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A Comparative Study on the Viscoelasticity and Morphology of Polyaniline Films Galvanostatically Grown on Bare and 4- Aminothiophenol-Modified Gold Electrodes Using an Electrochemical Quartz Crystal Impedance System and SEM

谢青季Qingji XIE† Youyu ZHANG Canhui XIANG Jianxin TANG Yunlong LI Qiuxiang ZHAO and Shouzhuo YAO

ANALYTICAL SCIENCES MAY 2001, VOL. 17,-0001,():

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摘要/描述

The equivalent-circuit parameters of the 9-MHz piezoelectric quartz crystal (PQC) resonance were measured in situ during the galvanostatic polymerization of aniline on 4-aminothiophenol(4-ATP)-modified and bare Au electrodes for ca. 2000s, respectively. Two polymerization media, 0.100mol L-1 aniline in 1.0mol L-1 H2SO4 and in 2.0mol L-1 HClO4 aqueous solutions, and two values of the current density, 12 and 36μA cm-2, were used. At identical levels of the resonant frequency shifts in the solutions, obviously greater increases in the motional resistance (R1) were found afteraniline polymerization on bare Au electrodes, though the absolute values of Δf0/ΔR1 were all large; also, the resonant frequency shifts in air (Δf0g) were considerably smaller for PANI films grown on bare Au electrodes. It is thus concluded that, under identical polymerization conditions, (1) the PANI film grown on a bare gold electrode is rougher, less compact, and can entrap solution more notably; (2) the deposition efficiency of PANI is higher on a 4-ATP-modified Au electrode, owing to a significantly greater observed "dry" frequency shift, and thus a greater "net" mass value of the polyaniline backbone. SEM observations have confirmed that PANI films on 4-ATP-modified Au electrodes were smoother and more compact than those grown on bare Au ones under identical polymerization conditions. In addition, a technique of simultaneous measurements of the electroacoustic admittance of the PQC resonance and the electrochemical impedance was used to monitor the adsorption of 4-ATP onto a PQC gold electrode.

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