Oxygen Vacancy-Electron Polarons Featured InSnRuO2 Oxides: Orderly and Concerted In-Ov-Ru-O-Sn Substructures for Acidic Water Oxidation.

Polymetallic oxides with extraordinary electrons/geometry structure ensembles, trimmed electron bands, and way-out coordination environments, built by an isomorphic substitution strategy, may create unique contributing to concertedly catalyze water oxidation, which is of great significance for proton exchange membrane water electrolysis (PEMWE). Herein, well-defined rutile InSnRuO₂ oxides with density-controllable oxygen vacancy (Ov)-free electron polarons are firstly fabricated by in situ isomorphic substitution, using trivalent In species as Ov generators and the adjacent metal ions as electron donors to form orderly and concerted In-Ov-Ru-O-Sn substructures in the tetravalent oxides. For acidic water oxidation, the obtained InSnRuO₂ displays an ultralow overpotential of 183 mV (versus RHE) and a mass activity (MA) of 103.02 A mg_Ru ^-1, respectively. For a long-term stability test of PEMWE, it can run at a low and unchangeable cell potential (1.56 V) for 200 h at 50 mA cm^-2, far exceeding current IrO₂||Pt/C assembly in 0.5 m H₂SO₄. Accelerated degradation testing results of PEMWE with pure water as the electrolyte show no significant increase in voltage even when the voltage is gradually increased from 1 to 5 A cm^-2. The remarkably improved performance is associated with the concerted In-Ov-Ru-O-Sn substructures stabilized by the dense Ov-electron polarons, which synergistically activates band structure of oxygen species and adjacent Ru sites and then boosting the oxygen evolution kinetics. More importantly, the self-trapped Ov-electron polaron induces a decrease in the entropy and enthalpy, and efficiently hinder Ru atoms leaching by increasing the lattice atom diffusion energy barrier, achieves long-term stability of the oxide. This work may open a door to design next-generation Ru-based catalysts with polarons to create orderly and asymmetric substructures as active sites for efficient electrocatalysis in PEMWE application.