A General Strategy to Atomically Dispersed Precious Metal Catalysts for Unravelling Their Catalytic Trends for Oxygen Reduction Reaction

Abstract

Atomically dispersed precious metal catalysts have emerged as a frontier in catalysis. However, a robust, generic synthetic strategy toward atomically dispersed catalysts is still lacking, which has limited systematic studies revealing their general catalytic trends distinct from those of conventional nanoparticle (NP)-based catalysts. Herein, we report a general synthetic strategy toward atomically dispersed precious metal catalysts, which consists of "trapping" precious metal precursors on a heteroatom-doped carbonaceous layer coated on a carbon support and "immobilizing" them with a SiO2 layer during thermal activation. Through the "trapping-and-immobilizing" method, five atomically dispersed precious metal catalysts (Os, Ru, Rh, Ir, and Pt) could be obtained and served as model catalysts for unravelling catalytic trends for the oxygen reduction reaction (ORR). Owing to their isolated geometry, the atomically dispersed precious metal catalysts generally showed higher selectivity for H2O2 production than their NP counterparts for the ORR. Among the atomically dispersed catalysts, the H2O2 selectivity was changed by the types of metals, with atomically dispersed Pt catalyst showing the highest selectivity. A combination of experimental results and density functional theory calculations revealed that the selectivity trend of atomically dispersed catalysts could be correlated to the binding energy difference between *OOH and *O species. In terms of 2 e(-) ORR activity, the atomically dispersed Rh catalyst showed the best activity. Our general approach to atomically dispersed precious metal catalysts may help in understanding their unique catalytic behaviors for the ORR.