Heteroatom-Driven Coordination Fields Altering Single Cerium Atom Sites for Efficient Oxygen Reduction Reaction.

Abstract

For current single-atom catalysts (SACs), modulating the coordination environments of rare-earth (RE) single atoms with complex electronic orbital and flexible chemical states is still limited. Herein, cerium (Ce) SAs supported on a P, S, and N co-doped hollow carbon substrate (Ce SAs/PSNC) for the oxygen reduction reaction (ORR) are reported. The as-prepared Ce SAs/PSNC possesses a half-wave potential of 0.90V, a turnover frequency value of 52.2s-1 at 0.85V, and excellent stability for the ORR, which exceeds the commercial Pt/C and most recent SACs. Ce SAs/PSNC-based liquid zinc-air batteries (ZABs) exhibit a high and stable open-circuit voltage of 1.49V and a maximum power density of 212mWcm-2 . As the catalyst of the air cathode, it also displays remarkable performance in flexible electronic devices. Theoretical calculations reveal that the introduction of S and P sites induces significant electronic modulations to the Ce SA active sites. The P and S dopings promote the electroactivity of Ce SAs and improve the overall site-to-site electron transfer within the Ce SAs/PSNC. This work offers a unique perspective for modulating RE-based SACs in a complex coordination environment toward superior electrocatalysis and broad applications in energy conversion and storage devices.