Asymmetrically coordinated single-atom catalysts: from synthetic strategy to structure-activity relationship

Abstract

Asymmetric coordination structures in single-atom catalysts (SACs) represent a frontier in electrocatalysis, offering tunable electronic environments and enhanced catalytic performance beyond traditional symmetric M–N₄ motifs. This review first categorizes asymmetric SACs into four structural families: (1) single-metal asymmetric coordination, achieved by heteroatom substitution or axial ligand incorporation; (2) non-contact multi-metal sites, where adjacent but unbonded metal atoms synergize electronically; (3) directly bimetallic-bonded asymmetric coordination structures; and (4) bridged multi-metal constructs connected via non-metal linkers (e.g., O, N, S). Key synthetic strategies, including metal–organic framework confinement, defect engineering, dual-solvent loading, and macrocyclic precursor mediation, are examined in detail. Then we summarize applications in oxygen reduction reaction and CO₂ reduction reaction catalysis, and highlight how asymmetric coordination tunes intermediate adsorption energies, breaks scaling relations, and enables tandem catalysis to improve activity, selectivity, and stability. Advanced characterization techniques - aberration-corrected scanning transmission electron microscopy with electron energy loss spectroscopy, synchrotron X-ray absorption spectroscopy, and time-of-flight secondary ion mass spectrometry - are discussed for their roles in resolving atomic dispersion, coordination environment, oxidation states, and dynamic evolution under operando conditions. Finally, challenges and future directions are outlined, including precise low-temperature assembly of heteronuclear sites, scalability, long-term stability under harsh reaction conditions, selective pathway control, and the integration of operando analyses with theoretical modeling to guide rational catalyst design.

Keywords

Single-atom catalysts / asymmetric coordination / electrocatalysis / oxygen reduction reaction / CO₂ reduction reaction

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