MOF-based and MOF-derived electrocatalysts for anodic reactions coupled with hydrogen evolution

Abstract

Energy-efficient and sustainable hydrogen production is essential for mitigating environmental pollution and enabling the energy transition, yet practical water electrolysis is hindered by the sluggish, energy-intensive oxygen evolution reaction (OER). Replacing the OER with thermodynamically and kinetically favorable value-added anodic reactions can lower the required voltage while co-producing useful chemicals and, in some cases, enabling wastewater remediation. Metal–organic frameworks (MOFs) provide a distinctive catalyst platform for such hybrid electrolysis: their modular architectures enable tunable compositions, deliberately engineered active sites and microenvironments, and adjustable adsorption/activation behaviors; moreover, they can serve as versatile precursors to derived conductive phases. Despite rapid progress, advances remain scattered across diverse anodic reactions and catalyst formats, and a MOF-centered framework linking materials engineering, reaction pathways, and coupled-cell performance is still needed. Here, we review MOF-based electrocatalysts (pristine MOFs, MOF composites, and MOF-derived materials) for coupling the hydrogen evolution reaction (HER) with OER-substituting anodic processes. We organize the literature by reaction classes, including alcohol/polyol oxidations (methanol, ethanol/ethylene glycol, glycerol, and benzyl alcohol), biomass-platform oxidations (5-hydroxymethylfurfural/furfural and glucose), and waste/inorganic oxidations (urea and hydrazine), highlighting catalyst performance and design strategies. We further summarize MOF-based bifunctional catalysts and recurring design principles, including self-supported architectures, MOF-derived phosphides/sulfides and mixed phases, heterostructure/interface engineering, and the roles of high-valent species and in situ reconstruction under operating conditions. Finally, key challenges and perspectives are outlined to guide next-generation MOF-based bifunctional catalysts for energy-saving hydrogen production coupled with green chemical synthesis.