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Studies of Nanosized Iron-Doped TiO2 Photocatalysts by Spectroscopic Methods

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Abstract

Iron-doped TiO2 nanoparticles with iron content in the range of 0.005 < Fe/Ti < 0.3 were prepared using the flame spray pyrolysis method and investigated with CW X-band electron paramagnetic resonance (EPR), X-ray diffraction, and Fourier transform infrared spectroscopy. This allowed for the clarification of the internal organization of Fe–TiO2 nanoparticles. Different types of Fe(III) centers were distinguished in the samples: isolated high-spin paramagnetic Fe(III) ions (S = 5/2) in rhombic ligand fields state at 0.005 < Fe/Ti < 0.05, and Fe(III) ferromagnetic clusters at Fe/Ti < 0.1. All Fe-doped samples had rather high activity for the photocatalytic mineralization of oxalic acid under visible light illumination (λ > 400 nm) at 25 °C. Correlations were made between EPR and photocatalytic activity results. The specific surface area [S] data allowed us to deduce that the isolated Fe(III) centers were responsible for the photomineralisation of oxalic acid, while the Fe(III) ferromagnetic aggregates decreased the total efficiency of the system.

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References

  1. D.F. Ollis, H. Al-Ekabi (eds.), Photocatalytic Purification and Treatment of Water and Air (Elsevier, Amsterdam, 1993)

    Google Scholar 

  2. A. Fujishima, K. Hashimoto, T. Watanabe, TiO 2 Photocatalysis. Fundamentals and Applications (BKC Inc., Tokyo, 1999)

    Google Scholar 

  3. X. Chen, S.S. Mao, Chem. Rev. 107, 2891 (2007)

    Article  Google Scholar 

  4. H. Zhang, G. Chen, D.W. Bahnemann, J. Mater. Chem. 19, 5089 (2009)

    Article  Google Scholar 

  5. K.I. Zamaraev, V.N. Parmon (eds.), Photocatalytic Conversion of Solar Energy. Heterogeneous, Homogeneous and Molecular Structurally-Organized Systems (Nauka, Novosibirsk, 1991). (in Russian)

    Google Scholar 

  6. M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann, Chem. Rev. 95, 69 (1995)

    Article  Google Scholar 

  7. A. Hagfeldt, M. Grätzel, Chem. Rev. 95, 49 (1995)

    Article  Google Scholar 

  8. C. Lettmann, K. Hildenbrand, H. Kisch, W. Macyk, W.F. Maier, Appl. Catal. B Environ. 32, 215 (2001)

    Article  Google Scholar 

  9. S. Sakthivel, H. Kisch, Angew. Chem. 115, 5057 (2003)

    Article  Google Scholar 

  10. S. Sakthivel, H. Kisch, Angew. Chem. Int. Ed. Engl. 42, 4908 (2003)

    Article  Google Scholar 

  11. S. Sakthivel, H. Kisch, ChemPhysChem 4, 487 (2003)

    Article  Google Scholar 

  12. S. Sakthivel, M. Janczarek, H. Kisch, J. Phys. Chem. B 108, 19384 (2004)

    Article  Google Scholar 

  13. S. Livraghi, A. Votta, M.C. Paganini, E. Giamello, Chem. Comm. 4, 498 (2005)

    Article  Google Scholar 

  14. S. Livraghi, M.C. Paganini, E. Giamello, A. Selloni, C.D. Valentin, G. Pacchioni, J. Am. Chem. Soc. 128, 15666 (2006)

    Article  Google Scholar 

  15. M. Grätzel, R.F. Howe, J. Phys. Chem. 94, 2566 (1990)

    Article  Google Scholar 

  16. J.A. Wang, R. Limas-Ballesteros, T. Lopez, A. Moreno, R. Gomez, O. Novaro, X. Bokhimi, J. Phys. Chem. B 105, 9692 (2001)

    Article  Google Scholar 

  17. H. Yamashita, M. Harada, J. Misaka, M. Takeuchi, B. Neppolian, M. Anpo, Catal. Today 84, 191 (2003)

    Article  Google Scholar 

  18. W.Y. Teoch, R. Amal, L. Maedler, S.E. Pratsinis, Catal. Today 120, 203 (2007)

    Article  Google Scholar 

  19. A. Carrington, A.D. McLachlan, Introduction to Magnetic Resonance with Applications to Chemistry and Chemical Physics (Harper & Row, New York, 1967)

