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

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.