Carbon Nanotubes/Polyaniline Chemically Modified Electrode: Preparation and Ascorbic Acid Detection

doi:10.15541/jim20170191

Abstract

Abstract:

Nickel catalyst was deposited on a graphite electrode (GE) surface by constant voltage deposition method. With the nickel catalyst, carbon nanotubes (CNTs) were grown in situ on the GE surface to prepare CNTs chemically modified electrode (GSCNTs-CME) by catalytic chemical vapor deposition. After that, polyaniline (PANI) was polymerized in situ on the GSCNTs-CME to obtain GSCNTs/PANI-CME by electrochemical polymerization. Morphology and structure of the obtained electrodes were characterized by scanning electron microscope. Detection performances of the GSCNTs/PANI-CME on ascorbic acid (AA) were evaluated on an electrochemical workstation. Results show that the CNTs grow uniformly on the GE surface and the original tubular structure is remained well. PANI is coated uniformly on the surface of CNTs in the obtained composite with a typical three-dimensional network structure. The GSCNTs/PANI-CMEs show excellent electrochemical response to AA, amongst which the GSCNTs/PANI-CME with small-diameter CNTs shows stronger electrochemical response (wider linear detection range and lower detection limit) to AA. And its linear detection range and detection limit are 1.0×10^-6~4.5×10^-4 mol/L and 1.0×10^-7mol/L (S/N = 3), respectively. Therefore, the GSCNTs/PANI-CME shows excellent stability, repeatability and reliability.

Key words: ascorbic acid, carbon nanotubes/polyaniline, chemically modified electrode, electrochemical detection, carbon nanotube diameter

CLC Number:

O657

DENG Min, JIANG Qi, FANG Yuan, LI Huan, QIU Jia-Xin, LU Xiao-Ying. Carbon Nanotubes/Polyaniline Chemically Modified Electrode: Preparation and Ascorbic Acid Detection[J]. Journal of Inorganic Materials, 2018, 33(1): 53-59.

Figures/Tables 7

Fig. 1 CV curves of the PANI electrochemical polymerization on different electrodes at 20 mV/s scan rate^E (A), electrodeⅠ(B) and electrodeⅡ(C)

Fig. 2 SEM images of the obtained CMEs^Electrode (A)Ⅰ; (B) Ⅲ; (C)Ⅱ; (D, E) Ⅳ; (F) PANI-CME

Fig. 3 CV curves of the obtained electrodes in substrate solution (a, pH=6.0 PBS) and detection solution (b, pH=6.0 PBS containing 5.0×10-5 mol/L AA) at a scan rate of 20 mV/s^Electrode: (A) GE; (B)Ⅰ; (C)Ⅱ; (D) PANI-CME; (E) Ⅲ; F, Ⅳ)

Fig. 4 Electrochemical test calibration curves of the AA based on the electrode Ⅳ ((A) CV curves at different AA concentrations: 0.5, 1.0, 5.0, 10.0, 50.0, 100.0, 200.0, 400.0, 450.0 and 500.0×10-6 mol/L in pH=6.0 PBS with 20 mV/s scan rate, the inset is an enlarged view; (B) relationship between the Ip and AA concentrations; (C) the calibration curve of AA concentration and Ip) and electrode Ⅲ ((D) CV curves in different AA concentrations: 1.0, 5.0, 10.0, 50.0, 100.0, 200.0, 400.0 and 450.0×10-6 mol/L in pH=6.0 PBS with 20 mV/s scan rate, the inset is an enlarged view; (E) relationship between the Ip and AA concentrations; (F) the calibration curve of AA concentration and Ip)

Table 1 Electrochemical determination performances of different electrodes for the AA

Modified electrode	Linear range/(mol·L^-1)	Detection limit/(mol·L^-1)	Ref.
PAn-p-aminobenzene sulfonic acid	(3.5-17.5)×10^-5	7.5×10^-6	[31]
Molecularly imprinted PAn	(5.0-40.0)×10^-5	1.8×10^-5	[32]
Poly (acriflavine) modified electrode	(3.0-20.0)×10^-5	1.5×10^-6	[33]
DBSA doped Polyaniline nanoparticles	(0.3-8.0)×10^-6	8.3×10^-6	[34]
modified electrode

Fig. 5 Data of the stability testing ((A) relationship between Ip and the storing time of the Ⅳwith 2.0×10-4 mol/L AA solution in pH 6.0 PBS at 20 mV/s scan rate) and data of the anti-jamming testing ((B) interferences: DA, dopamine; Glc, glucose; UA, uric acid))

Table 2 Determination of AA in the recovery experiments

Samples	Detected (×10^-6, mol·L^-1)	Added (×10^-6, mol·L^-1)	Found (×10^-6, mol·L^-1)	Recovery/%	RSD/ (%, n=6)
1	10.54	20.00	30.02	97.4	2.5
2		40.00	51.37	102.1	1.9
3		60.00	69.86	98.9	0.8
4		80.00	91.48	101.2	1.0

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