Mechanisms of methanol decomposition on platinum: A combined experimental and ab initio approach

D. Cao, G. Q. Lu, A. Wieckowski, S. A. Wasileski, M. Neurock

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211 Scopus citations

Abstract

The dual path mechanism for methanol decomposition on well-defined low Miller index platinum single crystal planes, Pt(111), Pt(110), and Pt(100), was studied using a combination of chronoamperometry, fast scan cyclic voltammetry, and theoretical methods. The main focus was on the electrode potential range when the adsorbed intermediate, CO ad, is stable. At such "CO stability" potentials, the decomposition proceeds through a pure dehydrogenation reaction, and the dual path mechanism is then independent of the electrodesubstrate surface structure. However, the threshold potential where the decomposition of methanol proceeds via parallel pathways, forming other than CO ad products, depends on the surface structure. This is rationalized theoretically. To gain insights into the controlling surface chemistry, density functional theory calculations for the energy of dehydrogenation were used to approximate the potential-dependent methanol dehydrogenation pathways over aqueous-solvated platinum interfaces.

Original languageEnglish (US)
Pages (from-to)11622-11633
Number of pages12
JournalJournal of Physical Chemistry B
Volume109
Issue number23
DOIs
StatePublished - Jun 16 2005

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