Coordination‐Modulated MOF‐Derived Electrocatalysts for Enhanced C─C Coupling in CO 2 to C 2 H 4 and C 2 H 5 OH Conversion

Electrochemical CO 2 reduction (CO 2 RR) to high‐value C 2 products‐ ethylene (C 2 H 4 ) and ethanol (C 2 H 5 OH)‐ offers a sustainable pathway to mitigate anthropogenic emissions and close the carbon cycle. However, high energy barriers for CO 2 activation impede large‐scale implementation, necessitating catalysts with exceptional activity, selectivity, and stability. Metal–organic frameworks (MOFs) have emerged as prime candidates by leveraging their tunable architecture, high surface areas, and customizable active sites to enhance CO 2 activation and direct C─C coupling for precise product control. This review comprehensively explores mechanistic pathways for C 2 H 4 and C 2 H 5 OH formation over MOF‐based catalysts through an integrated methodology: elucidating reaction mechanisms of key * CO intermediates during proton‐coupled electron transfers; resolving dynamic active sites via in situ spectroscopy; and uncovering energy barriers and reaction pathways through DFT calculation. We further outline strategic research directions, including machine learning‐guided MOF screening, heterobimetallic MOFs for synergistic catalysis, and cascade reactors decoupling CO 2 activation from C─C coupling. These advances position MOFs as transformative materials for enabling efficient, scalable carbon‐neutral CO 2 RR technologies, while ongoing challenges and development prospects are critically examined.