass-carbon electrode is as follows: with the alumina powder of 0.3 μm, 0.05 μm, naked glass-carbon electrode is polished to minute surface successively, then rinse with redistilled water, use nitric acid, acetone, redistilled water supersound washing more successively, 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 glassy 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, pyrrole concentrations 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, pyrrole concentrations 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-0.2v to+0.8v, and sweep velocity is 100mV/s, the scanning number of turns is 8 circles.
The above-mentioned Keggin-type heteropoly acid-polypyrrole-application of graphene composite material modified electrode in folic acid.
Advantageous Effects 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, compared to ordinary electrode, there is the advantage that overpotential is little and electron transfer rate is fast, 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.
Accompanying drawing explanation
Fig. 1 is that cyclic voltammetry electropolymerization prepares Py-PMo12, and polymerizing condition is 6 × 10
-3mol/LPy+1 × 10
-2mol/LPMo
12at 0.5mol/LH
2sO
4, voltage :+0.8to-0.2V, sweeps speed: 100mV/s;
Fig. 2 illustrates TEM and PMo of GR
12-PPy, PMo
12the SEM of-PPy/GR, wherein Fig. 2 a is the TEM figure of GR, and 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/LH
2sO
4a (), is containing 1 × 10
-6the 0.01mol/LH of mol/LFA
2sO
4b (), the electrode again obtained after process is at 0.01mol/LH
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 is containing 1.0 × 10
-6mol/LFA and not containing the 0.01mol/LH of FA
2sO
4the ratio that middle electric current reduces;
Fig. 5 illustrates PMo
12-PPy/GR/GCE 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 selects glass-carbon electrode, first grapheme modified in glassy carbon electrode surface, the sulfuric acid mixed solution electropolymerization be then placed in containing pyrroles, Keggin-type heteropoly acid obtains 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.
A kind of preparation process 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 μm, 0.05 μm, naked glass-carbon electrode is polished to minute surface successively, then rinse with redistilled water, use nitric acid, acetone, redistilled water supersound washing more successively, the supersound washing time is 20 ~ 40s, finally at room temperature drying for standby.Getting 6.0 μ L concentration is glassy carbon electrode surface after the graphene dispersion drop of 1mg/ml is coated in process, dries, obtained graphene modified electrode (GR/GCE) under being then placed in infrared lamp.Graphene dispersing solution is that Graphene or functionalization graphene ultrasonic disperse obtain in water, and concrete amount ratio is: 1mg Graphene or functionalization graphene ultrasonic disperse are in the water of 1ml.
(2) PMo
12the preparation of-PPy/GR/GCE
The graphene modified electrode (GR/GCE) step (1) prepared is immersed in containing 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, pyrrole concentrations is 6 × 10
-2mol/L, phosphomolybdic acid concentration is 5 × 10
-3mol/L, sulfuric acid concentration is 0.5mol/L.Employing cyclic voltammetry scans, and scanning voltage is-0.2v to+0.8v, and sweep velocity is 100mV/s, and the scanning number of turns is 8 circles.Scanned rear taking-up, used second distillation water wash, under room temperature, drying obtains phosphomolybdic acid-polypyrrole-graphene composite material modified electrode (PMo
12-PPy/GR/GCE).
Above-mentioned phosphomolybdic acid also can be replaced with phosphotungstic acid or silico-tungstic acid, prepares phosphotungstic acid-polypyrrole-graphene composite material modified electrode or silico-tungstic acid-polypyrrole-graphene composite material modified electrode with corresponding.
Phosphomolybdic acid-polypyrrole-graphene composite material the modified electrode of above-mentioned preparation, phosphotungstic acid-polypyrrole-graphene composite material modified electrode or silico-tungstic acid-polypyrrole-graphene composite material modified electrode all can be used for the mensuration of folic acid.
Below in conjunction with accompanying drawing, the invention will be further described:
Electrochemistry formated PMo
12-PPy/GR modified electrode, is immersed in the 0.5mol/LH containing pyrroles and phosphomolybdic acid by graphene modified electrode
2sO
4in solution, enclose in-0.2v to+0.8v scan round 8, 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 circle obtains the film modified electrod of character the best.
