Jan Höcker, Jon-Olaf Krisponeit, Thomas Schmidt, Jens Falta and Jan Ingo Flege.

Nanoscale (2017) 9, 9352-9358

http://dx.doi.org/10.1039/C6NR09760J

Cerium oxide is often applied in today's catalysts due to its remarkable oxygen storage capacity. The changes in stoichiometry during reaction are linked to structural modifications, which in turn affect its catalytic activity. We present a real-time in situ study of the structural transformations of cerium oxide particles on ruthenium(0001) at high temperatures of 700°C in ultra-high vacuum. Our results demonstrate that the reduction from CeO₂ to cubic Ce₂O₃ proceeds via ordered intermediary phases. The final reduction step from cubic to hexagonal Ce₂O₃ is accompanied by a lattice expansion, the formation of two new surface terminations, a partial dissolution of the cerium oxide particles, and a massive mass transport of cerium from the particles to the substrate. The conclusions allow for new insights into the structure, stability, and dynamics of cerium oxide nanoparticles in strongly reducing environments.