Coordination-Modulated MOF-Derived Electrocatalysts for Enhanced C─C Coupling in CO₂ to C₂H₄ and C₂H₅OH Conversion

Electrochemical CO₂ reduction (CO₂RR) to high-value C₂ products- ethylene (C₂H₄) and ethanol (C₂H₅OH)- offers a sustainable pathway to mitigate anthropogenic emissions and close the carbon cycle. However, high energy barriers for CO₂ 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 CO₂ activation and direct C─C coupling for precise product control. This review comprehensively explores mechanistic pathways for C₂H₄ and C₂H₅OH 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 CO₂ activation from C─C coupling. These advances position MOFs as transformative materials for enabling efficient, scalable carbon-neutral CO₂RR technologies, while ongoing challenges and development prospects are critically examined.