Fig. 2 illustrates TEM and 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 is PMo
12-PPy and PMo
12the stereoscan photograph of-PPy/GR, can see by Fig. 2 b, the PMo that particle is larger
12what-Ppy was uneven is dispersed in glassy carbon electrode surface, and that formed at graphene modified electrode surface is the PMo of fine uniform
12-Ppy particle (Fig. 2 c), can see the three-dimensional structure of a porous simultaneously.This mainly due to Graphene large specific surface area can be provided, coarse skeleton easily forms a three-dimensional structure, this three-dimensional structure is conducive to the electric transmission in electrochemical reaction.
Fig. 3 is under folic acid (FA) exists (a) and there is not 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 the redox reaction of FA to PMo12 has inhibiting effect, and strong adsorption is at electrode surface.After electrode being shifted out FA solution, modified electrode is at 0.5mol/LH
2sO
4the FA being adsorbed on electrode surface can be removed after a few circle of continuous circulation voltammetric scan, obtain a new electrode, as can be seen from Fig. 3 (c), PMo
12reduction peak current almost reached initial value.The steady-state response value (RSD) of this modified electrode is 8.0%.Can find, at PMo from experiment
12-PPy/GR/GCE surface FA is to PMo
12redox reaction have inhibiting effect.
The DPVs of the electrochemical behavior of different modifying electrode is studied.Different modifying electrode is at 0.01mol/LH
2sO
4middle ratio is at the 0.01mol/LH 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 a stephanoporate framework can embed more PMo
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, adsorbable more FA, strengthens FA and PMo
12electrical contact ability between-PPy.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 interference experiment in addition, prove material FA being existed to 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-, in optimal conditions all interference is not produced to FA electrochemical behavior.
In sum, the present invention utilizes the method for electropolymerization by PMo
12, PPy and GR combines and has constructed a novel modified electrode and PMo
12-PPy/GR/GCE.On this modified electrode surface, FA is to PMo
12redox reaction have strong inhibiting effect, utilize the advantage of this uniqueness can Sensitive Detection FA.Adding of Graphene imparts the more avtive spot of modified electrode, is conducive to sensitive determination folic acid.On modified electrode surface, PMo
12redox reaction be the process of a granule surface contral, at 0.01mol/LH
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
-7in good linear relationship within the scope of mol/L, 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 Shanghai Chen Hua instrument company CHI660C 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 (JEOLJEM-2100 is at 90KV).The configuration of folic acid titer to be dissolved in 0.1mol/LNaOH by 4.4mgFA and to be diluted to 100mL with intermediate water.Damping fluid is H
2sO
4and Na
2sO
4mixed liquor.The configuration water of all solution is redistilled water.
Claims (4)
1. 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, surface treatment is carried out to it, by graphene dispersion in aqueous, get graphene dispersion drop and be coated in glassy carbon electrode surface, dry under being placed in infrared lamp, obtained 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 containing pyrroles, Keggin-type heteropoly acid, cyclic voltammetry scans, scan rear taking-up, use second distillation water wash, under room temperature, drying obtains Keggin-type heteropoly acid-polypyrrole-graphene composite material modified electrode;
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 glassy carbon electrode surface;
Described Keggin-type heteropoly acid is phosphomolybdic acid, phosphotungstic acid or silico-tungstic acid;
In step (2): in described mixed solution, pyrrole concentrations 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;
In step (2): scanning voltage is-0.2v to+0.8v, and sweep velocity is 100mV/s, the scanning number of turns is 8 circles.
2. the preparation method of a kind of Keggin-type heteropoly acid-polypyrrole-graphene composite material modified electrode according to claim 1, 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 μm, 0.05 μm, naked glass-carbon electrode is polished to minute surface successively, then rinse with redistilled water, use nitric acid, acetone, redistilled water supersound washing more successively, finally at room temperature dry.
3. the preparation method of a kind of Keggin-type heteropoly acid-polypyrrole-graphene composite material modified electrode according to claim 1, is characterized in that: in described mixed solution, pyrrole concentrations is 6 × 10
-2mol/L, phosphomolybdic acid concentration is 5 × 10
-3mol/L, sulfuric acid concentration is 0.5mol/L.
4. the application of the electrode obtained by preparation method in folic acid of a kind of Keggin-type heteropoly acid-polypyrrole-graphene composite material modified electrode as claimed in claim 1.
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