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Synergistic Effects of Co and Fe on the Oxygen Evolution Reaction Activity of LaCoxFe1−xO3

Füngerlings, A. and Koul, A. and Dreyer, M. and Rabe, A. and Morales, D.M. and Schuhmann, W. and Behrens, M. and Pentcheva, R.

CHEMISTRY - A EUROPEAN JOURNAL
Volume: Pages:
DOI: 10.1002/chem.202102829
Published: 2021

Abstract
In a combined experimental and theoretical study we assess the role of Co incorporation on the OER activity of LaCoxFe1−xO3. Phase pure perovskites were synthesized up to (Formula presented.) in 0.025/0.050 steps. HAADF STEM and EDX analysis points towards FeO2-terminated (001)-facets in LaFeO3, in accordance with the stability diagram obtained from density functional theory calculations with a Hubbard U term (DFT+U). Linear sweep voltammetry conducted in a rotating disk electrode setup shows a reduction of the OER overpotential and a nonmonotonic trend with x, with double layer capacitance measurements indicating an intrinsic nature of activity. This is supported by DFT+U results that show reduced overpotentials for both Fe and Co reaction sites with the latter reaching values of 0.32–0.40 V, ∼0.3 V lower than for Fe. This correlates with a stronger reduction of the binding energy difference of the *O and *OH intermediates towards an optimum value of 1.6 eV for (Formula presented.), the OH deprotonation being the potential limiting step in most cases. Significant variations of the magnetic moments of both surface and subsurface Co and Fe during OER demonstrate that the beneficial effect is a result of a concerted action involving many surrounding ions, which extends the concept of the active site. © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH

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