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Unprecedented structural sensitivity toward average terrace width: Nafion adsorption at Pt{hkl} electrodes

Ahmed, Mujib, Morgan, David John, Attard, Gary Anthony, Wright, Edward, Thompsett, David and Sharman, Jonathan 2011. Unprecedented structural sensitivity toward average terrace width: Nafion adsorption at Pt{hkl} electrodes. Journal of Physical Chemistry C 115 (34) , pp. 17020-17027. 10.1021/jp2044042

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Abstract

Ultrathin Nafion overlayers ranging from 0 to 3.3 nm in thickness have been deposited on platinum single crystal electrodes in order to study their voltammetric behavior as a function of both Nafion surface coverage and platinum surface step density. Unusual structural sensitivity of Nafion-induced voltammetric peaks ascribable to Nafion interactions with step sites is observed as a function of average terrace width. For stepped surfaces containing both {111} and {100} terraces, average terrace widths of 2–3 atoms give rise to the most intense Nafion-step electrosorption peaks. Rapid quenching of the Nafion-step voltammetric peaks is observed as the average terrace width is gradually increased until for >5 atom wide terraces all such electrochemical features are completely attenuated. This rapid diminution of the step-Nafion voltammetric peak, within just three atoms of terrace width, is unprecedented, and a parallel with the “splitting” of hydrogen underpotential deposition (HUPD) step peaks in perchloric acid aqueous electrolyte for closely spaced steps is noted. On the basis of these measurements, it is suggested that Nafion is a molecular probe of adsorbed OH species on Pt electrodes.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Subjects: Q Science > QD Chemistry
Publisher: American Chemical Society
ISSN: 1932-7447
Funders: EPSRC
Last Modified: 20 Oct 2017 09:56
URI: http://orca-mwe.cf.ac.uk/id/eprint/9825

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