Tailoring the Co 3d-O 2p Covalency in LaCoO3 by Fe Substitution To Promote Oxygen Evolution Reaction

LaCoO3 is an active, stable catalyst in alkaline solution for oxygen evolution reaction (OER). With lower cost, it is a potential alternative to precious metal oxides like IrO2 and RuO2 in water electrolysis. However, room still remains for improving its activity according to recent understandings of OER on perovskite oxides. In this work, Fe substitution has been introduced in LaCoO3 to boost its OER performance. Density function theory (DFT) calculation verified that the enhanced performance originates from the enhanced Co 3d-O 2p covalency with 10 at% Fe substitution in LaCoO3. Both DFT calculations and Superconducting Quantum Design (SQUID) magnetometer (MPMS-XL) showed a Co3+ spin state transition from generally low spin state (LS: t(2g)(6) e(g)(0), S = 0) to a higher spin state with the effect of 10 at% Fe substitution. X-ray absorption near-edge structure (XANES) supports DFT calculations on an insulator to half-metal transition with 10 at% Fe substitution, induced by spin state transition. The half-metallic LaCo0.9Fe0.1O3 possesses increased overlap between Co 3d and O 2p states, which results in enhanced covalency and promoted OER performance. This finding enlightens a new way of tuning the metaloxygen covalency in oxide catalysts for OER.