Exsolution reactions enable the synthesis of oxide-supported metal nanoparticles, which are desirable as catalysts in green energy conversion technologies. It is crucial to precisely tailor the nanoparticle characteristics to optimize the catalysts' functionality, and to maintain the catalytic performance under operation conditions. We use chemical (co)-doping to modify the defect chemistry of exsolution-active perovskite oxides and examine its influence on the mass transfer kinetics of Ni dopants towards the oxide surface and on the subsequent coalescence behavior of the exsolved nanoparticles during a continuous thermal reduction treatment. Nanoparticles that exsolve at the surface of the acceptor-type fast-oxygen-ion-conductor SrTi0.95Ni0.05O3-δ (STNi) show a high surface mobility leading to a very low thermal stability compared to nanoparticles that exsolve at the surface of donor-type SrTi0.9Nb0.05Ni0.05O3-δ (STNNi). Our analysis indicates that the low thermal stability of exsolved nanoparticles at the acceptor-doped perovskite surface is linked to a high oxygen vacancy concentration at the nanoparticle-oxide interface. For catalysts that require fast oxygen exchange kinetics, exsolution synthesis routes in dry hydrogen conditions may hence lead to accelerated degradation, while humid reaction conditions may mitigate this failure mechanism.

Advanced Light Source Lawrence Berkeley National Laboratory Berkeley CA 94720 USA

Central Facility for Electron Microscopy RWTH Aachen University 52064 Aachen Germany

Department of Engineering and Applied Sciences University of Bergamo 24044 Dalmine Italy

Department of Materials Imperial College London London SW7 2AZ United Kingdom

Department of Physics and Astronomy University of California Davis California CA 95616 USA

Dyson School of Design Engineering Imperial College London London SW7 2DB United Kingdom

Ernst Ruska Centre for Microscopy and Spectroscopy with Electrons Materials Science and Technology Forschungszentrum Juelich GmbH 52425 Juelich Germany

Institute for Electronic Materials RWTH Aachen University 52074 Aachen Germany

Institute of Energy Materials and Devices Materials Synthesis and Processing Forschungszentrum Juelich GmbH 52425 Jülich Germany

Institute of Mineral Engineering RWTH Aachen University 52062 Aachen Germany

Instituto de Ciencia de Materiales de Madrid 28049 Madrid Spain

Juelich Aachen Research Alliance 52425 Juelich Germany

New Technologies Research Centre University of West Bohemia 301 00 Pilsen Czech Republic

Next Generation Fuel Cell Research Center Kyushu University 744 Motooka Nishi ku Fukuoka 819 0395 Japan

Peter Gruenberg Institute for Electronic Materials Forschungszentrum Juelich GmbH 52425 Juelich Germany

Universität Stuttgart Institute for Manufacturing Technologies of Ceramic Components and Composites 70569 Stuttgart Germany

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