Oxalic acid adsorption and oxidation at platinum single crystal electrodes

Oxalic acid adsorption and oxidation processes have been studied at platinum single crystal electrodes with basal orientations. Cyclic voltammetry and charge displacement experiments have been combined with in situ external reflection infrared experiments for the study of oxalic acid adsorption at potentials below 0.70 V. Whereas reversible anion-like adsorption is observed for Pt(100) and Pt(111) electrodes, oxalic acid is reduced at Pt(110) leading to the formation of an irreversibly bonded adsorbate which has been identified as adsorbed CO from the infrared spectra. Spectroscopic data confirm the potential dependent behaviour of oxalic acid adsorption on Pt(111) and Pt(100) electrodes derived from electrochemical data. At the same time, the infrared spectra show distinct C-O stretching bands for adsorbates on Pt(100) and P(111). In acidic solutions (pH = 1), for which oxalic acid and bioxalate anions predominate as solution species, oxalate anions are adsorbed at the Pt(100) electrode surface whereas bioxalate anions seem to be the adsorbed species at Pt(111). In neutral solutions, oxalate anions are adsorbed on both Pt(111) and Pt(100) surfaces. No intermediates coming from oxalic acid other than adsorbed CO for Pt(110) and adsorbed (bi)oxalate anions for Pt(111) and Pt(100) are detected during the oxidation of oxalic acid. Adsorbate bands are observed between 1400 and 1600 cm(-1) for the Pt(111) electrode for potentials between 0.85 and 1.0 V. These bands are related to adsorbed carbonate anions formed in the presence of carbon dioxide molecules generated from oxalic acid oxidation. (C) 2003 Elsevier B.V. All rights reserved.