Structure sensitivity and nanoscale effects in electrocatalysis

This review discusses the role of the detailed nanoscale structure of catalytic surfaces on the activity of various electrocatalytic reactions of importance for fuel cells, hydrogen production, and other environmentally important catalytic reactions, such as carbon monoxide oxidation, methanol and ethanol oxidation, ammonia oxidation, nitric oxide reduction, hydrogen evolution, and oxygen reduction. Specifically, results and insights obtained from surface-science single-crystal-based model experiments are linked to experiments on well-defined shape-controlled nanoparticles. A classification of structure sensitive effects in electrocatalysis is suggested, based both on empirical grounds and on quantum-chemical viz. thermochemical considerations. The mutual relation between the two classification schemes is also discussed. The review underscores the relevance of single-crystal modeling of nanoscale effects in catalysis, and points to the special role of two kinds of active sites for electrocatalysis on nanoparticulate surfaces: (i) steps and defects in (111) terraces or facets, and (ii) long-range (100) terraces or facets.