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Transition (Mn, Fe) and rare earth (La, Pr) metal doped ceria solid solutions for high performance photocatalysis: Effect of metal doping on catalytic activity

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Abstract

In this work, various transition and rare earth metal ions (M3+; M = Mn3+, Fe3+, La3+, and Pr3+) doped CeO2 solid solutions were prepared by a simple sol–gel method for the degradation of an organic dye, Rhodamine B (RhB) as a model pollutant. The as-prepared samples were thoroughly studied by various characterization techniques to understand the surface and optical properties. The XRD results suggested formation of solid solutions, and TEM studies confirmed the nanosized nature of the ceria particles. The Raman and XPS results revealed that the doping of metal ions enhanced the formation of Ce3+ ions associated with the oxygen vacancies. The doping of M3+ ions in the CeO2 lattice strongly influenced the band gap tuning of undoped CeO2 (3.01 eV) from the UV to Visible region (i.e., 2.45–2.90 eV). Photoluminescence studies suggested that doping of M3+ cations suppresses the recombination rate of photogenerated electron–hole pairs. The photocatalytic activity results indicated that the doped CeO2 samples exhibit substantially enhanced photocatalytic performance for the degradation of RhB compared to undoped CeO2. The better catalytic activity of doped CeO2 samples could be attributed to the presence of defects (Ce3+ ions and oxygen vacancies), which play a prominent role as trapping centres for excited electrons and inhibit the recombination process. The scavengers tests confirmed that the generation of highly reactive hydroxyl (·OH) and super oxide (·O2−) radicals are actively involved in the photodegradation process. This work rendered a new concept for rational design and development of doped CeO2-based materials as better photocatalysts.

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Acknowledgements

PV thanks the University Grants Commission (UGC)-Dr. D. S. Kothari Postdoctoral Fellowship (DSKPDF) Scheme, New Delhi for his postdoctoral research fellowship. The authors thank the RMIT microscopy and microanalysis facility (RMMF) for allowing the use of their microscopic instruments.

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Authors and Affiliations

  1. Department of Chemistry, Osmania University, Hyderabad, 500 007, India

    Perala Venkataswamy & M. Vithal

  2. Centre for Advanced Materials and Industrial Chemistry (CAMIC), School of Applied Sciences, RMIT University, GPO Box 2476, Melbourne, 3001, Australia

    Deshetti Jampaiah, Ahmad Esmaielzadeh Kandjani & Ylias M. Sabri

  3. CSIR-Indian Institute of Chemical Technology, Uppal Road, Hyderabad, 500 007, India

    Benjaram M. Reddy

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  1. Perala Venkataswamy
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Venkataswamy, P., Jampaiah, D., Kandjani, A.E. et al. Transition (Mn, Fe) and rare earth (La, Pr) metal doped ceria solid solutions for high performance photocatalysis: Effect of metal doping on catalytic activity. Res Chem Intermed 44, 2523–2543 (2018). https://doi.org/10.1007/s11164-017-3244-5

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