From Single-atom to Bi-atom and Ordered Multi-atom: Not Just a Number Changing for Electrocatalysis

Abstract

Atomically dispersed catalysts, i.e., single-atom catalysts (SACs), have attracted considerable interest because of their 100% atom utilization and unique geometric and electronic structures relative to nanoparticles. Atomic manipulation enables the construction of well-defined active sites on an atom-by-atom basis, which is particularly intriguing for electrocatalysis. Bi-atom catalysts (BACs) represent an important branch, where atomic pairs can markedly enhance the efficiency and selectivity of electrocatalysis. Emerging as a new subclass, ordered multiatom catalysts (OMACs) have received significant attention recently. Unlike randomly distributed single atoms, the OMACs possess ordered atomic arrangements, like atomic arrays and ordered single-atom alloys. Geometrically, this order could enhance intrinsic activity and reaction selectivity by making interatomic distance just right or customizing atomic arrangements for the lower activation energy pathway, and simultaneously improve the density of active sites to some extent. Electronically, this order may induce new electronic states and/or strong orbital hybridization between neighboring atoms, thereby enabling unexpected activity. The ensemble effect and/or synergistic effect would become feasible by rational regulation of atomic arrangements and components of OMACs. We herein reviewed the recent advance from single-atom to biatom and ordered multiatom mainly emphasizing OMACs, discussed their synthesis, characterizations, and electrocatalytic applications, and finally proposed some challenges and prospects for better developing single-atom catalysis.

Keywords

Single-atom catalysts / Bi-atom catalyst / Ordered multiatom catalyst / Ensemble effect / Synergistic effect

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