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.