Organometallic Frameworks for Efficient Electrocatalytic CO₂ Reduction Reactions

The electrocatalytic conversion of CO₂ to value-added chemicals driven by renewable electricity offers a viable strategy to reduce atmospheric CO₂ concentration and realize energy storage. Crystalline porous metal-organic frameworks (MOFs) with periodically ordered isolated metal active sites and large surface areas represent promising CO₂ reduction reaction (CO₂RR) catalysts due to their rapid CO₂ adsorption kinetics. However, conventional MOFs typically exhibit insufficient CO₂RR 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 CO₂RR performances. The distinctive σ-π coordination motif between alkyne moieties and metal centers endows these frameworks with enhanced electron transfer capability, superior CO₂ activation ability, and significantly improved CO₂RR 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 CO₂ electroreduction processes.