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Synthesis of ordered multivalent Mn-TiO2 nanospheres with tunable size: A high performance visible-light photocatalyst

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Abstract

A facile and reproducible method has been developed for the synthesis of ordered anatase Mn-TiO2 nanospheres with controllable sizes in the range 200–300 nm by simply varying the amount of manganese(II) chloride added. The samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), and transmission electron microscope (TEM) measurements, and it was found that the manganese exists in multivalent forms (Mn4+/ Mn3+) and substitutes for some of the Ti4+ in the anatase TiO2 lattice. The presence of Mn significantly influences the morphology and high-temperature stability of TiO2, and extends its light absorption range. Surface photovoltage and photocurrent measurements revealed that an electronic interaction between the Mn and TiO2 was present, in which Mn served as an electron acceptor and effectively inhibited the charge recombination in TiO2; this is thought to be responsible for the highly efficient photocatalytic activity of the material in the degradation of rhodamine B (RhB) under visible-light irradiation ( λ > 420 nm).

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References

  1. Hoffmann, M. R.; Martin, S. T.; Choi, W. Y.; Bahnemannt, D. W. Environmental applications of semiconductor photocatalysis. Chem. Rev. 1995, 95, 69–96.

    Article  CAS  Google Scholar 

  2. Fujishima, A.; Rao, T. N.; Tryk, D. A.; Titanium dioxide photocatalysis. J. Photochem. Photobiol. C: Photochem. Revs. 2000, 1, 1–21.

    Article  CAS  Google Scholar 

  3. O’regan, B.; Grätzel, M. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 films. Nature 1991, 353, 737–740.

    Article  Google Scholar 

  4. Luo, H.; Takata, T.; Lee, Y.; Zhao, J.; Domen, K.; Yan, Y. Photocatalytic activity enhancing for titanium dioxide by codoping with brom ine and chlorine. Chem. Mater. 2004, 16, 846–849.

    Article  CAS  Google Scholar 

  5. Yang, H. G.; Sun, C. H.; Qiao, S. Z.; Zou, J.; Liu, G.; Smith, S. C.; Cheng, H. M.; Lu, G. Q. Anatase TiO2 single crystals with a large percentage of reactive facets. Nature 2008, 453, 638–641.

    Article  CAS  Google Scholar 

  6. Anpo, M.; Takeuchi, M. The design and development of highly reactive titanium oxide photocatalysts operating under visible light irradiation. J. Catal. 2003, 216, 505–516.

    Article  CAS  Google Scholar 

  7. Keller, V.; Bernhardt, P.; Garin, F. Photocatalytic oxidation of butyl acetate in vapor phase on TiO2, Pt/TiO2 and WO3/TiO2 catalysts. J. Catal. 2003, 215, 129–138.

    Article  CAS  Google Scholar 

  8. Kwon, Y. T.; Song, K. Y.; Lee, W. L.; Choi, G. J.; Do, Y. R. Photocatalytic behavior of WO3-loaded TiO2 in an oxidation reaction. J. Catal. 2000, 191, 192–199.

    Article  CAS  Google Scholar 

  9. Miyauchi, M.; Nakajima, A.; Hashimoto, K.; Watanabe, T. A highly hydrophilic thin film under 1 mu·W/cm2 UV illumination. Adv. Mater. 2000, 12, 1923–1927.

    Article  CAS  Google Scholar 

  10. Tade, H.; Kokubu, A.; Iwasaki, M.; Ito, S. Deactivation of TiO2 photocatalyst by coupling with WO3 and the electrochemically assisted high photocatalytic activity of WO3. Langmuir 2004, 20, 4665–4670.

    Article  Google Scholar 

  11. Marcì, G.; Palmisano, L.; Sclafani, A.; Venezia, A. M.; Campostrini, R.; Carturan, G.; Martin, C.; Rives, V.; Solana, G. Influence of tungsten oxide on structural and surface properties of sol-gel prepared TiO2 employed for 4-nitrophenol photodegradation. J. Chem. Soc. Faraday Trans. 1996, 92, 819–821.

    Article  Google Scholar 

  12. Li, J. X.; Xu, J. H.; Dai, W. L.; Li, H. X.; Fan, K. N. One-pot synthesis of twist-like helix tungsten-nitrogencodoped titania photocatalysts with highly improved visible light activity in the abatement of phenol. Appl. Catal. B 2008, 82, 233–243.

