Advancing MOFs for electrocatalytic ORR, UOR, and CO2RR: From fundamentals to device integration and deployment challenges

Metal-organic frameworks (MOFs) offer a uniquely tunable platform for electrocatalysis, yet their path from fundamental promise to industrial application remains a critical challenge. This review comprehensively examines the role of MOFs in three pivotal electrochemical reactions: oxygen reduction reaction (ORR), urea oxidation reaction (UOR), and carbon dioxide reduction reaction (CO 2 RR). The fundamental mechanisms of these reactions, bolstered by insights from density functional theory (DFT) calculations, are discussed to provide a foundational understanding of the electrocatalytic processes at the molecular level. The review further explores the integration of MOFs into real-world electrochemical devices, including fuel cells, metal-air batteries, urea electrolysis and CO 2 electrolyzers, with an emphasis on their potential for energy production, hydrogen generation, wastewater treatment, and carbon utilization. The challenges of scaling up MOF-based technologies for industrial applications are critically analyzed, covering technoeconomic considerations, sustainability factors, and mitigation strategies such as MOF hybrids, post-synthetic modifications, as well as advanced composite systems such as polyoxometalate@MOF (POM@MOF) and covalent organic framework@MOF (COF@MOF) heterostructures. Finally, this review maps a forward-looking roadmap to address the deployment challenges for MOFs in ORR, UOR, and CO 2 RR systems. This integrated perspective underscores the potential of MOFs to bridge the gap from fundamental mechanisms to real-world application, accelerating their role in sustainable electrochemical energy devices.