Aging mechanisms of nanoceria and pathways for preserving optimum morphology

Thermal aging can modify the unique properties of a nanomaterial via structural change. Mechanistic understanding of the aging process, including accelerated aging under high-temperature operating conditions, is a first step towards property preservation via controlling, limiting, or suppressing aging-related processes. Here, we use molecular dynamics to simulate thermal aging of ceria nanocubes and nanorods, which transform into nanopolyhedra; comparisons with experimental TEM images are presented alongside. We find that morphology changes proceed via the turbulent mobility of CexOy surface clusters from one part of the nanoceria to another. For nanorods and nanocubes, catalytically important {100} and {110} surfaces are eroded, whereas the relative area of {111} surfaces increase. Detailed analysis of the simulations reveals that atoms in the CexOy clusters do not all move simultaneously. Rather, (-O-Ce-O-Ce-O-)n ‘chains’ (subsets of the larger CexOy clusters) move with collective motion, while the atoms inside the chains move in a ‘worm-like’ fashion. This reduces the activation energy barrier associated with all the atoms in the chain simultaneously moving into an activated (saddle point) configuration. We predict gadolinium-doped ceria nanocubes, charge-compensated by oxygen vacancies, age faster than undoped and fully oxidised ceria nanocubes. In particular, dopants that increase catalytic activity, may also accelerate aging by introducing oxygen vacancies that break the (-O-Ce-O-Ce-O-)n chains into smaller chains with reduced activation energies. Accordingly, we advocate that when doping is used to confer catalytic activity, experiment should also target the collective motion of surface (-O-Ce-O-Ce-O-)n chains to maximise thermal stability.