Atomic Coordination Engineering of MOF Nanostructures for CO2 Electroreduction to High-Value Multi-Carbon Products at Industrial-Level Current Density.

Metal-organic frameworks (MOFs) have shown great promise for electrochemical carbon dioxide (CO2) reduction into value-added chemicals/fuels, thereby supporting the balance of carbon-neutral energy cycle. The multi-carbon (C2+) 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 CO2 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-N4Br2 and Cu-N4 sites. In CO2 electroreduction, Cu-Trz-Br demonstrates much enhanced selectivity toward C2+ products compared to common counterparts with only Cu-N4 sites, enabling efficient C2+ production under industrial-level current density. In situ studies and theoretical calculations reveal that the coordination regulation of Cu-N4Br2 sites promotes CO2 adsorption and activation, as well as effectively enhances local *CO availability near Cu-Trz-Br, thereby facilitating C-C coupling toward C2+ products.