Abstract
Nanoporous metals formed by electrochemical dealloying are seeing increased attention as catalysts for fuel cells because they combine the positive attributes of high geometric surface area, facile processing, and an active core/shell composition profile. Analysis of oxygen reduction in such materials is complicated by the problem of the coupled reaction/diffusion kinetics of oxygen in the small (<5 nm) pores of the material. In porous electrocatalytic media, we show that such kinetics lead to a potential-dependent active surface area that has little to do with the surface area measured by hydrogen underpotential deposition (UPD) - at high overpotential, the effective area participating in oxygen reduction is approximately equal to the geometric area, and this effective area grows when approaching lower overpotentials for oxygen reduction where there is a decreased reaction rate.
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