    Article  CAS  Google Scholar 

  13. Xue, M.; Huang, L.; Wang, J. Q.; Wang, Y.; Gao, L.; Zhu, J. H.; Zou, Z. G. The direct synthesis of mesoporous structured MnO2/TiO2 nanocomposite: A novel visible-light active photocatalyst with large pore size. Nanotechnology 2008, 19, 185604–185611.

    Article  Google Scholar 

  14. Zou, X. X.; Li, G. D.; Guo, M. Y.; Li, X. H.; Liu, D. P.; Su, J.; Chen, J. S. Heterometal alkoxides as precursors for the preparation of porous Fe- and Mn-TiO2 photocatalysts with high efficiencies. Chem. Eur. J. 2008, 14, 11123–11131.

    Article  Google Scholar 

  15. Bhattacharyya, K.; Varma, S.; Tripathi, A. K.; Bharadwaj, S. R.; Tyagi, A. K. Effect of vanadia doping and its oxidation state on the photocatalytic activity of TiO2 for gas-phase oxidation of ethane. J. Phys. Chem. C 2008, 112, 19102–19112.

    CAS  Google Scholar 

  16. Yang, M.; Wang, D. J.; Peng, L.; Xie, T. F.; Zhao, Y. Photoelectric response mechanisms dependent on RuN3 and CuPc sensitized ZnO nanoparticles to oxygen gas. Nanotechnology 2006, 17, 4567–4571.

    Google Scholar 

  17. Matsumoto, Y.; Murakami, M.; Shono, T.; Hasegawa, T.; Fukumura, T.; Kawasaki, M.; Ahmet, P.; Chikyow, T.; Koshihara, S.; Koinuma. H. Room-temperature ferromagnetism in transparent transition metal-doped titanium dioxide. Science 2001, 291, 854–856.

    Article  CAS  Google Scholar 

  18. Padmanabhan, S. C.; Pillai, S. C.; Colreavy, J.; Balakrishnan, S.; McCormack, D. E.; Perova, T. S.; Gun’ko, Y.; Hinder, S. J.; Kelly, J. M. A simple sol-gel processing for the development of high-temperature stable photoactive anatase titania. Chem. Mater. 2007, 19, 4474–4481.

    Article  CAS  Google Scholar 

  19. Kapteijn, F.; Vanlangeveld, A. D.; Mouljin, J. A.; Andreini, A.; Vuurman, M. A.; Turek, A. M.; Jehng, J. M.; Wachs, I. E. Alumina-supported manganese oxide catalysts: I. characterization: Effect of precursor and loading. J. Catal. 1994, 150, 94–104.

    Article  CAS  Google Scholar 

  20. Pena, D. A.; Uphade, B. S.; Smirniotis, P. G. TiO2-supported metal oxide catalysts for low-temperature selective catalytic reduction of NO with NH3. I. evaluation and characterization of first row transition metals. J. Catal. 2004, 221, 421–431.

    Article  CAS  Google Scholar 

  21. Ettireddy, P. R.; Ettireddy, N.; Mamedov, S.; Boolchand, P.; Smirniotis, P. G.. Surface characterization studies of TiO2 supported manganese oxide catalysts for low temperature SCR of NO with NH3. Appl. Catal. B 2007, 76, 123–134.

    Article  CAS  Google Scholar 

  22. Poinsignon, C.; Berthomé, G..; Prélot, B.; Thomas, F.; Villiéras, F. Manganese dioxides surface properties studied by XPS and gas adsorption. J. Electrochem. Soc. 2004, 151, A1611–A1616.

    Article  CAS  Google Scholar 

  23. Carver, J. C.; Schweitzer, G. K.; Carlson, T. A. Use of X-ray photoelectron spectroscopy to study bonding in chromium, manganese, iron, and cobalt compounds. J. Chem. Phys, 1972, 57, 973–982.

    Article  CAS  Google Scholar 

  24. Zhang, L. H.; Koka, R. V. A study on the oxidation and carbon diffusion of TiC in alumina-titanium carbide ceramics using XPS and raman spectroscopy. Mater. Chem. Phys. 1998, 57, 23–32.

