Electrocatalytic CO(2) Reduction on CuO(x) Nanocubes: Tracking the Evolution of Chemical State, Geometric Structure, and Catalytic Selectivity using Operando Spectroscopy

The direct electrochemical conversion of carbon dioxide (CO(2)) into multi‐carbon (C(2+)) products still faces fundamental and technological challenges. While facet‐controlled and oxide‐derived Cu materials have been touted as promising catalysts, their stability has remained problematic and poorly understood. Herein we uncover changes in the chemical and morphological state of supported and unsupported Cu(2)O nanocubes during operation in low‐current H‐Cells and in high‐current gas diffusion electrodes (GDEs) using neutral pH buffer conditions. While unsupported nanocubes achieved a sustained C(2+) Faradaic efficiency of around 60 % for 40 h, the dispersion on a carbon support sharply shifted the selectivity pattern towards C(1) products. Operando XAS and time‐resolved electron microscopy revealed the degradation of the cubic shape and, in the presence of a carbon support, the formation of small Cu‐seeds during the surprisingly slow reduction of bulk Cu(2)O. The initially (100)‐rich facet structure has presumably no controlling role on the catalytic selectivity, whereas the oxide‐derived generation of under‐coordinated lattice defects, can support the high C(2+) product yields.