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Characterization of CeO2–Fe2O3 Mixed Oxides: Influence of the Dopant on the Structure

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Abstract

CeFex (x = 0, 1, 3, 5, 10, 15 and 20 at.%) mixed oxides synthesized by an adapted Pechini method were characterized by Raman spectroscopy, high-resolution transmission electron microscopy, electron paramagnetic resonance, magnetization and 57Fe Mössbauer spectroscopy (57Fe-MS) measurements in order to evaluate the oxygen vacancies formation and the chemical environment of Fe+3 inserted into the CeO2 crystalline lattice. Fe+3 introduction into the CeO2 structure resulted in an increase of the oxygen vacancies concentration, which indicates that this is the predominant charge compensation mechanism in the formation of CeFex solid solutions by the Pechini method. Fe+3 insertion in CeO2 led to the formation of substitutional solid solutions, in which Fe+3 replaced octahedral Ce+4 sites in the crystalline lattice. Fe+3 could be found in the form of isolated sites with orthorhombic distortion or Fe+3 species in pairs or clusters coupled by strong spin–spin interactions. No evidence of Fe+3 insertion into tetrahedral interstitial sites was found. Isolated Fe+3 species showed a less distorted chemical environment and greater ionic character of the Fe–O bonds than the clusters, being the concentration of both type sites approximately equal for all the Fe+3 doped contents. It was found that pure CeO2 and all the CeFex mixed oxides presented ferromagnetic properties even at room temperature possibly due to their small crystallite size and the presence of oxygen vacancies. At high Fe+3 concentrations (above 10 at.%), probably super-exchange interactions (Fe+3–O−2–Fe+3), with an antiferromagnetic character, also took place, reducing the ferromagnetism of the CeFex mixed oxides.

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Acknowledgements

The authors thank the Foundation for Research Support of the State of Rio de Janeiro (FAPERJ) and the National Counsel of Technological and Scientific Development (CNPq) for financial support (scholarship). We thank Rosa B. Scorzelli for made available the Mössbauer facility at Centro Brasileiro de Pesquisas Físicas (CBPF)—Brazil. The authors also acknowledge Núcleo de Microscopia da COPPE-UFRJ for the use of the facilities.

Funding

Funding was provided by Universidade Federal do Rio de Janeiro.

Author information

Author notes

  1. Rodrigo Brackmann

    Present address: Department of Chemistry, Federal University of Technology - Paraná (UTFPR), Via do Conhecimento, Km 01, Fraron, C.P. 571, Pato Branco, Paraná, CEP 85503-390, Brazil

Authors and Affiliations

  1. Chemical Engineering Program, Laboratory Nucleus of Catalysis COPPE/UFRJ, Federal University of Rio de Janeiro, Ilha do Fundão, C.P. 68502, Rio de Janeiro, CEP 21941-914, Brazil

    Rodrigo Brackmann, Fabio Souza Toniolo & Martin Schmal

  2. Institute of Science and Technology, Federal University of the Valleys of Jequitinhonha and Mucuri (UFVJM), Rodovia MGT 367, km 583, n° 5000, Diamantina, MG, 39.100-000, Brazil

    Edivaldo dos Santos Filho

  3. Department of Physicochemistry, Chemistry Institute, Fluminense Federal University (UFF), R. Outeiro de S. J. Batista s/n, Niterói, RJ, CEP 24020-150, Brazil

    Odivaldo Cambraia Alves

  4. Institute of Physics, Federal University of Rio de Janeiro, Ilha do Fundão, C.P. 68528, Rio de Janeiro, CEP 21941-972, Brazil

    Ângelo Marcio de Souza Gomes

  5. Metallurgical and Materials Engineering Program - COPPE1, Federal University of Rio de Janeiro, Ilha do Fundão, C.P. 68505, Rio de Janeiro, CEP 21941-972, Brazil

    Carla Brandão Woyames

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  1. Rodrigo Brackmann
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  4. Odivaldo Cambraia Alves
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  7. Martin Schmal
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Corresponding author

Correspondence to Martin Schmal.

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Brackmann, R., Toniolo, F.S., dos Santos Filho, E. et al. Characterization of CeO2–Fe2O3 Mixed Oxides: Influence of the Dopant on the Structure. Top Catal 61, 1694–1706 (2018). https://doi.org/10.1007/s11244-018-1031-1

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  • DOI: https://doi.org/10.1007/s11244-018-1031-1

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