A Combinatorial Approach to the Study of Particle Size Effects on Supported Electrocatalysts: Oxygen Reduction on Gold

Abstract

A novel high-throughput technique has been developed for the investigation of the influence of supported metal particle size and the support on electrocatalytic activity. Arrays with a gradation of catalyst particle sizes are fabricated in a physical vapor deposition system that also allows selection of the support material. Simultaneous electrochemical measurements at all electrodes in the array, together with determination of the actual particle size distribution on each of the electrodes by transmission electron microscopy (TEM), then allows rapid determination of the activity as a function of catalyst center size. The procedure is illustrated using data for the reduction of oxygen on gold nanoparticles supported on both substoichiometric titanium dioxide (TiO_x) and carbon and the conclusions are verified using voltammetry at rotating disk electrodes. Gold centers with diameters in the range 1.4−6.3 nm were investigated and it is demonstrated that, with both supports, the catalytic activity for oxygen reduction decays rapidly for particle sizes below 3.0 nm. This may be observed as a decrease in current at constant potential or an increase in the overpotential for oxygen reduction.