Ultrafine RuIr Alloy Nanoparticles Embedded in N‐Doped Porous Carbon Nanofibers From Energetic Metal–Organic Frameworks for Hydrogen Evolution Electrocatalysis

Designing efficient and durable electrocatalysts for alkaline hydrogen evolution reaction (HER) is pivotal to a sustainable hydrogen economy. Here, we embed ultrafine RuIr alloy nanoparticles in N-doped porous carbon nanofibers (NCNFs) by electrospinning energetic metal-organic framework (MOF) precursors followed by pyrolysis. The resulting RuIr@NCNFs exhibit an overpotential as low as 22 mV at 10 mA cm^-2 in 1.0 M KOH, surpassing commercial Pt/C, and exhibit negligible activity decay over 12 h of continuous operation. Combined density functional theory and spectroscopy indicate Ir → Ru charge redistribution that optimizes ΔG_H _* and facilitates water dissociation (Volmer), thereby accelerating the overall alkaline HER kinetics. Meanwhile, Ir incorporation mitigates Ru oxidation, enhancing long-term durability. Additionally, the N-doped porous carbon scaffold enhances electronic conductivity and mass transport, further boosting performance. This work highlights how bimetallic synergy coupled with MOF-derived carbon architectures enables highly active and robust alkaline HER catalysts with technologically relevant durability.