Atomic Coordination Engineering of MOF Nanostructures for CO ₂ Electroreduction to High‐Value Multi‐Carbon Products at Industrial‐Level Current Density

Metal–organic frameworks (MOFs) have shown great promise for electrochemical carbon dioxide (CO 2 ) reduction into value‐added chemicals/fuels, thereby supporting the balance of carbon‐neutral energy cycle. The multi‐carbon (C 2+ ) production on MOF electrocatalysts is of great significance but remains challenging due to inefficient C–C coupling. Here, we report the atomic coordination regulation of MOF nanostructures (Cu‐Trz‐Br) for efficient CO 2 electroreduction by rationally designing dual‐site Cu catalysts. The crystallographic structure of Cu‐Trz‐Br is determined by three‐dimensional electron diffraction and Rietveld refinement against high‐resolution powder X‐ray diffraction data, which feature unique mixed coordination modes of Cu–N 4 Br 2 and Cu–N 4 sites. In CO 2 electroreduction, Cu‐Trz‐Br demonstrates much enhanced selectivity toward C 2+ products compared to common counterparts with only Cu–N 4 sites, enabling efficient C 2+ production under industrial‐level current density. In situ studies and theoretical calculations reveal that the coordination regulation of Cu–N 4 Br 2 sites promotes CO 2 adsorption and activation, as well as effectively enhances local *CO availability near Cu‐Trz‐Br, thereby facilitating C–C coupling toward C 2+ products.