Single‐Atom Alloys for the Electrochemical Oxygen Reduction Reaction

Single‐atom alloys (SAAs) consisting of isolated transition‐metal atoms doped in the surface of coinage metal hosts exhibit unique catalytic properties, harnessing the high activity of the dopant metals with the selectivity of the coinage metal hosts. Here we use density functional theory (DFT) to study SAAs comprised of Ni, Pd, Pt, Co and Rh doped into Ag and Au hosts, as candidate electrocatalysts for the oxygen reduction reaction (ORR) in proton‐exchange membrane (PEM) fuel‐cells. Our calculations reveal that the PdAu SAA exhibits a slightly lower theoretical overpotential, enhanced selectivity for 4‐e(−) ORR, and tolerance to CO‐poisoning compared to Pt(111). While the number of active sites of PdAu SAA is lower than that of Pt(111), the aforementioned desirable properties could bring the overall catalytic performance thereof close to that of Pt/C, indicating that the PdAu SAA could be a viable material for electrocatalytic ORR in PEM fuel‐cells.