Cobalt-free layered perovskites RBaCuFeO5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction

Elena Marelli; Jike Lyu; Mickaël Morin; Maxime Leménager; Tian Shang; N. Sena Yüzbasi; Dino Aegerter; Jinzhen Huang; Niéli D. Daffé; Adam H. Clark; Denis Sheptyakov; Thomas Graule; Maarten Nachtegaal; Ekaterina Pomjakushina; Thomas J. Schmidt; Matthias Krack; Emiliana Fabbri; Marisa Medarde

doi:10.1039/D3EY00142C

Cobalt-free layered perovskites RBaCuFeO_5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction†

Elena Marelli,‡^ab Jike Lyu,

‡^a Mickaël Morin,^ac Maxime Leménager,^a Tian Shang,^ad N. Sena Yüzbasi,

^e Dino Aegerter,

^b Jinzhen Huang,

^b Niéli D. Daffé,^f Adam H. Clark,

^g Denis Sheptyakov,

^h Thomas Graule,^e Maarten Nachtegaal,^g Ekaterina Pomjakushina,^a Thomas J. Schmidt,

^bi Matthias Krack,

*^j Emiliana Fabbri

*^b and Marisa Medarde

*^a

Author affiliations

* Corresponding authors

^a Laboratory for Multiscale Materials Experiments, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland
E-mail: marisa.medarde@psi.ch

^b Electrochemistry Laboratory, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland
E-mail: emiliana.fabbri@psi.ch

^c Excelsus Structural Solutions (Swiss) AG, PARK InnovAARE, CH-5234 Villigen PSI, Switzerland

^d Key Laboratory of Polar Materials and Devices (MOE), School of Physics and Electronic Science, East China Normal University, Shanghai, China

^e High Performance Ceramics, EMPA, Swiss Federal Laboratories for Materials Science and Technology, CH-8600 Dübendorf, Switzerland

^f Laboratory for Condensed Matter, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland

^g Laboratory for Synchrotron Radiation and Femtochemistry, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland

^h Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland

ⁱ Laboratory of Physical Chemistry, ETH Zürich, CH-8093 Zürich, Switzerland

^j Laboratory for Materials Simulations, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland
E-mail: matthias.krack@psi.ch

Abstract

Co-based perovskite oxides are intensively studied as promising catalysts for electrochemical water splitting in an alkaline environment. However, the increasing Co demand by the battery industry is pushing the search for Co-free alternatives. Here we report a systematic study of the Co-free layered perovskite family RBaCuFeO_5+δ (R = 4f lanthanide), where we uncover the existence of clear correlations between electrochemical properties and several physicochemical descriptors. Using a combination of advanced neutron and X-ray synchrotron techniques with ab initio DFT calculations we demonstrate and rationalize the positive impact of a large R ionic radius in their oxygen evolution reaction (OER) activity. We also reveal that, in these materials, Fe³⁺ is the transition metal cation the most prone to donate electrons. We also show that similar R³⁺/Ba²⁺ ionic radii favor the incorporation and mobility of oxygen in the layered perovskite structure and increase the number of available O diffusion paths, which have an additional, positive impact on both, the electric conductivity and the OER process. An unexpected result is the observation of a clear surface reconstruction exclusively in oxygen-rich samples (δ > 0), a fact that could be related to their superior OER activity. The encouraging intrinsic OER values obtained for the most active electrocatalyst (LaBaCuFeO_5.49), together with the possibility of industrially producing this material in nanocrystalline form should inspire the design of other Co-free oxide catalysts with optimal properties for electrochemical water splitting.

EES Catalysis

Cobalt-free layered perovskites RBaCuFeO_5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction†

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Cobalt-free layered perovskites RBaCuFeO_5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction

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EES Catalysis

Cobalt-free layered perovskites RBaCuFeO5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction†

Abstract

Supplementary files

Article information

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Cobalt-free layered perovskites RBaCuFeO5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction

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Cobalt-free layered perovskites RBaCuFeO_5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction†

Cobalt-free layered perovskites RBaCuFeO_5+δ (R = 4f lanthanide) as electrocatalysts for the oxygen evolution reaction