Bifunctional fluorine doped Ru/RuO clusters with dynamic electron modification and strong metal-support interaction boost proton exchange membrane water electrolyzer.

The sluggish kinetics and inherent instability over the Ru/RuO clusters are still enormous challenges in proton exchange membrane (PEM) water electrolyzer. Herein, we innovatively report synergistic modulation of dynamic electron modification and strong metal-support interaction (SMSI) to activate and stabilize bifunctional fluorine doped Ru/RuO clusters anchored on carbon nanotube (CNT), thus achieving efficient and stable acidic overall water splitting. Theoretical and experimental studies found that surface metal-fluorine modification layer could dynamically regulate the interfacial electronic environment to stabilize and activate multiple active Ru species; and the SMSI between Ru/RuO cluster and CNT maintains stable electronic environment for dynamic electron modification and avoids migrating or shedding of active species in acidic environment. Therefore, the PEM electrolyzer assembled with optimal F-Ru/RuO@CNT can operate stably for 100 h at a high current density of 100 mA cm, which is the first time that bifunctional Ru-based nanocatalysts applied to PEM device at a high current density.