Tuning Bifunctional Oxygen Electrocatalysts by Changing the A-Site Rare-Earth Element in Perovskite Nickelates
Perovskite-structured (ABO 3 ) transition metal oxides are promising bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). In this paper, we investigate a set of epitaxial rare earth nickelates (RNiO 3 ) thin films with controlled A-site isovalent substitution to correlate their structure and physical properties with ORR/OER activities. The ORR activity is shown to decrease monotonically with decreasing the A-site element ionic radius which lowers the conductivity of the RNiO 3 (R = La, La 0.5 Nd 0.5 , La 0.2 Nd 0.8 , Nd, Nd 0.5 Sm 0.5 , Sm, Gd) films, with LaNiO 3 being the most conductive and active. On the other hand, the OER activity initially increases upon substituting La with Nd and is maximal at La 0.2 Nd 0.8 NiO 3 , in which oxygen vacancies (VOs) start to form. Moreover, the OER activity remains comparable within error through Sm-doped NdNiO 3 . Beyond that, we cannot reliably measure activity due to the potential voltage drop across the film. The improved OER activity is ascribed to the partial reduction of Ni 3+ to Ni 2+ as a result of VOs, which increases the average occupancy of the e g antibonding orbital to more than one. Our work highlights the importance of tuning A-site elements as an effective strategy for balancing the ORR and OER activities of bifunctional electrocatalysts.