Bicontinuous RuO₂ nanoreactors for acidic water oxidation

Improving activity and stability of Ruthenium (Ru)-based catalysts in acidic environments is eager to replace more expensive Iridium (Ir)-based materials as practical anode catalyst for proton-exchange membrane water electrolyzers (PEMWEs). Here, a bicontinuous nanoreactor composed of multiscale defective RuO₂ nanomonomers (MD-RuO₂-BN) is conceived and confirmed by three-dimensional tomograph reconstruction technology. The unique bicontinuous nanoreactor structure provides abundant active sites and rapid mass transfer capability through a cavity confinement effect. Besides, existing vacancies and grain boundaries endow MD-RuO₂-BN with generous low-coordination Ru atoms and weakened Ru-O interaction, inhibiting the oxidation of lattice oxygen and dissolution of high-valence Ru. Consequently, in acidic media, the electron- and micro-structure synchronously optimized MD-RuO₂-BN achieves hyper water oxidation activity (196 mV @ 10 mA cm^-2) and an ultralow degradation rate of 1.2 mV h^-1. A homemade PEMWE using MD-RuO₂-BN as anode also conveys high water splitting performance (1.64 V @ 1 A cm^-2). Theoretical calculations and in-situ Raman spectra further unveil the electronic structure of MD-RuO₂-BN and the mechanism of water oxidation processes, rationalizing the enhanced performance by the synergistic effect of multiscale defects and protected active Ru sites.