Altering Ligand Fields in Single-Atom Sites through Second-Shell Anion Modulation Boosts the Oxygen Reduction Reaction

Abstract

Single-atom catalysts based on metal-N₄ moieties and anchored on carbon supports (defined as M-N-C) are promising for oxygen reduction reaction (ORR). Among those, M-N-C catalysts with 4d and 5d transition metal (TM_4d,5d) centers are much more durable and not susceptible to the undesirable Fenton reaction, especially compared with 3d transition metal based ones. However, the ORR activity of these TM_4d,5d-N-C catalysts is still far from satisfactory; thus far, there are few discussions about how to accurately tune the ligand fields of single-atom TM_4d,5d sites in order to improve their catalytic properties. Herein, we leverage single-atom Ru-N-C as a model system and report an S-anion coordination strategy to modulate the catalyst's structure and ORR performance. The S anions are identified to bond with N atoms in the second coordination shell of Ru centers, which allows us to manipulate the electronic configuration of central Ru sites. The S-anion-coordinated Ru-N-C catalyst delivers not only promising ORR activity but also outstanding long-term durability, superior to those of commercial Pt/C and most of the near-term single-atom catalysts. DFT calculations reveal that the high ORR activity is attributed to the lower adsorption energy of ORR intermediates at Ru sites. Metal-air batteries using this catalyst in the cathode side also exhibit fast kinetics and excellent stability.