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Significance The benefits of passing from massive catalytic electrodes to a set of nanoparticles of the same material is an issue of considerable current interest. This process relates to the domain of fuels cells and, more generally, to contemporary energy challenges. When several products are concurrently formed, the question arises regarding the possible effect of such nanoscaling on product selectivity. It is tempting to view these effects as relevant to the exclusive domain of purely chemical factors, such as creation of surface defects triggered by nanoparticle deposition. Although such factors might be important in some circumstances, it is shown that product selectivity may well result from the coupling of competitive chemical steps with short-distance transport of the reactants.

Catalysis at the nanoscale may change selectivity