Abstract

The electrochemical capture and transformation of carbon dioxide (CO2) (ECC) has recently emerged as a transformative alternative to conventional sorbent-based processes, enabling fully reversible operation under mild conditions and direct compatibility with renewable energy sources. This review focuses on redox-active metal–organic frameworks (MOFs) as electrosorbent materials for the electrochemical capture of CO2. Rather than encompassing all electrochemical CO2 capture technologies, we use molecular, polymeric, and COF-based systems as a framework to define what makes a MOF truly “redox-active” for CO2 electrosorption and how its performance can be assessed. This includes capacitive versus faradic electrosorption mechanisms and design strategies based on the redox chemistry associated with metal nodes, π-conjugated ligands, and strongly redox-active units such as tetrathiafulvalene, viologen, and ferrocene. The way in which defects affect hybrid MOF composites was highlighted, and in situ and operando spectroscopic techniques have improved the understanding of the reaction mechanism in carbon dioxide capture and release under controlled potential. Research comparing carbonaceous materials, redox polymers, and hybrid structures has highlighted both the opportunities and limitations of MOFs, particularly in terms of energy efficiency, scalability, structural robustness, and reproducibility. From a broader perspective, redox-active MOFs occupy a unique position at the intersection of coordination chemistry, electrochemistry, and materials engineering for large-scale applications. In this review, we analyze how redox activity in MOFs—at the metal nodes, ligands, and extended structures—can be harnessed to design energy-efficient, cyclic electrochemical CO2 capture systems. Furthermore, we propose cross-cutting metrics and design rules that enable meaningful comparisons between materials and device architecture.