The role of atomic ensembles in the reactivity of bimetallic electrocatalysts.

Bimetallic electrodes are used in a number of electrochemical processes, but the role of particular arrangements of surface metal atoms (ensembles) has not been studied directly. We have evaluated the electrochemical/catalytic properties of defined atomic ensembles in atomically flat PdAu(111) electrodes with variable surface stoichiometry that were prepared by controlled electrodeposition on Au(111). These properties are derived from infrared spectroscopic and voltammetric data obtained for electrode surfaces for which the concentration and distribution of the respective metal atoms are determined in situ by atomic resolution scanning tunneling microscopy with chemical contrast. Palladium monomers are identified as the smallest ensemble ("critical ensemble") for carbon monoxide adsorption and oxidation, whereas hydrogen adsorption requires at least palladium dimers.