Significantly enhanced electrocatalytic activity of Au 25 clusters by single platinum atom doping

Abstract The search for highly active catalysts with low-Pt content to advance the commercialization of fuel cells is continuing to receive ample attention. Herein, we report that by doping a single Pt atom into Au 25 to form Pt 1 Au 24 nanoclusters, the electrocatalytic activity for the direct formic acid oxidation (FAO) to carbon dioxide is enhanced significantly. The mass activity of Pt 1 Au 24 (3.7 A mg Pt+Au − 1 ) is nearly 12 and 34 times greater than that of Pt nanoclusters and the commercial Pt/C catalyst, respectively. Density functional theory (DFT) calculations and potential-dependent thermodynamic analyses provide fundamental insights into the reaction mechanism illustrating that FAO proceeds through the carboxyl (COOH) intermediate on Pt 1 Au 24 . The present study not only develops a novel class of single-Pt atom doped Au nanocluster electrocatalysts for fuel cells with high utilization of Pt, but also provides insight into the mechanism of FAO on Pt-doped Au nanoclusters. Moreover, this study begins to shed light on the structure-activity relationship and helps to provide a strategy to design new catalysts by tuning their catalytic properties at the atomic level.