From MOF Precursors to Active Sites: Defect-Engineered Nanocatalysts for Electrochemical Water Splitting

Controlling electrocatalyst performance at the nanoscale is one of the central challenges in energy materials research. Metal-organic frameworks have emerged as a uniquely powerful platform for meeting that challenge: their ordered porosity, tunable coordination environments, and atomically precise metal-ligand architecture translate, through controlled thermal and chemical conversion, into nanostructured oxides, phosphides, sulfides, nitrides, carbides, and carbon-supported hybrids with programmable active-site distributions. This nanoscale structural control over composition, defect density, and coordination geometry is what distinguishes MOF-derived catalysts from conventionally synthesised materials, and it is what makes them a compelling subject for the hydrogen and oxygen evolution reactions.Yet a central question remains largely unresolved: what is the true catalytic active phase in these materials, and how does it form, evolve, and degrade under real operating conditions? Most studies characterise catalysts before and after testing, leaving the dynamic structural changes that govern both activity and stability poorly understood. Closing this gap requires combining deliberate defect and active-site engineering with operando characterisation and theory, and ultimately testing whether the resulting insights translate into meaningful performance in working electrolysers.This Research Topic brings together original research and focused reviews that address these open questions. We are particularly interested in work that moves beyond synthesis-and-screening toward a mechanistic understanding of how vacancies, coordination-unsaturated sites, heteroatom dopants, and phase boundaries control catalytic behaviour at the nanoscale, and how that behaviour holds up under conditions relevant to practical electrolysis. Studies that couple nanoscale characterisation with device-level validation are especially welcome.Submissions are welcome on the following themes, among others:· Defect and vacancy engineering in MOF-derived nanocatalysts: design strategies and their effect on HER and OER activity· Interface, strain, and amorphous/crystalline boundary engineering· Identification and tracking of the real active phase under reaction conditions· Operando and in situ characterisation (XAS, Raman, electron microscopy) of structural evolution during electrolysis· Single-atom and dual-atom catalysts derived from MOF precursors: structure-activity relationships at the nanoscale· Computational approaches, including DFT and machine learning, for active-site prediction and catalyst design· Heteroatom-doped carbon frameworks as noble-metal-free alternatives· Stability and active-phase durability under device-relevant current densities and extended operation Topic editors: Sivalingam Gopi, A.G. Ramu, Silambarasan Perumal Source: https://www.frontiersin.org/research-topics/82529/from-mof-precursors-to-active-sites-defect-engineered-nanocatalysts-for-electrochemical-water-splitting