CN104458881B - Modified electrode detects the new electrode materials of p-nitrophenol, preparation method and the detection to p-nitrophenol thereof - Google Patents
Modified electrode detects the new electrode materials of p-nitrophenol, preparation method and the detection to p-nitrophenol thereof Download PDFInfo
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- CN104458881B CN104458881B CN201410626111.3A CN201410626111A CN104458881B CN 104458881 B CN104458881 B CN 104458881B CN 201410626111 A CN201410626111 A CN 201410626111A CN 104458881 B CN104458881 B CN 104458881B
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- carbon nanotube
- walled carbon
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- aminoferrocene
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Abstract
The present invention relates to a kind of new electrode materials for p-nitrophenol detection and Synthesis and applications thereof, it is a kind of Single Walled Carbon Nanotube-Aminoferrocene compound substance prepared by diazo-reaction for raw material with Single Walled Carbon Nanotube and Aminoferrocene, and modifies glassy carbon electrode detection trace nitro-phenolic compound using it as electrode material.Electrochemical results shows this modified electrode and significantly reduces the oxidation peak current potential that p-nitrophenol responds, and peak current strengthens greatly.The method current-responsive is fast, highly sensitive, detectability is low, has a good application prospect.
Description
Technical field
The present invention relates to a kind of new electrode materials to p-nitrophenol detection and Synthesis and applications thereof, specifically based on preparation method and the electrochemical applications of functionalization Single Walled Carbon Nanotube-Aminoferrocene compound, belong to field of Environment Protection.
Background technology
Since Ijima in 1991 has found one dimension tubulose carbon simple substance, because it has very high conductivity and fabulous current-carrying performance, because of but for chemistry and biological chemistry detection ideal material.When being used as the electrode material of Electrochemical Detection, they demonstrate the ability having and strengthen electro transfer greatly.Carbon nano tube modified electrode can reduce the overpotential of substrate, increases current-responsive, reduces detection limit, shows unique superiority in Study of electrocatalysis.
Although the detection method of nitro-phenolic compound has a lot at present, as: chromatogram analysis method, high performance liquid chromatography, high performance capillary electrophoresis and vapor-phase chromatography, most methods complicated operation, cost consuming time.Electrochemical Detection nitro-phenolic compound because of have simple to operate, be swift in response, highly sensitive and do not need processing sample, advantages such as direct-detection and be subject to extensive concern.
Because Single Walled Carbon Nanotube has higher length-diameter ratio and bigger serface, it is made to be very beneficial for being used as the matrix of high density stationary probe molecule, this electrode modified material making Single Walled Carbon Nanotube become desirable.Therefore we have studied the Single Walled Carbon Nanotube with large pi-conjugated system-Aminoferrocene compound that Single Walled Carbon Nanotube and Aminoferrocene are prepared by diazo-reaction, and carry out Electrochemical Detection with the electrode pair p-nitrophenol that this compound is modified.Because its large pi-conjugated system is conducive to the resonance state of System forming Charger transfer, expand the flow range of pi-electron, strengthen the electron transfer rate in electrochemical reaction.Utilize Single Walled Carbon Nanotube to the high absorption property with phenolic compound simultaneously, with Single Walled Carbon Nanotube-Aminoferrocene compound modified electrode, realize detecting the high sensitive electrochemical of p-nitrophenol.
Summary of the invention
The object of this invention is to provide a kind of model electrochemical material detected fast for trace p-nitrophenol phenol.Utilize the design feature of Single Walled Carbon Nanotube, prepare Single Walled Carbon Nanotube-Aminoferrocene compound, using it as novel electrode decorative material with Aminoferrocene by diazo-reaction.With Single Walled Carbon Nanotube-Aminoferrocene compound modified electrode, detect trace nitro-phenolic compound by differential pulse method, and it is carried out quantitatively.Single Walled Carbon Nanotube prepared by the present invention-Electrochemical Detection of Aminoferrocene compound to p-nitrophenol has highly sensitive, that detectability is low, the range of linearity is wider feature, can be used for realizing the detection to trace nitro-phenolic compound.
The present invention is prepared is the Single Walled Carbon Nanotube-Aminoferrocene compound detecting p-nitrophenol for detecting the electrode modified material of trace nitro-phenolic compound, Single Walled Carbon Nanotube: the ratio of Aminoferrocene is 1: 0.1 ~ 2.
Described Single Walled Carbon Nanotube refers to that the carbon atom that molecular skeleton is arranged by hexagonal lattice forms, and the one dimension tube type material containing oxy radical obtained through functionalization.Its length is 1 ~ 10 μM.
