PAN molecules generated in HClO 4 were anomalously shorter than those formed in H 2SO 4. 2009, 131, 6468), the rate of polymerization was slower in HClO 4 and the produced PAN molecules tended to aggregate on the Au(111) electrode. Compared with the results observed in H 2SO 4 ( Leeet al. With aniline molecules arranging in a way similar to the backbone of PAN in HClO 4, they readily coupled with each other to produce linear polymeric chains aligned predominantly in the ⟨110⟩ directions of the Au(111). Raising the potential to 0.9 V or more positive values triggered the oxidation and polymerization of aniline. The coverage of aniline admolecule on Au(111) was lower in BSA than in HClO 4. These structures consisted of intermingled aniline molecules and perchlorate or BSA − anions zigzagging in the ⟨110⟩ directions in HClO 4 and in the ⟨121⟩ directions in BSA. At the onset potential of aniline’s oxidation, ∼0.8 V, aniline molecules were adsorbed in highly ordered arrays, designated as (3 × 2√3) and (4 × 2√3) in perchloric acid and BSA, respectively. In situ scanning tunneling microscopy (STM) was used to study the adsorption and polymerization of aniline on Au(111) single-crystal electrode in 0.1 M perchloric acid and 0.1 M benzenesulfonic acids (BSA) containing 30 mM aniline, respectively.
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