Organometallic Frameworks for Efficient Electrocatalytic CO ₂ Reduction Reactions

ABSTRACT The electrocatalytic conversion of CO 2 to value‐added chemicals driven by renewable electricity offers a viable strategy to reduce atmospheric CO 2 concentration and realize energy storage. Crystalline porous metal‐organic frameworks (MOFs) with periodically ordered isolated metal active sites and large surface areas represent promising CO 2 reduction reaction (CO 2 RR) catalysts due to their rapid CO 2 adsorption kinetics. However, conventional MOFs typically exhibit insufficient CO 2 RR current densities stemming from inherent low electrical conductivity and sluggish electron transfer kinetics. Introducing Metal‐C bonds into the framework can directly regulate the electronic structure of the metal center, optimizing intermediate adsorption. Herein, we synthesized two organometallic frameworks featuring carbon‐silver connectivity to enhance the CO 2 RR performances. The distinctive σ‐π coordination motif between alkyne moieties and metal centers endows these frameworks with enhanced electron transfer capability, superior CO 2 activation ability, and significantly improved CO 2 RR performance. Crucially, these materials achieve exceptional CO Faraday efficiencies (FE CO ) exceeding 90% when operated at industrially relevant current densities (> 500 mA cm −2 ), surpassing most reported MOF‐based systems. This work establishes a novel design paradigm for organometallic frameworks and accelerates their practical deployment in industrial CO 2 electroreduction processes.