High‐Index‐Facet Metal‐Alloy Nanoparticles as Fuel Cell Electrocatalysts

Abstract A method to introduce high‐index facets into colloidally synthesized nanoparticles is used to produce compositionally uniform Pt–M (M = Ni, Co, and Cu) and Rh–M (M = Ni and Co) tetrahexahedral nanoparticles. The realization of this method allows for a systematic study of catalyst activity as a function of particle composition for various electrooxidation reactions of liquid fuels (formic acid, methanol, and ethanol). The individual contributions of their high‐index facets, internal alloying of transition metals, and surface Bi modification to their electrocatalytic properties are experimentally explored, resulting in three key findings. First, the presence of high‐index facets is favorable for improving the catalytic activity for all three classes of reactions studied. Second, the effect of transition metal alloying on catalytic activity differs from reaction to reaction. For methanol electrooxidation in an acid electrolyte, due to the contribution from surface Bi modification being negligible, transition metal alloying can significantly the improve overall catalytic efficiency. However, for the other studied reactions, where the surface Bi is highly favorable for improving catalytic activity, there is little influence from transition metal alloying. Finally, multimetallic tetrahexahedral particles have improved stabilities during prolonged operation compared to their monometallic counterparts due to the presence of the alloyed transition metal atoms.