Jump to main content
Jump to site search

Issue 48, 2019
Previous Article Next Article

Ab initio insights into the structural, energetic, electronic, and stability properties of mixed CenZr15−nO30 nanoclusters

Author affiliations

Abstract

Mixed CeO2–ZrO2 nanoclusters have the potential to play a crucial role in nanocatalysis, however, the atomistic understanding of those nanoclusters is far from satisfactory. In this work, we report a density functional theory investigation combined with Spearman rank correlation analysis of the energetic, structural and electronic properties of mixed CenZr15−nO30 nanoclusters as a function of the composition (n = 0, 1,…,14, 15). For instance, we found a negative excess energy for all putative global minimum CenZr15−nO30 configurations with a minimum at about n = 6 (i.e., nearly 40% Ce), in which both the oxygen anion surroundings and cation radii play a crucial role in the stability and distribution of the chemical species. We found a strong energetic preference of Zr4+ cations to occupy larger coordination number sites, i.e., the nanocluster core region, while the Ce4+ cations are located near vacuum exposed O-rich regions. As expected, we obtained an almost linear decrease of the average bond lengths by replacing Ce4+ by Zr4+ cations in the (ZrO2)15 nanoclusters towards the formation of mixed CenZr15−nO30 nanoclusters, which resulted in a shift towards higher vibrational frequencies. Besides, we also observed that the relative stability of the mixed oxides is directly correlated with the increase (decrease) of the Zr d-state (Ce f-state) contribution to the highest occupied molecular orbital with the increase of the Zr content, hence driving the gap energy towards higher values.

Graphical abstract: Ab initio insights into the structural, energetic, electronic, and stability properties of mixed CenZr15−nO30 nanoclusters

Back to tab navigation

Supplementary files

Article information


Submitted
27 Aug 2019
Accepted
15 Nov 2019
First published
18 Nov 2019

Phys. Chem. Chem. Phys., 2019,21, 26637-26646
Article type
Paper

Ab initio insights into the structural, energetic, electronic, and stability properties of mixed CenZr15−nO30 nanoclusters

P. Felício-Sousa, J. Mucelini, L. Zibordi-Besse, K. F. Andriani, Y. Seminovski, R. C. Prati and J. L. F. Da Silva, Phys. Chem. Chem. Phys., 2019, 21, 26637
DOI: 10.1039/C9CP04762J

Social activity

Search articles by author

Spotlight

Advertisements