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Ilika paper published by Chemical Science – Reversible perovskite electrocatalysts for oxygen reduction/oxygen evolution

Abstract
The identification of electrocatalysts mediating both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are prerequisite for the development of reversible fuel cells and rechargeable metal–air batteries. The question remains as to whether a bifunctional catalyst, or a single catalyst site, will exhibit potentials converging to +1.23 VRHE. Transition metal-based perovskites provide tunable catalysts where site substitution can influence both ORR and OER, however substitution in the pseudo-binary phases results in an anti-correlation in ORR and OER activities. We reveal that LaxMnyNi1−yO3−δ, compositions with lanthanum A-site sub-stoichiometry exhibit reversible activity correlating with the appearance of the Mn3+/Mn4+ redox couple. The Mn3+/Mn4+ couple is associated with Mn4+ co-existing with Mn3+ in the bulk, as La3+ is substituted by Ni2+ at the A-site to create a mixed valent system. We also show that a direct A-site substitution by the Ca2+ cation in LaxCa1−xMnyO3−δ perovskites also results in the creation of Mn4+, the appearance of the Mn3+/Mn4+ redox couple, and a concomitant reversible activity. These results highlight a general strategy of optimising oxide electrocatalysts with reversible activity.

Ilika plc (LON: IKA) has world class expertise in accelerated materials innovation, including in the automotive, aeronautical and electronic components sectors. Global brands such as Rolls-Royce and Toyota have long-term collaborations with Ilika. High throughput technology enables functional materials to be made, characterised and tested up to 100 times faster than traditional techniques. Robust datasets enhance intellectual property value, optimise product performance and reduce time to market, thereby maximising return on R&D investment.

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