Structure and Surface Relaxation of CeO2 Nanoparticles Unveiled by Combining Real and Reciprocal Space Total Scattering Analysis
Marco Scavini, Federica Bertolotti, Jonadri Mlloja, Filippo Umbri, Anna Bosc, Serena Cappelli, Stefano Checchia, Cesare Oliva, P. Fumagalli, Davide Ceresoli, Mariangela Longhi, Antonietta Guagliardi, Mauro Coduri
Abstract
NPs were produced by an inverse micellae wet synthetic path and then annealed at different temperatures. X-ray total scattering data were analyzed by combining real-space-based Pair Distribution Function analysis and the reciprocal-space-based Debye Scattering Equation method with atomistic models. Subtle atomic-scale relaxations occur at the nanocrystal surface. The structural analysis was corroborated by ab initio DFT and force field calculations; micro-Raman and electron spin resonance added important insights to the NPs' defective structure. The combination of the above techniques suggests a core-shell like structure of ultrasmall NPs. These exhibit an expanded outer shell having a defective fluorite structure, while the inner shell is similar to the bulk structure. The presence of partially reduced O2-δ species testifies to the high surface activity of the NPs. On increasing the annealing temperature, the particle dimensions increase, limiting disorder as a consequence of the progressive surface-to-volume ratio reduction.