Metal‐Organic Framework‐Derived Partially Oxidized Cu Electrocatalysts for Efficient CO2 Reduction Reaction Toward C2+ Products

ABSTRACT Cu‐based metal‐organic frameworks (Cu‐MOFs) electrocatalysts are promising for CO 2 reduction reactions (CO 2 RR) to produce valuable C 2+ products. However, designing suitable active sites in Cu‐MOFs remains challenging due to their inherent structural instability during CO 2 RR. Here we propose a synergistic strategy through thermal annealing and electrochemical‐activation process for in‐situ reconstruction of the pre‐designed Cu‐MOFs to produce abundant partially oxidized Cu (Cu δ+ ) active species. The optimized MOF‐derived Cu δ+ electrocatalyst demonstrates a highly selective production of C 2+ products, with the Faradaic Efficiency (FE) of 78 ± 2% and a partial current density of −46 mA cm −2 at −1.06 V RHE in a standard H‐type cell. Our findings reveal that the optimized Cu δ+ ‐rich surface remains stable during electrolysis and enhances surface charge transfer, leading to an increase in the concentration of *CO intermediates, thereby highly selectively producing C 2+ compounds. This study advances the controllable formation of MOF‐derived Cu δ+ ‐rich surfaces and strengthens the understanding of their catalytic role in CO 2 RR for C 2+ products.