Synergistic catalysis of Zn Single Atoms and Co Clusters for Highly Selective CO 2 Electroreduction to CO

ABSTRACT Electrochemical CO 2 reduction to CO provides a promising route for renewable electricity‐driven carbon recycling, yet developing catalysts that simultaneously achieve high CO selectivity, large current density, and long‐term stability remains challenging. Herein, we report a MOF‐derived Zn single atom–Co few‐atom cluster catalyst embedded in N‐doped carbon, denoted as Zn SA –Co Clu /NC. Microscopy and X‐ray absorption spectroscopy confirm the preserved polyhedral morphology, homogeneous metal distribution, atomic dispersion of Zn species, and the presence of highly undercoordinated Co cluster‐related motifs with detectable Co–Co coordination. The Zn SA –Co Clu /NC delivers a FE CO approaching 98% and a markedly enhanced CO partial current density compared with Co SA /NC, Zn SA /NC and Co Clu /NC. In a flow‐cell electrolyzer, it reaches an industrially relevant current density of −800 Ma cm −2 at −1.0 V vs. RHE and maintains stable CO production for 60 h at −500 mA cm −2 . In situ X‐ray Absorption Fine Structure (XAFS) reveals opposite potential‐dependent electronic evolution of Zn and Co centers, evidencing dynamic interfacial charge redistribution within the Zn single atom–Co cluster ensemble. This cooperative electronic interaction optimizes CO 2 activation and CO‐forming intermediate adsorption, thereby enabling selective and high‐rate CO production.