    Google Scholar 

  20. H.A. Kuska, M.T. Rogers, ESR of First Row Transition Metal Complex Ions (Interscience Publ., New York, 1968)

    Google Scholar 

  21. S.A. Al’tshuler, B.M. Kozyrev, Electron Paramagnetic Resonance of Compounds of Intermediate Group Elements (Nauka, Moscow, 1972)

    Google Scholar 

  22. B.A. Goodman, J.B. Raynor, in: E. S. R. of Transition Metal Complexes, Adv. Inorg. Chem. Radiochem. vol 13, eds. by H.J. Emeléus, A.G. Sharpe (1970), pp. 135–362

  23. F.A. Walker, Coord. Chem. Rev. 185–186, 471 (1999)

    Article  Google Scholar 

  24. R.D. Dowsing, J.F. Gibson, J. Chem. Phys. 50, 294 (1969)

    Article  ADS  Google Scholar 

  25. T. Oösterhuis, Structure and Bonding: Biochemistry vol 20, 59 (Springer, Berlin, 1974)

    Google Scholar 

  26. R. Aasa, J. Chem. Phys. 52, 3919 (1970)

    Article  ADS  Google Scholar 

  27. A. Amorelli, J.C. Evans, C.C. Rowlands, T.A. Egerton, J. Chem. Soc. Faraday Trans. 1(83), 3541 (1987)

    Article  Google Scholar 

  28. J. Moser, M. Grätzel, R. Gallay, Helv. Chim. Acta 70, 1596 (1987)

    Article  Google Scholar 

  29. Hombikat UV 100, Technical Information, Sachtleben Chemie GmbH. www.sachtleben.com. Accessed 9 Feb 2015

  30. V.A. Hiremath, A. Venkataraman, Bull. Mater. Sci. 26, 391 (2003)

    Article  Google Scholar 

  31. C. Lemire, S. Bertarione, A. Zecchina, D. Scarano, Phys. Rev. Lett. 94, 166101 (2005)

    Article  ADS  Google Scholar 

  32. A.A. Davydov, Infrared Spectroscopy of Adsorbed Species on the Surface of Transition Metal Oxides (Wiley, New York, 1984)

    Google Scholar 

  33. B. Dillmann, F. Rohr, O. Seiferth, G. Klivenyi, M. Bender, K. Homann, I.N. Yakovkin, D. Ehrlich, M. Bäumer, H. Kuhlenbeck, H.-J. Freund, Faraday Discuss. 105, 295 (1996)

    Article  ADS  Google Scholar 

  34. L. Verdonck, S. Hoste, F.F. Roelandt, G.P. Van der Kelen, J. Mol. Struct. 79, 273 (1982)

    Article  ADS  Google Scholar 

  35. P. Cambier, Clay Miner. 21, 191 (1986)

    Article  Google Scholar 

  36. Y. Cong, J. Zhang, F. Chen, M. Anpo, D. He, J. Phys. Chem. C 111, 10618 (2007)

    Article  Google Scholar 

  37. J. Zhu, W. Zheng, B. He, M. Anpo, J. Mol. Catal. A 216, 35 (2004)

    Article  Google Scholar 

  38. K. Nagaveni, M.S. Hegde, G. Madras, J. Phys. Chern. B 108, 20204 (2004)

    Article  Google Scholar 

  39. R. Krzyminiewski, Z. Kruczynski, B. Dobosz, A. Zajllc, A. Mackiewicz, E. Leporowska, S. Folwaczna, Appl. Magn. Reson. 40, 321 (2011)

    Article  Google Scholar 

  40. L.F. Gamarra, W.M. Pontuschka, E. Amaro Jr., A.J. Costa-Filho, G.E.S. Brito, E.D. Vieira, S.M. Carneiro, D.M. Escriba, A.M.F. Falleiros, V.L. Salvador, Mater. Sci. Eng. C 28, 519 (2008)

    Article  Google Scholar 

  41. Y. Fujita, K. Tsuchiya, S. Abe, Y. Takiguchi, S. Kubo, H. Sakurai, Forensic Sci. Int. 152, 39 (2005)

    Article  Google Scholar 

  42. A.M. Maghraby, M.A. Ali, Radial. Phys. Chem. 76, 1600 (2007)

    Article  ADS  Google Scholar 

  43. L.M. Moreira, A.L. Poli, J.P. Lyon, J. Saade, A.J. Costa-Filho, H. Imasato, Camp. Biochem. Phys. B 150, 292 (2008)

    Article  Google Scholar 

  44. J.M. Kolesar, W.R. Scheiman, P.G. Geiger, K.D. Holen, A.M. Traynor, D.B. Alberti, J.P. Thomas, C.R. Chitambar, G. Wilding, W.E. Antholine, J. Inorg. Biochem. 102, 693 (2008)

