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Zn-doping and oxygen vacancy effects on the reactivity and properties of monoclinic and tetragonal ZrO2: a DFT study

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Abstract

Zirconia oxide (ZrO2) is a material that has aroused great interest in the scientific community for its general use in various technological applications, such as fuel cells, solar cells, electronic devices, catalysis, dental biomaterial and ceramics. When it is applied as a catalyst, the doping and vacancy effects of their crystalline phases are important properties to guide new developments. This work investigates tetragonal and monoclinic crystalline phases of the Zn-doped ZrO2 by periodic density functional calculations. Changes in the electronic and acid-basic properties were performed by Bader charge analysis, the density of states calculations (DOS) and the projected density of states (PDOS). The formation of oxygen vacancies was also evaluated. The calculated oxygen vacancy formation energies indicate that it is much easier to generate oxygen vacancy in the Zn-doped ZrO2 than in the pure material; in addition, oxygen vacancy formation is favored in the monoclinic phase. Bader charge analyses and projected density of states indicated that the doping of ZrO2 with Zn creates more basic and acid sites. The most stable material is the Zn-doped 3-fold coordinated Zr atom of the m-ZrO2, which can be used for future developments and applications.

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Acknowledgements

The authors acknowledge the financial support from FAPERJ, CAPES and CNPq. R. C. Mancera and L. T. Costa thanks for the Computing Resources from OSCAR and CENAPAD Server. Luciano T. Costa also acknowledges the support from PRINT-CAPES-UFF and CAPES/STINT projects (Grant Numbers 17846692372, CAPES/PRINT 1038152P and 88881.465529/2019-01)

Funding

Rafael C. Mancera reports financial support was provided by CAPES, Luciano T Costa reports financial support was provided by National Council for Scientific and Technological Development.

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Authors and Affiliations

  1. MolMod-CS - Instituto de Química, Universidade Federal Fluminense, Campos de Valonginho s/n, Centro, Niterói, 24020-14, Rio de Janeiro, Brazil

    Rafael R. C. Mancera, Viviane S. Vaiss & Luciano T. Costa

  2. Departamento de Ingeniería Química, Universidad Nacional Autónoma de Honduras, Boulevard Suyapa, Ciudad Universitaria, Tegucigalpa, Honduras

    Oliver E. E. Espino

  3. Departamento de Engenharia Química e de Materiais, Pontifícia Universidade Católica do Rio de Janeiro, Rua Marquês de São Vicente, 225, Gávea, Rio de Janeiro, 22451-900, Rio de Janeiro, Brazil

    Roberto R de Avillez

  4. Divisão de Catálise, Biocatálise e Processos Químicos, Instituto Nacional de Tecnologia, Av Venezuela 82, sala 518, Praça Mauá, Rio de Janeiro, 20081-312, Rio de Janeiro, Brazil

    Lucia G. Appel

Authors
  1. Rafael R. C. Mancera
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Contributions

Rafael C. Mancera: investigation, methodology, validation, writing — original draft; Viviane S. Vaiss: writing — review, supervision; R. R de Avillez: conceptualization, writing — review; Lucia Appel: conceptualization, writing — review; Luciano T. Costa: funding acquisition, project administration, supervision, writing — review and editing, resources, conceptualization.

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Correspondence to Viviane S. Vaiss or Luciano T. Costa.

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Mancera, R.R.C., Vaiss, V.S., Espino, O.E.E. et al. Zn-doping and oxygen vacancy effects on the reactivity and properties of monoclinic and tetragonal ZrO2: a DFT study. J Mol Model 28, 358 (2022). https://doi.org/10.1007/s00894-022-05328-z

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