Layer-by-layer Assembled Graphene/Polyaniline Nanocomposite Film and Applied in Electrochemical Sensing†

doi:10.7503/cjcu20140834

Abstract

Abstract:

A novel graphene-polyaniline nanocomposite thin film was prepared by means of electrostatic layer-by-layer(LBL) assembly of positive charged graphene sheets modified by poly(acrylic acid)(PAA-Gr) and negatively charged polyaniline(PANI). The use of PAA not only enhanced the dispersibility of the graphene sheets, but also provided a positive charge to the graphene thus facilitating the growth of multilayered films. Ultraviolet-visible spectrophotometry was used in the present work to monitor the LBL assembly process of {PAA-Gr/PANI}_n multilayered films. Fourier transform infrared spectroscopy, X-ray diffraction patterns, scanning electron microscopy and cyclic voltammetry results demonstrated the successful fabrication of {PAA-Gr/PANI}_n hybrid multilayered films. Application of the {PAA-Gr/PANI}_n hybrid film in electrochemical sensing was further demonstrated using H₂O₂ as a model analyte. The {PAA-Gr/PANI}_n hybrid film was shown to have excellent electrocatalytic activity towards H₂O₂. The proposed {PAA-Gr/PANI}_n film based sensor exhibited a wide linear detection range for H₂O₂ from 0.005 mmol/L to 0.3 mmol/L with a low detection limit of 1×10^-6 mol/L.

Key words: Graphene, Polyaniline, Layer-by-layer assembly, Hydrogen peroxide sensor

CLC Number:

O631.2

TrendMD:

SUN Jun, ZHU Zhengyi, LAI Jianping, LUO Jing, LIU Xiaoya. Layer-by-layer Assembled Graphene/Polyaniline Nanocomposite Film and Applied in Electrochemical Sensing^†[J]. Chem. J. Chinese Universities, 2015, 36(3): 581.

Figures/Tables 11

Scheme 1 Preparation processes of PAA-Gr and {PAA-Gr/PANI}n

Fig.1 FTIR spectra of Gr(a), PAA(b) and PAA-Gr(c)

Fig.2 XRD patterns of GO(a), Gr(b) and PAA-Gr(c)

Fig.3 FTIR(A) and UV-Vis(B) spectra of PAA-Gr(a), PANI(b) and {PAA-Gr/PANI}n(c)

Fig.4 UV-Vis spectra of {PAA-Gr/PANI}n multilayer films(n from 1 to 12)(A) and intensity of UV-Vis spectra for different bilayers at 298 nm(a) and 715 nm(b)(B)

Fig.5 SEM images of bare GCE surface(A), PAA-Gr(B), {PAA-Gr/PANI}3(C) and {PAA-Gr/PANI}5(D) on the GCE electrode

Fig.6 Cyclic voltammograms(CV) curves of {PAA-Gr/PANI}n multilayer modified GCE electrode with 4(a), 8(b), 12(c), 16(d), 20(e) bilayers(A) and EIS spectra(B) of {PAA-Gr/PANI}n multilayer modified GCE electrode with 0(a), 4(b), 8(c), 12(d) bilayers in 2 mmol/L K3[Fe(CN)6]+0.2 mol/L KCl

Fig.7 CV curves of {PAA-Gr/PANI}20 at different scan rates in 0.2 mmol/L H2SO4 (A) and peak currents of {PAA-Gr/PANI}20 as a function of scan rates(B) (A) Scan rate/(mV·s-1): a. 25; b. 50; c. 75; d. 100; e. 125; f. 150, g. 175; h. 200.(B) a. Peak 1; b. peak 2; c. peak 3; d. peak 4.

Fig.8 CV curves of {PAA-Gr/PANI}20 modified GCE electrode in 0.1 mol/L PBS with various pH value Scan rate: 50 mV/s. pH value: a. 2; b. 3; c. 4; d. 5; e. 7; f. 8; g. 9.

Fig.9 CV curves(A) and peak currents(B) of {PAA-Gr/PANI}20 modified GCE electrode in H2O2 for different concentrations c(H2O2)/(mmol·L-1): a. 0.3; b. 0.25; c. 0.20; d. 0.15; e. 0.10; f. 0.05, g. 0.01; h. 0.008; i. 0.005; j. 0. Scan rate: 50 mV/s.

Table 1 Comparison of the performance of various H2O2 sensors*

Electrode material	Detection limit/(μmol·L^-1)	Linear range/(μmol·L^-1)	Ref.
Graphene/Au NPs/Chitosan	180	200—4200	[33]
Ag/Graphene/GCE	28	100—40000	[34]
MnO₂/GO/GCE	0.8	5—600	[35]
Graphene/Nafion/Azure I/Au	10	30—5000	[36]
HRP/Graphene	1.17	3.5—329	[37]
PSS-GS/PANI	6	100—1500	[10]
(PEI/PAA-Graphene)₃		100—1000	[38]
{PAA-Gr/PANI}_n	1.0	5—300	This work

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