Na-doped ruthenium perovskite electrocatalysts with improved oxygen evolution activity and durability in acidic media.

Retuerto, María; Pascual, Laura; Calle-Vallejo, Federico; Ferrer, Pilar; Gianolio, Diego; Pereira, Amaru González; García, Álvaro; Torrero, Jorge et al. · Nat Commun · 2019

basic_science · Level V

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Abstract

The design of active and durable catalysts for the H<sub>2</sub>O/O<sub>2</sub> interconversion is one of the major challenges of electrocatalysis for renewable energy. The oxygen evolution reaction (OER) is catalyzed by SrRuO<sub>3</sub> with low potentials (ca. 1.35 V<sub>RHE</sub>), but the catalyst's durability is insufficient. Here we show that Na doping enhances both activity and durability in acid media. DFT reveals that whereas SrRuO<sub>3</sub> binds reaction intermediates too strongly, Na doping of ~0.125 leads to nearly optimal OER activity. Na doping increases the oxidation state of Ru, thereby displacing positively O p-band and Ru d-band centers, weakening Ru-adsorbate bonds. The enhanced durability of Na-doped perovskites is concomitant with the stabilization of Ru centers with slightly higher oxidation states, higher dissolution potentials, lower surface energy and less distorted RuO<sub>6</sub> octahedra. These results illustrate how high OER activity and durability can be simultaneously engineered by chemical doping of perovskites.