Understanding electrochemical switchability of perovskite-type exsolution catalysts.

Opitz, Alexander K; Nenning, Andreas; Vonk, Vedran; Volkov, Sergey; Bertram, Florian; Summerer, Harald; Schwarz, Sabine; Steiger-Thirsfeld, Andreas et al. · Nat Commun · 2020

basic_science · Level V

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Abstract

Exsolution of metal nanoparticles from perovskite-type oxides is a very promising approach to obtain catalysts with superior properties. One particularly interesting property of exsolution catalysts is the possibility of electrochemical switching between different activity states. In this work, synchrotron-based in-situ X-ray diffraction experiments on electrochemically polarized La<sub>0.6</sub>Sr<sub>0.4</sub>FeO<sub>3-δ</sub> thin film electrodes are performed, in order to simultaneously obtain insights into the phase composition and the catalytic activity of the electrode surface. This shows that reversible electrochemical switching between a high and low activity state is accompanied by a phase change of exsolved particles between metallic α--Fe and Fe-oxides. Reintegration of iron into the perovskite lattice is thus not required for obtaining a switchable catalyst, making this process especially interesting for intermediate temperature applications. These measurements also reveal how metallic particles on La<sub>0.6</sub>Sr<sub>0.4</sub>FeO<sub>3-δ</sub> electrodes affect the H<sub>2</sub> oxidation and H<sub>2</sub>O splitting mechanism and why the particle size plays a minor role.