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.