    Article  CAS  Google Scholar 

  25. Gu, D. E.; Liu, Y.; Yang, B. C.; Hu, Y. D. Facile preparation of micro-mesoporous carbon-doped TiO2 photocatalysts with anatase crystalline walls under template-free condition. Chem. Commun. 2008, 21, 2453–2455.

    Article  Google Scholar 

  26. Akrige, J. R.; Kennedy, J. H. Absorption and emission spectroscopy and magnetic susceptibility of sodium β-alumina doped with Mn, Co, and Ni. J. Solid State Chem. 1979, 29, 63–72.

    Article  Google Scholar 

  27. Leglet, M.; Bizi, M.; Jorgensen, C. K. Influence de la distribution cationique et de la nature des interactions magnetiques sur l’intensite des transitions de paires de l’ion Fe3+ dans quelques spinelles mixtes. J. Solid State Chem. 1990, 86, 82.

    Article  Google Scholar 

  28. Stubican, V. S.; Greskovich, C. Trivalent and divalent chromium ions in spinels. Geochimica et Cosmochimica Acta 1975, 39, 875–881.

    Article  CAS  Google Scholar 

  29. Lavalille, F.; Gourier, D.; Lejus, A. M.; Vivien, D. Optical and ESR investigations of lanthanum aluminates LaMg1−x MnxO19 single crystals with magnetoplumbite-like structure. J. Solid State Chem. 1983, 49, 180–187.

    Article  Google Scholar 

  30. Gallardo-Amores, J. M.; Armaroli, T.; Ramis, G.; Finocchio, E.; Busca, G. A study of anatase-supported Mn oxide as catalysts for 2-propanol oxidation. Appl. Catal. B 1999, 22, 249–259.

    Article  CAS  Google Scholar 

  31. Liu, G.; Zhao, Y. N.; Sun, C. H.; Li, F.; Lu, G. Q.; Cheng, H. M. Synergistic effects of B/N doping on the visible-light photocatalytic activity of mesoporous TiO2. Angew. Chem. Int. Ed. 2008, 47, 4516–4520.

    Article  CAS  Google Scholar 

  32. Du, Y.; Yang, M.; Yu, J. H; Pan, Q. H; Xu, R. R. An unexpected photoelectronic effect from [Co(en)3]2(Zr2F12)(SiF6)·4H2O, a compound containing an H-bonded assembly of discrete [Co(en)3]3+, (Zr2F12)4−, and (SiF6)2− ions. Angew. Chem. Int. Ed. 2005, 117, 7988–7990.

    Article  Google Scholar 

  33. Jakob, M.; Levanon, H.; Kamat, P. V. Charge dstribution between UV-irradiated TiO2 and gold nanoparticles: Determination of shift in the Fermi level. Nano Lett. 2003, 3, 353–358.

    Article  CAS  Google Scholar 

  34. Fu, H. B.; Pan, C. S.; Yao, W. Q.; Zhu, Y. F. Charge distribution between UV-irradiated TiO2 and gold nanoparticles: Determination of shift in the Fermi level. J. Phys. Chem. B 2005, 109, 22432–22439.

    Article  CAS  Google Scholar 

  35. Konstantinou, I. K.; Albanis, T. A. TiO2-assisted photocatalytic degradation of azo dyes in aqueous solution: Kinetic and mechanistic investigations: A review. Appl. Catal. B 2004, 49, 1–14.

    Article  CAS  Google Scholar 

  36. Xu, Y. H.; Lei, B.; Guo, L. Q.; Zhou, W. Y.; Liu, Y. Q. Preparation, characterization and photocatalytic activity of manganese doped TiO2 immobilized on silica gel. J. Hazard. Mater. 2008, 160, 78–82.

    Article  CAS  Google Scholar 

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Correspondence to Xinglin Li or Tengfeng Xie.

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Li, H., Wang, D., Fan, H. et al. Synthesis of ordered multivalent Mn-TiO2 nanospheres with tunable size: A high performance visible-light photocatalyst. Nano Res. 4, 460–469 (2011). https://doi.org/10.1007/s12274-011-0102-4

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  • DOI: https://doi.org/10.1007/s12274-011-0102-4

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