Metal Substitution Steering Electron Correlations in Pyrochlore Ruthenates for Efficient Acidic Water Oxidation.

Abstract

Exploring the advanced oxygen evolution reaction (OER) electrocatalysts is highly desirable toward sustainable energy conversion and storage, yet improved efficiency in acidic media is largely hindered by its sluggish reaction kinetics. Herein, we rationally manipulate the electronic states of the strongly electron correlated pyrochlore ruthenate Y₂Ru₂O₇ alternative through partial A-site substitution of Sr²⁺ for Y³⁺, efficiently improving its intrinsic OER activity. The optimized Y_1.7Sr_0.3Ru₂O₇ candidate observes a highly intrinsic mass activity of 1018 A g_Ru^-1 at an overpotential of 300 mV with excellent durability in 0.5 M H₂SO₄ electrolyte. Combining synchrotron-radiation X-ray spectroscopic investigations with theoretical simulations, we reveal that the electron correlations in the Ru 4d band are weakened through coordinatively geometric regulation and charge redistribution by the exotic Sr²⁺ cation, enabling the delocalization of Ru 4d electrons <i>via</i> an insulator-to-metal transition. The induced Ru-O covalency promotion and band alignment rearrangement decreases the charge transfer energy to accelerate interfacial charge transfer kinetics. Meanwhile, the chemical affinity of oxygen intermediates is also rationalized to weaken the metal-oxygen binding strength, thus lowering the energy barrier of the overall reaction. This work offers fresh insights into designing advanced solid-state electrocatalysts and underlines the versatility of electronic structure manipulation in tuning catalytic activity.