Rational Design of MOF‐Based Electrocatalysts for Selective CO ₂ Reduction

ABSTRACT The electrochemical CO ₂ reduction reactions (eCO ₂ RR) offer a promising route to convert waste CO ₂ into valuable fuels and chemicals, yet their practical deployment hinges on the development of catalysts that can deliver high selectivity at industrially relevant current densities. Metal–organic frameworks (MOFs) have emerged as a versatile platform for eCO ₂ RR catalyst design, owing to their high surface areas, atomically tunable active sites, chemically functionalizable pore environments, and well‐defined structures. Herein, recent advances in MOF‐based electrocatalysts for selective CO ₂ reduction are comprehensively summarized, with the discussion organized according to target product scope to reflect the distinct catalytic requirements of each reaction pathway. For C ₁ products (CO, CH ₄ , HCOOH), we discuss how ligand engineering, bimetallic synergy, and microenvironment modulation have been deployed to meet the distinct catalytic requirements of each pathway. For C ₂₊ products (ethylene, ethanol), we analyze strategies for enabling C─C coupling and controlling post‐coupling hydrogenation pathways, including reconstruction guidance, tandem catalysis, and secondary coordination sphere engineering. By providing a comprehensive overview of recent progress and design strategies, this review outlines prospective research directions, aiming to provide insights for the rational development of next‐generation MOF‐based electrocatalysts for selective CO ₂ reduction.