| Full text | |
| Author(s): |
Felicio-Sousa, Priscilla
[1]
;
Mucelini, Johnatan
[1]
;
Zibordi-Besse, Larissa
[1]
;
Andriani, Karla F.
[1]
;
Seminovski, Yohanna
[2]
;
Prati, Ronaldo C.
[3]
;
Da Silva, Juarez L. F.
[1]
Total Authors: 7
|
| Affiliation: | [1] Univ Sao Paulo, Sao Carlos Inst Chem, POB 780, BR-13560970 Sao Carlos, SP - Brazil
[2] Univ Politecn Valencia, Inst Tecnol Quim, Avda los Naranjos S-N, E-46022 Valencia - Spain
[3] Fed Univ ABC, Ctr Math Comp Sci & Cognit, Av Estados 5001, BR-09210580 Santo Andre, SP - Brazil
Total Affiliations: 3
|
| Document type: | Journal article |
| Source: | Physical Chemistry Chemical Physics; v. 21, n. 48, p. 26637-26646, DEC 28 2019. |
| Web of Science Citations: | 0 |
| 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, horizontal ellipsis ,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. (AU) | |
| FAPESP's process: | 18/11152-0 - Catalyst design for direct conversion of methane to methanol: an ab initio Density Functional Theory investigation |
| Grantee: | Karla Furtado Andriani |
| Support Opportunities: | Scholarships in Brazil - Post-Doctoral |
| FAPESP's process: | 17/11631-2 - CINE: computational materials design based on atomistic simulations, meso-scale, multi-physics, and artificial intelligence for energy applications |
| Grantee: | Juarez Lopes Ferreira da Silva |
| Support Opportunities: | Research Grants - Research Centers in Engineering Program |