Electronic Structure Engineering of Single‐Atom Ru Sites via Co–N4 Sites for Bifunctional pH‐Universal Water Splitting

The development of bifunctional water-splitting electrocatalysts that are efficient and stable over a wide range of pH is of great significance but challenging. Here, an atomically dispersed Ru/Co dual-sites catalyst is reported anchored on N-doped carbon (Ru/Co-N-C) for outstanding oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in both acidic and alkaline electrolytes. The Ru/Co-N-C catalyst requires the overpotential of only 13 and 23 mV for HER, 232 and 247 mV for OER to deliver a current density of 10 mA cmgeo-2 in 0.5 m H2 SO4 and 1 m KOH, respectively, outperforming benchmark catalysts Pt/C and RuO2 . Theoretical calculations reveal that the introduction of Co-N4 sites into Ru/Co-N-C efficiently modify the electronic structure of Ru by enlarging Ru-O covalency and increasing Ru electron density, which in turn optimize the bonding strength between oxygen/hydrogen intermediate species with Ru sites, thereby enhancing OER and HER performance. Furthermore, the incorporation of Co-N4 sites induces electron redistribution around Ru-N4, thus enhancing corrosion-resistance of Ru/Co-N-C during acid and alkaline electrolysis. The Ru/Co-N-C has been applied in a proton exchange membrane water electrolyzer and steady operation is demonstrated at a high current density of 450 mA cmgeo-2 for 330 h.