Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode

TitleDensity functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode
Publication TypeJournal Article
Year of Publication2007
AuthorsSkulason E, Karlberg GS, Rossmeisl J, Bligaard T, Greeley J, Jonsson H, Norskov JK
JournalPhysical Chemistry Chemical Physics
Volume9
Issue25
Pagination3241-3250
ISBN Number1463-9076
Accession Numberhttp://apps.isiknowledge.com/InboundService.do?Func=Frame&product=WOS&action=retrieve&SrcApp=EndNote&Init=Yes&SrcAuth=ResearchSoft&mode=FullRecord&UT=000247367200005
Keywordsab-initio, adsorption, fuel-cell, oxygen reduction, platinum, proton-transfer reactions, single-crystal, total-energy calculations, transition-metal surfaces, water
Abstract

We present results of density functional theory calculations on a Pt(111) slab with a bilayer of water, solvated protons in the water layer, and excess electrons in the metal surface. In this way we model the electrochemical double layer at a platinum electrode. By varying the number of protons/electrons in the double layer we investigate the system as a function of the electrode potential. We study the elementary processes involved in the hydrogen evolution reaction, 2(H+ + e(-)) -> H-2, and determine the activation energy and predominant reaction mechanism as a function of electrode potential. We confirm by explicit calculations the notion that the variation of the activation barrier with potential can be viewed as a manifestation of the Bronsted - Evans - Polanyi-type relationship between activation energy and reaction energy found throughout surface chemistry.

URLhttp://apps.isiknowledge.com/InboundService.do?Func=Frame&product=WOS&action=retrieve&SrcApp=EndNote&Init=Yes&SrcAuth=ResearchSoft&mode=FullRecord&UT=000247367200005
08/12/2009