A Bismuth‐Based Zeolitic Organic Framework with Coordination‐Linked Metal Cages for Efficient Electrocatalytic CO2 Reduction to HCOOH

Abstract Zeolitic metal–organic frameworks (ZMOFs) have emerged as one of the most promsing catalysts for energy conversion, but they suffer from either weak bonding between metal‐organic cubes (MOCs) that decrease their stability during catalysis processes or low activity due to inadequate active sites. In this work, through ligand‐directing strategy, we successfully obtain an unprecedented bismuth‐based ZMOF (Bi‐ZMOF) featuring a ACO topological crystal structure with strong coordination bonding between the Bi‐based cages. As a result, it enables efficient reduction of CO 2 to formic acid (HCOOH) with Faradaic efficiency as high as 91 %. A combination of in situ surface‐enhanced infrared absorption spectroscopy and density functional theory calculation reveals that the Bi−N coordination contributes to facilitating charge transfer from N to Bi atoms, which stabilize the intermediate to boost the reduction efficiency of CO 2 to HCOOH. This finding highlights the importance of the coordination environment of metal active sites on electrocatalytic CO 2 reduction. We believe that this work will offer a new clue to rationally design zeolitic MOFs for catalytic reaction