Tuning the Electrocatalytic Activity of Perovskites through Active Site Variation and Support Interactions

We present a series of perovskite electrocatalysts that are highly active for both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in an aqueous alkaline electrolyte. Lanthanum-based perovskites containing different transition metal active sites (LaBO3, B = Ni, Ni0.75Fe0.25, Co, Mn) are synthesized by a general colloidal method, yielding phase pure catalysts of homogeneous morphology and surface area (8–14 m2/g). Each perovskite’s ability to catalyze the OER and ORR is examined using thin film rotating disk electrochemistry (RDE). LaCoO3 supported on nitrogen-doped carbon is shown to be ∼3 times more active for the OER than high-surface-area IrO2. Furthermore, LaCoO3 is demonstrated to be highly bifunctional by having a lower total overpotential between the OER and ORR (ΔE = 1.00 V) than Pt (ΔE = 1.16) and Ru (ΔE = 1.01). The OER and ORR pathways are perturbed by the introduction of peroxide disproportionation functionality via support interactions and selective doping of the catal...

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