Adsorption States of Pyridinecarboxylic Acids on Gold Electrode Surface Studied by Infrared Reflection Absorption Spectroscopy

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  • NANBU Noritoshi
    Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology Department of Nanochemistry, Faculty of Engineering, Tokyo Polytechnic University
  • KITAMURA Fusao
    Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology
  • OHSAKA Takeo
    Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology
  • TOKUDA Koichi
    Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology

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Other Title
  • 赤外反射分光法による金電極表面におけるピリジンカルボン酸の吸着状態の検討
  • セキガイ ハンシャ ブンコウホウ ニ ヨル キン デンキョク ヒョウメン ニ オケル ピリジンカルボンサン ノ キュウチャク ジョウタイ ノ ケントウ

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Abstract

Adsorption behavior of three isomeric pyridinecarboxylic acids (picolinic acid: 2-PCA, nicotinic acid: 3-PCA, and isonicotinic acid: 4-PCA) on a smooth polycrystalline gold electrode surface was investigated in three electrolytic solutions, 0.1 mol dm−3 HClO4, NaClO4, and NaOH aqueous solutions, by in situ Fourier transform infrared reflection absorption spectroscopy (FT-IRAS). The reversible adsorption/desorption and reorientation of the PCAs were observed over the potential range investigated. The adsorbed PCAs existed as either zwitterions or anions, i.e., the carboxylate group of the PCA molecule was not protonated. In the HClO4 aqueous solution, it was found that as the electrode potential became more positive, adsorbed 3- and 4-PCAs reoriented from a flat (parallel) configuration to a vertical one that binds to the surface through lone pairs of electrons on the two oxygen atoms of the carboxylate group. In the NaClO4 aqueous solution, adsorbed 3-PCA and 4-PCA anions showed the flat configurations. In the NaOH aqueous solution, 3-PCA and 4-PCA anions adsorbed in the flat and the vertical configuration, respectively. No significant adsorption of 2-PCA was observed in the HClO4 and the NaOH aqueous solution. 2-PCA anion adsorbed in the flat configuration only in the NaClO4 aqueous solution. These findings indicate the ortho effect on adsorption.<br>

Journal

  • BUNSEKI KAGAKU

    BUNSEKI KAGAKU 56 (6), 457-464, 2007

    The Japan Society for Analytical Chemistry

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