Multiscale Modeling of Agglomerated Ceria Nanoparticles: Interface Stability and Oxygen Vacancy Formation

The interface formation and its effect on redox processes in agglomerated ceria nanoparticles (NPs) have been investigated using a multiscale simulation approach with standard density functional theory (DFT), the self-consistent-charge density functional tight binding (SCC-DFTB) method, and a DFT-parameterized reactive force-field (ReaxFF). In particular, we have modeled Ce₄₀O₈₀ NP pairs, using SCC-DFTB and DFT, and longer chains and networks formed by Ce₄₀O₈₀ or Ce₁₃₂O₂₆₄ NPs, using ReaxFF molecular dynamics simulations. We find that the most stable {111}/{111} interface structure is coherent whereas the stable {100}/{100} structures can be either coherent or incoherent. The formation of {111}/{111} interfaces is found to have only a very small effect on the oxygen vacancy formation energy, E _vac. The opposite holds true for {100}/{100} interfaces, which exhibit significantly lower E _vac values than the bare surfaces, despite the fact that the interface formation eliminates reactive {100} facets. Our results pave the way for an increased understanding of ceria NP agglomeration.