Elucidating the activity of stepped Pt single crystals for oxygen reduction

The unexpectedly high measured activity of Pt[ n (111) × (111)] and Pt[ n (111) × (100)] stepped single crystal surfaces towards the oxygen reduction reaction (ORR) is explained utilizing the hydroxyl binding energy as the activity descriptor. Using this descriptor (estimated using experimental data...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2014-01, Vol.16 (27), p.13625-13629
Main Authors: Bandarenka, Aliaksandr S, Hansen, Heine A, Rossmeisl, Jan, Stephens, Ifan E. L
Format: Article
Language:English
Subjects:
Binding energy
Physical chemistry
Reduction
Single crystals
Solvation
Stepped
Surface chemistry
Volcanoes
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Summary:The unexpectedly high measured activity of Pt[ n (111) × (111)] and Pt[ n (111) × (100)] stepped single crystal surfaces towards the oxygen reduction reaction (ORR) is explained utilizing the hydroxyl binding energy as the activity descriptor. Using this descriptor (estimated using experimental data obtained by different groups), a well-defined Sabatier-type volcano is observed for the activities measured for the Pt[ n (111) × (111)] and Pt[ n (111) × (100)] stepped single crystals, in remarkable agreement with earlier theoretical studies. We propose that the observed destabilisation of *OH species at these surfaces is due to the decreased solvation of the adsorbed hydroxyl intermediates on adjacent terrace sites. The activity of stepped Pt can be described by a Sabatier type volcano, according to a voltammetric analysis.
ISSN:1463-9076
1463-9084
DOI:10.1039/c4cp00260a