Structure-Activity Relationships in Metal-Organic Framework-based Catalysts for Electrochemical CO₂ Reduction

Abstract

Metal-organic frameworks (MOFs) have emerged as a versatile platform for electrochemical CO₂ reduction (CO₂RR), offering a unique combination of molecular-level tunability and solid-state robustness. This review surveys recent advances in MOF-based and MOF-derived catalysts from the perspective of solid-state chemistry, with particular emphasis on how structural parameters govern catalytic pathways and performance. Rather than merely summarizing material systems, we critically examine how the engineering of metal nodes, from isolated single sites to cooperative bimetallic motifs, modulates the adsorption energetics of key reaction intermediates. We further discuss the synergistic roles of ligand functionalization, pore architecture, and defect chemistry in regulating the local electronic structure and microenvironment of active sites. By correlating coordination geometry, charge-transfer behavior, and intermediate binding with catalytic activity and product selectivity, this review establishes a structure-activity framework to guide the rational design of next-generation MOF-based electrocatalysts for CO₂RR.

Keywords

Metal-organic framework / CO₂ electroreduction / Structure-activity relationship / Coordination environment / Defect chemistry

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