Electrocatalysis by Mass-Selected Ptn Clusters.

Abstract

Mass-selected Ptn+ ion deposition in ultrahigh vacuum (UHV) was used to prepare a series of size-selected electrodes with Ptn (n ≤ 14) clusters supported on either glassy carbon (GC) or indium tin oxide (ITO). After characterization of the physical properties of the electrodes in UHV, an in situ method was used to study electrocatalytic activity for the oxygen reduction and ethanol oxidation reactions, without significant air exposure. For each reaction studied, there are similarities between the catalytic properties of Ptn-containing electrodes and those of nanoparticulate or bulk Pt electrodes, but there are also important differences that provide mechanistic insights. For all systems, strong cluster size effects were observed. For comparison, select experiments were done under identical conditions but with the Ptn electrodes exposed to air prior to electrochemical studies, resulting in strong modification/suppression of catalytic activity due to adventitious contaminants. For ethanol oxidation at Ptn/ITO, activity varies with size nonmonotonically, by more than an order of magnitude. The sharp size dependence persists during at least 30 to 40 cycles through the Pt redox potential, indicating that processes that would tend to broaden the size distribution are not efficient. All but the least active sizes are substantially more active per mass of Pt, than Pt nanoparticles under the same conditions. The oscillatory dependence of activity on size is anticorrelated with the binding energy of the Pt 4d core level, demonstrating that activity is controlled by the electronic structure of the supported clusters. For oxygen reduction at Ptn/ITO, the branching between water and hydrogen peroxide production is strongly dependent on cluster size, with small clusters selectively producing peroxide with high activity. The selectivity appears to be related to the size of the active site, with no obvious correlation to Pt electronic properties. The most unusual effect seen was for Ptn/GC, studied under acid conditions appropriate to oxygen reduction. Pt7 and a few other cluster sizes show "normal" oxygen reduction activity, similar to what is measured for Pt nanoparticles on GC under the same conditions. Many of the small clusters, however, are found to catalyze highly efficient oxidation, by water, of the glassy carbon support, with essentially no overpotential. The high activity for carbon oxidation for many Ptn/GC electrodes and the absence of significant carbon oxidation for a GC electrode with Pt nanoparticles raise the question of whether small Pt clusters may be responsible for much of the corrosion observed in Pt/carbon electrodes. This system provides another example where activity for oxidation catalysis is anticorrelated with the Pt core level binding energies, indicating that it is electronic, rather than geometric, structure that limits activity.