Manipulating Surface Reconstruction of a Metal–Organic Framework to Achieve Molecule‐Enhanced CO ₂ Electroreduction

ABSTRACT The electrochemical reconstruction behavior of metal–organic frameworks (MOFs) profoundly affects their catalytic performance, but their effective regulation remains a major challenge. Herein, we propose a facile single‐atom‐driven strategy to manipulate the surface reconstruction of a gallogen‐based MOF, engineering an efficient active structure of ellagic acid and monatomic Cu co‐modified bismuth oxycarbonate, achieving organic–inorganic dual‐modulation. The reconstructed organic–inorganic hybrid electrocatalyst demonstrates notable performance for CO 2 electroreduction to formate with a maximal Faraday efficiency of 99.4% ± 1.5%. Moreover, throughout the continuous electrocatalysis period of 600 h at 250 mA·cm −2 , the formate Faraday efficiency always maintains above 95.2% ± 2.4%. The corresponding charge transfer amount for formate generation reaches 507600 C·cm −2 , representing one of the best among CO 2 ‐to‐formate electrocatalysts and setting a record among bismuth‐based electrocatalysts. A series of operando and non‐operando characterization techniques combined with theoretical calculations reveal that the dual‐modulation of monatomic Cu and ellagic acid optimizes the p ‐band center of Bi sites, thereby enhancing the adsorption of key * OCHO intermediate. This work establishes a molecular enhancement paradigm for engineering high‐performance electrocatalysts by harnessing surface reconstruction of MOFs.