Spatially‐Directed C─C Coupling inside Three‐dimensional Metal‐organic Frameworks for CO ₂ Electroreduction to C ₂ Products

The CO₂ electroreduction reaction to fuels and chemicals is a promising strategy for storing intermittent energy (such as sunlight and wind power) and closing the carbon cycle. Producing multi-carbon oxygenates and hydrocarbons (C₂₊) with broader applicability is highly desirable. However, the difficulty of the C─C coupling reaction hinders the conversion of CO₂ to C₂₊ products with high energy input, low reaction rate, and poor selectivity. Here, we construct a three-dimensional (3D) Fe-quinoxalinedithiol (Fe-QDT)-based metal-organic framework (MOF) featuring dual Fe sites within its ordered channel walls, enabling efficient interwall electrocatalysis for C₂ coupling reactions. We found that dual Fe sites can co-catalyze the dimerization of *OCH₂ to *OCH₂CH₂O*, thus facilitating the generation of C₂ products. The free energy changes for the potential-limiting steps in the electroreduction of C₂ species are -0.010 and 0.045 eV for CH₃CH₂OH and C₂H₄, respectively, which are significantly lower than those for other C₂ products. Consequently, the Fe-QDT MOFs demonstrate high activity and selectivity in converting CO₂ to CH₃CH₂OH and C₂H₄. This work designs a novel and efficient active site for C─C coupling and provides valuable insights into the design principles of electrocatalysts for C₂ products.