Binary Pd−Ni Nanoalloy Particles over Carbon Support with Superior Alkaline Formate Fuel Electrooxidation Performance

Formate is the one legitimate carbon‐neutral fuel that has the capability of being considered an alternative to alcohol fuels amidst the growing demand for efficient fuel‐cell systems. In this manuscript, we demonstrate, for the first time, a class of binary Pd−Ni alloy nanoparticles over two different carbon supports showing exceptional enhancement of the formate oxidation reaction (FOR) performance in alkaline medium, compared to Pd/C. The synergistic effects of Pd and oxophilic Ni along with the electronic structure alteration of Pd induced through alloying resulted in an effective change in its catalytic ability, leading to a 5‐time enhancement in the overall current density along with a lower overpotential during formate oxidation compared to Pd/C. The more active Pd catalytic sites of the nanoalloy helped to yield mass activities as high as 4.5 A mg−1Pd and 7.8 A mg−1Pd during FOR. The structural and electrochemical analysis justifies the synergistic effects and alterations in the Pd lattice ensuing a superior enhancement of electrochemically active Pd sites.