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We report a theoretical investigation of temperature, size, and composition effects on the structural, energetic, and electronic properties of the (La4O6)n, (La2Ce2O7)n, and (Ce4O8)n nanoclusters (NCs) for n = 10, 18. Furthermore, we investigated the single O vacancy formation energy as a function of the geometric location within the NC. Our calculations are based on the combination of force-field molecular dynamics (MD) simulations and density functional theory calculations. We identified a phase transition from disordered to ordered structures for all NCs via MD simulations and structural analysis, e.g., radius changes, radial distribution function, common neighbor analysis, etc. The transition is sharp for La36Ce36O126, La20Ce20O70, and Ce72O144 due to the crystalline domains in the core and less abrupt for Ce40O80, La40O60, and La72O108. As expected, radius changes are abrupt at the transition temperature, as are morphological differences between NCs located below and above the transition temperature. We found a strong dependence on the O vacancy formation energy (Evac) and its location within the NCs. For example, for La40O60, Evac decreases almost linearly as the distance from the geometric center increases; however, the same trend was not observed for Ce40O80, while there are large deviations from the linear trend for La20Ce20O70. Evac has smaller values for Ce40O80 and higher values for La40O60, that is, almost three times, while Evac has intermediate values for mixed oxides, as expected from weighted averages. Therefore, the mixture of one formula unit of La2O3 with two formula units of CeO2 has the effect of increasing the stability of CeO2 (binding energy), which increases the magnitude of the formation energy of the O vacancy. [ABSTRACT FROM AUTHOR]

The combination of ceria (CeO2) with different metal oxides (MO2), e.g. Ce1−xMxO2, has been strategically used to enhance its intrinsic properties. Moreover, the controlled synthesis of mixed oxide nanoparticles (NPs) opens the opportunity to explore the size dependence and chemical composition of the physical–chemical properties. However, our atomic-level understanding of how the physical–chemical and thermodynamic characteristics change with particle size and composition remains far from satisfactory. Here, we used force-field molecular dynamics simulations to investigate the effects of composition (x) and size on the physical–chemical properties of Ce1−xZrxO2 NPs with diameter from 1 (32 cations) up to 3 nm (256 cations), where x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0. We found abrupt changes in potential energy versus temperature for NPs with more than 108 cations, indicating a structural phase transition from disordered to ordered structures, which was confirmed by the radial distribution function. We found a linear relationship between the phase transition temperature (Tpt) and the size and composition of the NPs: the increase in the molar fraction of Zr4+ and the reduction in particle size are related to lower Tpt temperature and less defined decays of potential energy versus temperature. NPs larger than 56 cations show a radial distribution function with several peaks, which is related to the order of cations and anions in these structures. These peaks gradually disappear as the size decreases and the fraction of Zr4+ increases. Similar trends were observed with X-ray diffraction analysis; for example, fluorite-like motifs occur even with 56 cations in the case of ceria, but only for NPs with 108 cations for zirconia. Common neighbor analysis confirmed that NPs with well-defined values of the temperature Tpt have face-centered cubic (fcc)-like domains in the core region. The number of ordered fcc cations increases with increasing NP size and decreasing Zr4+ concentration. Finally, we observed that ceria nucleate first during simulated annealing and occupy highly coordinated sites within the core, while Zr4+ prefers the lowest coordinated sites on the surface. [ABSTRACT FROM AUTHOR]

The combination of ceria (CeO 2 ) with different metal oxides ( M O 2 ), e.g. Ce 1- x M x O 2 , has been strategically used to enhance its intrinsic properties. Moreover, the controlled synthesis of mixed oxide nanoparticles (NPs) opens the opportunity to explore the size dependence and chemical composition of the physical-chemical properties. However, our atomic-level understanding of how the physical-chemical and thermodynamic characteristics change with particle size and composition remains far from satisfactory. Here, we used force-field molecular dynamics simulations to investigate the effects of composition ( x ) and size on the physical-chemical properties of Ce 1- x Zr x O 2 NPs with diameter from 1 (32 cations) up to 3 nm (256 cations), where x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0. We found abrupt changes in potential energy versus temperature for NPs with more than 108 cations, indicating a structural phase transition from disordered to ordered structures, which was confirmed by the radial distribution function. We found a linear relationship between the phase transition temperature ( T pt ) and the size and composition of the NPs: the increase in the molar fraction of Zr 4+ and the reduction in particle size are related to lower T pt temperature and less defined decays of potential energy versus temperature. NPs larger than 56 cations show a radial distribution function with several peaks, which is related to the order of cations and anions in these structures. These peaks gradually disappear as the size decreases and the fraction of Zr 4+ increases. Similar trends were observed with X-ray diffraction analysis; for example, fluorite-like motifs occur even with 56 cations in the case of ceria, but only for NPs with 108 cations for zirconia. Common neighbor analysis confirmed that NPs with well-defined values of the temperature T pt have face-centered cubic (fcc)-like domains in the core region. The number of ordered fcc cations increases with increasing NP size and decreasing Zr 4+ concentration. Finally, we observed that ceria nucleate first during simulated annealing and occupy highly coordinated sites within the core, while Zr 4+ prefers the lowest coordinated sites on the surface.