Zhang Guirong, Zhao Xueru, X. Xiaoming
Jun 14, 2012
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Journal
Acta Chimica Sinica
Abstract
The in situ UV-Vis spectra of electropolymerization of m -toluidine and o -toluidine on indium tin oxide (ITO) conducting glass electrode by potentiostatic method in sulfuric acid of 0.5 mol•L - 1 show that the electropolymerization of o -toluidine is faster than that of m -toluidine under the same condition. The current transient curves of electrolyzing m -toluidine and o -toluidine at potential 0.9 V (vs saturated Ag/AgCl) indicate that both poly( m -toluidine) and poly( o -toluidine) are deposited on ITO electrode in three-dimen-sional progressive nucleation (3DPN) at the beginning of electropolymerization; then the electropolymerization of o -toluidine keeps in branch chain reaction and the electopolymerization of m -toluidine becomes slow greatly. Due to the difference of the electropolymerization of them, the scan electron microscope morphol-ogy of poly( o -toluidine) is granulous and porous and that of poly( m -toluidine) is compact and slightly smooth. DFT geometry optimization using B3LYP/6-31G** basis set for the tetramer of o -toluidine and m -toluidine demonstrates that the emeraldine base (EB) for tetramer of m -toluidine has curly structure but EB for tetramer of o -toluidine not, which implies that the conformation difference between poly( m -toluidine) and poly( o -toluidine) might be main cause of the difference of their electropolymerization.