The step that the preparation method that the invention provides the electrode modified material detecting trace nitro-phenolic compound comprises is as follows:
1) oxidation reaction of Single Walled Carbon Nanotube: according to dosage Single Walled Carbon Nanotube is joined the concentrated sulphuric acid: ultrasonic disperse (water bath sonicator 60 W in red fuming nitric acid (RFNA) (3:1) mixed solution, 6 h), stirring and refluxing 4 h in 80 DEG C of oil baths, being washed to pH is 5, is frozen into dry powder for subsequent use.
2) preparation of Single Walled Carbon Nanotube-Aminoferrocene compound: under argon shield; according to dosage by the N of Single Walled Carbon Nanotube; the DMF solution of dinethylformamide solution and 0.5 M HCl solution, Aminoferrocene and sodium nitrite stir and spend the night at 0 DEG C.After product DMF washes three times, be scattered in DMF solution for subsequent use.
3) the solution 6 μ L getting step 2 drips in electrode surface, natural drying film forming, is used for detecting p-nitrophenol.
The remarkable advantage of the electrode modified material based on Single Walled Carbon Nanotube-Aminoferrocene compound prepared by the present invention is: the overpotential that can reduce substrate, increases current-responsive, improves sensitivity, reduces detectability, widens the range of linearity, and respond fast.Can be used as the electrode modified material of nitro-phenolic compound sensor.
Accompanying drawing explanation
The Single Walled Carbon Nanotube (A) of synthesis and the transmission electron microscope picture of Single Walled Carbon Nanotube-Aminoferrocene compound (B) in Fig. 1 embodiment 1
The infrared spectrogram of the Single Walled Carbon Nanotube-Aminoferrocene compound (A) synthesized in Fig. 2 embodiment 1, Aminoferrocene (B) and Single Walled Carbon Nanotube (C).
The Raman spectrogram of the Single Walled Carbon Nanotube-Aminoferrocene compound (A) synthesized in Fig. 3 embodiment 1, Single Walled Carbon Nanotube (B) and Aminoferrocene compound (C).
The cyclic voltammetry curve that Single Walled Carbon Nanotube in Fig. 4 embodiment 1-Aminoferrocene compound (A) modified electrode, Single Walled Carbon Nanotube (B) modified electrode and naked glass-carbon electrode (C) detect 100 μMs of p-nitrophenols, sweep velocity is 0.05 V/s.
The differential pulse voltammetry curve (A) that Single Walled Carbon Nanotube in Fig. 5 embodiment 1-Aminoferrocene compound modified electrode detects the p-nitrophenol of variable concentrations and calibration curve (B) thereof.
Single Walled Carbon Nanotube in Fig. 6 embodiment 1-Aminoferrocene compound modified electrode responds (A) and calibration curve (B) thereof to the ampere of the p-nitrophenol of variable concentrations.
Embodiment
Below by embodiment, 1 couple of the present invention is specifically described; they are only for being further detailed the present invention; limiting the scope of the invention can not be interpreted as; those skilled in the art makes some nonessential improvement and adjustment according to the content of the invention described above, all belongs to scope.
Embodiment 1:
The first step: the purifying of Single Walled Carbon Nanotube:
The Single Walled Carbon Nanotube taking 200 mg joins the 150 mL concentrated sulphuric acids: in red fuming nitric acid (RFNA) (3:1) mixed solution, ultrasonic 3 h, and ultrasonic 3 h again after 20 min, stirring and refluxing 4 h in 80 DEG C of oil baths, being washed to pH is 5, is frozen into dry powder.
Second step: the preparation of Single Walled Carbon Nanotube-Aminoferrocene:
Precision takes 16 mg Aminoferrocenes and is placed in 50 mL flasks, adds that 4 mL DMFs are ultrasonic makes it be uniformly dispersed, and then adds in 6 mL 0.5 M hydrochloric acid solutions and stirs, then add 8.4 mg sodium nitrites.Stir under the state of argon shield, ice bath to 0 DEG C keeps 30 min.In addition, precision takes 4 mg Single Walled Carbon Nanotube and adds to 10 mL N, in dinethylformamide, ultrasonic 30 min make it be uniformly dispersed, then add in above-mentioned system, 0 DEG C of stirring is spent the night, and reaction product passes through centrifuging, with N, dinethylformamide by three times ultrasonic, dispersion and centrifuge cycle washed product Single Walled Carbon Nanotube-Aminoferrocene, then product is scattered in about 1 mL DMF for subsequent use.
