Multifunctional metal–organic framework-based electrocatalysts: from CO2 reduction and ammonia synthesis to urea production

The urgent need for sustainable chemical production has spurred interest in electrocatalytic technologies powered by renewable electricity. Among these, electrocatalytic carbon dioxide reduction (ECR), electrocatalytic ammonia synthesis (EAS), and particularly electrocatalytic urea synthesis (EUS) offer promising strategies for green carbon–nitrogen conversion. EUS stands out by co-reducing CO 2 and nitrogen sources (e.g., N 2 , NO, NO 2 − , NO 3 − ) to enable C–N bond formation, presenting unique opportunities for resource efficiency and emissions reduction. However, its practical implementation is limited by insufficient catalytic activity, selectivity, and durability; incomplete understanding of C–N coupling pathways; and competition from side reactions. Metal–organic framework (MOF)-based materials have emerged as versatile platforms for electrocatalysis owing to their tunable metal nodes and ligand chemistry, multifunctional active sites, and hierarchically porous architectures that afford efficient mass transport. Accordingly, MOF-based platforms are poised to lower the intrinsic C–N coupling barrier, coordinate dual-substrate delivery and co-adsorption, suppress parasitic hydrogen evolution reaction (HER), and improve charge transport and durability in EUS. This review categorizes MOF functionalization strategies for active site design and microenvironment modulation. It then evaluates representative advances with MOF-based materials in ECR, EAS, and EUS, with a particular focus on elucidating structure–mechanism–performance correlations. Drawing on insights from ECR and EAS, we propose transferable design principles to guide the rational development of MOF-based systems for efficient EUS. Finally, we highlight persistent challenges and outline future research directions to advance cross-reaction design strategies and accelerate the practical deployment of MOF-based electrocatalysts. This review outlines functionalization strategies for metal–organic frameworks (MOFs) to enhanced electrocatalysis. Drawing on established literature on MOF-based electrocatalysts for CO 2 reduction and ammonia synthesis, it links active-site and microenvironment engineering to urea synthesis, evaluates the roles of electrolytes, reactor architecture, and external fields, and ultimately distills transferable design principles for sustainable C–N conversion.