Molecularly Distorted Local Structure in Bi2CuO4 Oxide to Stabilize Lattice Oxygen for Efficient Formate Electrosynthesis

Abstract The electrochemical CO 2 reduction reaction (CO 2 RR) provides an economically feasible way for converting green energy into valuable chemical feedstocks and fuels. Great progress has been achieved in the understanding and synthesis of oxidized‐based precatalysts; however, their dynamical changes of local structure under operando conditions still hinder their further applications. Here a molecularly distorted Bi 2 CuO 4 precatalyst for efficient CO 2 ‐to‐formate conversion is reported. X‐ray absorption fine structure (XAFS) results and theoretical calculations suggest that the distorted structure with molecularly like [CuO 4 ] 6− unit rotation is more conducive to the structural stability of the sample. Operando XAFS and scanning transmission electron microscopy (STEM) results prove that quite a bit of lattice oxygen can remain in the distorted sample after CO 2 RR. Electrochemical measurements of the distorted sample show an excellent activity and selectivity with a high formate partial current density of 194.6 mA cm −2 at an extremely low overpotential of −400 mV. Further in situ surface‐enhanced infrared absorption spectroscopy (SEIRAS) and density functional theory (DFT) calculations illustrate that the retained oxygen can optimize the adsorption of *OCHO intermediate for the enhanced CO 2 RR performance.