Short communication
Comments on the paper by H. Shiroishi, Y. Ayato, K. Kunimatsu and T. Okada entitled “Study of adsorbed water on Pt during methanol oxidation by ATR-SEIRAS (surface-enhanced infrared absorption spectroscopy)” [J. Electroanal. Chem. 581 (2005) 132]

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Abstract

The conclusions of a recently reported ATR-SEIRAS study of the electrooxidation of methanol on polycrystalline platinum are briefly commented, emphasising that the reported new band corresponding to water adsorbed on the CO-covered Pt electrode cannot be the oxygen-containing adsorbate necessary to oxidise the adsorbed CO formed on the electrode surface upon oxidative adsorption of methanol necessary for further methanol oxidation.

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Cited by (12)

  • Interactions between interfacial water and CO adsorbed on Pt and Pt-Ru alloy surfaces under electrochemical conditions: Density-functional theory study

    2010, Electrochimica Acta
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    Although the O–H stretching frequency of a hydrogen-bonded system is often thought to undergo a significant amount of red shift, that of the water molecule hydrogen-bonded to CO(bridge) is not the case [42]. The corresponding frequency is computed to be 3645 cm−1 for CO(bridge) on pure Pt (Fig. 2a) and 3614 cm−1 on PtRu alloy (Fig. 2b), both in good agreement with the experimental values of 3650 cm−1 ± 20 cm−1 on platinum [13,15–27,36] and 3610 cm−1 ± 20 cm−1 on PtRu alloy [18,19]. These high values for the O–H stretching frequency are somewhat unexpected.

  • Density-functional theory study of interactions between water and carbon monoxide adsorbed on platinum under electrochemical conditions

    2009, Chemical Physics Letters
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    However, Model 2 is inconsistent with the growth (during CO adsorption) of the positive peak at 1640 cm−1 that was observed for H–O–H bending: this value is quite close to that expected for bulk water, i.e., with water-to-water hydrogen bonds. Cuesta has pointed out a possible problem with Model 2, i.e., that the typical cyclic voltammogram for a high coverage CO-adsorbed surface exhibits virtually no current for H desorption in the 0.05–0.4 V region, and thus there should be no water molecules in direct contact with the surface [48]. Cuesta also argued that similar results reported earlier [31] represent the existence of a new adsorbed water species at the CO-covered Pt–electrolyte interface and that the band around 3660 cm−1[20] corresponds to interfacial water interacting with the CO layer, but not with the underlying Pt surface.

  • Catalytic effects produced by cathodisation of platinum electrodes in sulphuric solutions

    2008, International Journal of Hydrogen Energy
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    The catalytic activity of platinum depends on the surface structure, facetting, number of defects or kinks, and the presence of ions and other adsorbed intermediate species [1–5].

  • Catalytic effects on methanol oxidation produced by cathodization of platinum electrodes

    2007, Journal of Colloid and Interface Science
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    This is a strong proof that the water molecules coexist with the resultant carbon monoxide and are the species directly reacting with carbon monoxide, promoting further methanol oxidation [122]. The change in the structure of the interfacial water layer brought about by methanol adsorption is responsible for the difference between the experimentally determined pzc of the CO-covered Pt(111), 1.10 V, and the estimated potential of zero free charge of clean Pt(111), 0.23 V. From these values it has been calculated that the average angle between the dipole moment of water and the platinum surface, at room temperature and at the pzc, decreases from 7.85° for clean Pt(111) to 1.46° for the CO-covered Pt(111) [123]. Chang and Weaver [124] found that coadsorption of water at lower carbon monoxide coverages on Pt(111) in the electrochemical environment favors COads binding in bridging sites.

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