Test result is as shown in Fig. 1 ~ 6.Wherein, the transmission electron microscope picture of the Single Walled Carbon Nanotube (A) of the purifying in Fig. 1 embodiment 1 and Single Walled Carbon Nanotube-Aminoferrocene compound (B)
The infrared spectrogram of the Single Walled Carbon Nanotube-Aminoferrocene compound (A) synthesized in Fig. 2 embodiment 1, Aminoferrocene (B) and Single Walled Carbon Nanotube (C).
The Raman spectrogram of the Single Walled Carbon Nanotube-Aminoferrocene compound (A) synthesized in Fig. 3 embodiment 1, Single Walled Carbon Nanotube (B) and Aminoferrocene compound (C).
The cyclic voltammetry curve that Single Walled Carbon Nanotube in Fig. 4 embodiment 1-Aminoferrocene compound (A) modified electrode, Single Walled Carbon Nanotube (B) modified electrode and naked glass-carbon electrode (C) detect 100 μMs of p-nitrophenols, sweep velocity is 0.05 V/s.
The differential pulse voltammetry curve (A) that Single Walled Carbon Nanotube in Fig. 5 embodiment 1-Aminoferrocene compound modified electrode detects the p-nitrophenol of variable concentrations and calibration curve (B) thereof.
Single Walled Carbon Nanotube in Fig. 6 embodiment 1-Aminoferrocene compound modified electrode responds (A) and calibration curve (B) thereof to the ampere of the p-nitrophenol of variable concentrations.
Claims (2)
1. modified electrode detects a preparation method for the electrode material of p-nitrophenol, it is characterized in that the step comprised:
The preparation of Single Walled Carbon Nanotube-Aminoferrocene compound: under argon shield, by the N of Single Walled Carbon Nanotube, dinethylformamide solution and 0.5 M hydrochloric acid solution, the N of Aminoferrocene, dinethylformamide solution and sodium nitrite stir and spend the night at 0 DEG C, product N, after dinethylformamide washes three times, be scattered in N, in dinethylformamide solution, the mass ratio of Single Walled Carbon Nanotube and Aminoferrocene is 1: 0.1 ~ 2, the mass ratio of Single Walled Carbon Nanotube and sodium nitrite is 1: 0.5 ~ 10, hydrochloric acid is 1: 0.01 ~ 0.5 with the amount of substance ratio of sodium nitrite.
2. the electrode material that prepared by method described in claim 1 is detecting the application in trace nitro-phenolic compound.
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| CN201410626111.3A CN104458881B (en) | 2014-11-10 | 2014-11-10 | Modified electrode detects the new electrode materials of p-nitrophenol, preparation method and the detection to p-nitrophenol thereof |
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| CN104458881B true CN104458881B (en) | 2015-10-28 |
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| US20100313054A1 (en) * | 2009-06-05 | 2010-12-09 | Samsung Electronics Co. Ltd. | Apparatus and method for current saving in portable terminal |
| CN102590305A (en) * | 2011-01-12 | 2012-07-18 | 哈尔滨工业大学 | Sensitive membrane for electrochemical biosensors and preparation method thereof |
| CN103196985A (en) * | 2013-04-26 | 2013-07-10 | 黑龙江大学 | Method for measuring p-nitrophenol in water system |
| CN104034772A (en) * | 2014-06-18 | 2014-09-10 | 许昌学院 | Preparation method and application of modification electrode |
| CN104101633A (en) * | 2014-07-29 | 2014-10-15 | 无锡百灵传感技术有限公司 | Method for preparing electrochemical sensor based on carbon nano tube and vinyl ferrocene modified carbon paste electrode |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100313054A1 (en) * | 2009-06-05 | 2010-12-09 | Samsung Electronics Co. Ltd. | Apparatus and method for current saving in portable terminal |
| CN102590305A (en) * | 2011-01-12 | 2012-07-18 | 哈尔滨工业大学 | Sensitive membrane for electrochemical biosensors and preparation method thereof |
| CN103196985A (en) * | 2013-04-26 | 2013-07-10 | 黑龙江大学 | Method for measuring p-nitrophenol in water system |
| CN104034772A (en) * | 2014-06-18 | 2014-09-10 | 许昌学院 | Preparation method and application of modification electrode |
| CN104101633A (en) * | 2014-07-29 | 2014-10-15 | 无锡百灵传感技术有限公司 | Method for preparing electrochemical sensor based on carbon nano tube and vinyl ferrocene modified carbon paste electrode |
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