(Invited) Core-Shell Fe₃O₄@CoFe₂O₄ Spinel Nanoparticles for the Oxygen Evolution Reaction in Alkaline Media

Transition metal oxides have attracted much attention as promising anode materials for anion exchange membrane water electrolysis (AEMWE). Herewith we introduce core-shell nanoparticles comprised of a Fe 3 O 4 core and a CoFe 2 O 4 shell as prospective catalysts for the oxygen evolution reaction (OER) at the cathode of an AEMWE. We show that confining the active component in a thin (~1-2 nm) shell and taking advantage from the core-shell synergistic interaction allows one to reach an exceptional OER activity of 2800 A at 1.65 V vs. RHE per gram of cobalt [1]. We further show that to correctly determine the OER activity, it is necessary to study the OER in a wide interval of the catalyst loadings [2]. To shed light of the origin of the aforementioned synergistic effect between the core and the shell, the Fe 3 O 4 @CoFe 2 O 4 nanoparticles were investigated using operando near edge X-ray absorption fine structure (NEXAFS) spectroscopy in a total electron yield (TYE) detection mode, under potential and during the OER conditions [3] . We documented a strong influence of the Fe3O4 core on the redox behavior of the CoFe2O4 shell under the OER conditions. Contrary to the previously studied Co 3 O 4 anode, whose surface at high potentials has been shown to transform into CoOOH [4], the shell of the Fe 3 O 4 @CoFe 2 O 4 nanoparticles maintains its spinel structure with Co(II) stabilized by the Fe(III) of the core. The results suggest the occurrence of a cation-redox OER mechanism involving cooperative redox behavior between Co and Fe atoms. It is remarkable that the core-shell structure is essentially preserved under the OER conditions. Figure 1. Left-hand side: cartoon showing the composition of the core-shell nanoparticle and charge transfer from Co to Fe occurring under positive polarization. Right-hand side: Fe L-edge difference spectra acquired at 1.2, 1.4 and 1.8 V vs RHE (the reference itself taken at 1.0 V vs. RHE). Reproduced from Ref. [3]. Finally, we study the influence of the shell composition by replacing Co by Ni on the OER activity and stability of core-shell nanoparticles. Acknowledgements The authors are indebted to S. Hettler and R. Arenal of INMA (Zaragoza, Spain), S. Holdcroft of SFU (Vancouver, Canada) and J. Velasco-Vélez of Alba Synchrotron facility (Spain) for their cooperation. We thank the HZB für Materialien und Energie for the allocation of synchrotron radiation beamtime. Financial support from Jean-Marie-Lehn foundation is gratefully acknowledged. REFERENCES [1] L. Royer, S. Hettler, R. Arenal, T. Asset, B. Rotonnelli, A. Bonnefont, E. Savinova, B. Pichon, submitted. [2] L. Royer, J. Guehl, M. Zilbermann, T. Dintzer, C. Leuvrey, B. Pichon, E. Savinova, A. Bonnefont, submitted. [3] L. Royer, A. Bonnefont, T. Asset, B. Rotonnelli, J. Velasco-Vélez, S. Holdcroft, S. Hettler, R. Arenal, B. Pichon, E. Savinova, ACS Catalysis, https://doi.org/10.1021/acscatal.2c04512. [4] F. Reikowski, F. Maroun, I. Pacheco, T. Wiegmann, P. Allongue, J. Stettner, O. Magnussen, ACS Catal. 2019, 9 (5), 3811–3821; https://doi.org/10.1021/acscatal.8b04823. Figure 1

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