    Article  Google Scholar 

  45. C. Fabregaa, T. Andreua, A. Cabota, J.R. Morante, J. Photochem. Photobiol. A Chem. 211, 170 (2010)

    Article  Google Scholar 

  46. G. Pecchi, P. Reyes, T. Lypez, R. Gymez, A. Moreno, J.L.G. Fierro, A. Martнnez-Arias, J. Sol. Gel. Sci. Technol. 27, 205 (2003)

    Article  Google Scholar 

  47. J. Soria, J.C. Conesa, V. Augugliaro, L. Palmisano, M. Schiavello, A. Sclafani, J. Phys. Chem. A 95, 274 (1991)

    Article  Google Scholar 

  48. R. Arroyo, G. Cyrdoba, J. Padilla, V.H. Lara, Mater. Lett. 54, 397 (2002)

    Article  Google Scholar 

  49. A.M. Ruiz, A. Cornet, J.R. Morante, Sens. Actuators B 100, 256 (2004)

    Article  Google Scholar 

  50. S. Güler, B. Rameev, R.I. Khaibullin, H. Bayrakdar, B. Aktaş, Phys. Stat. Sol. A 203, 1533 (2006)

    Article  ADS  Google Scholar 

  51. S. Yu, H.J. Yun, D.M. Lee, J. Yi, J. Mater. Chem. 22, 12629 (2012)

    Article  Google Scholar 

  52. C. Adán, A. Bahamonde, M. Fernández-Garcia, A. Martinez-Arias, Appl. Catal. B 72, 11 (2007)

    Article  Google Scholar 

  53. H. Khan, I.K. Swati, Ind. Eng. Chem. Res. 55, 6619 (2016)

    Article  Google Scholar 

  54. B. Santara, P.K. Giri, K. Imakita, M. Fujii, Nanoscale 5, 5476 (2013)

    Article  ADS  Google Scholar 

  55. S. Stoll, A. Schweiger, J. Magn. Reson. 178, 42 (2006)

    Article  ADS  Google Scholar 

  56. A. Abragam, The Principles of Nuclear Magnetism (Clarendon Press, Oxford, 1961)

    Google Scholar 

  57. Y.S. Lebedev, V.I. Muromtsev, EPR and Relaxation of the Stabilized Radicals (Khimiya, Moscow, 1971)

    Google Scholar 

  58. A.I. Kokorin, in: The Method of Spin Labels and Probes. Problems and Perspectives, eds. by N.M. Emanuel, R.I. Zhdanov (Nauka, Moscow, 1986), p. 61

  59. L.J. Berliner, G.R. Eaton, S.S. Eaton (eds.), Distance Measurements in Biological Systems by EPR (Kluwer Acad./Plenum Publ., New York, 2000)

    Google Scholar 

  60. A.I. Kokorin, in: Chemical Physics of Nanostructured Semiconductors, eds. by A.I. Kokorin, D.W. Bahnemann (VSP, Utrecht, Boston, 2003) p. 203

  61. O.V. Krylov, Heterogeneous Catalysis (Nauka, Novosibirsk, 2003)

    Google Scholar 

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Acknowledgements

A.I.K. thanks Russian Foundation for Basic Research (Grant No. 16-53-00136-Bel-a) for financial support. EPR measurements were partially done at the equipment of the User Facilities Center of M.V. Lomonosov Moscow State University. We thank Prof. E.A. Konstantinova and A.A. Minnekhanov from the same Center for their help in EPR spectra calculations.

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Authors and Affiliations

  1. N. N. Semenov International Center of Chemical Physics (ICCP), Moscow, Russian Federation

    A. I. Kokorin

  2. School of Chemical Sciences and Engineering, UNSW, Sydney, NSW, 2052, Australia

    R. Amal

  3. School of Energy and Environment, City University of Hong, Kowloon, Hong Kong SAR

    W. Y. Teoh

  4. Institute of General and Inorganic Chemistry, National Academy of Sciences of Belarus, Minsk, Belarus

    A. I. Kulak

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  1. A. I. Kokorin
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Kokorin, A.I., Amal, R., Teoh, W.Y. et al. Studies of Nanosized Iron-Doped TiO2 Photocatalysts by Spectroscopic Methods. Appl Magn Reson 48, 447–459 (2017). https://doi.org/10.1007/s00723-017-0873-1

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