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Synthesis and layer-by-layer self-assembly of titania nanosheets controllably doped with binary transition metal ions

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Abstract

Here, we describe the synthesis of novel titania nanosheets controllably doped with binary transition metal ions and their layer-by-layer self-assembly. The tailored Mn and Fe doping in exfoliated Ti0.6Mnx/2Fe(0.8-x)/2O2 (x = 0.0–0.4) nanosheets is achieved by systematically changing the molar ratio of Mn/Fe in K0.8Ti1.2MnxFe0.8-xO4 using a codoping strategy. The protonated layered crystals exhibit a delaminated behavior in the tetrabutylammonium hydroxide solution and are exfoliated into colloidal single sheets, which are characterized by a large lateral size and a thickness in molecular dimension. The resulted nanosheets are able to be layer-by-layer deposited with oppositely charged polymers into a composite organic/inorganic system.

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REFERENCES

  1. T. Bak, J. Nowotny, M. Rekas, and G.G. Scorrell: Photo-electrochemical hydrogen generation from water using solar energy. Materials-related aspects. Int. J. Hydrogen Energy 27, 991 (2002).

    Article  CAS  Google Scholar 

  2. C. Guillard, S. Horikoshi, N. Watanabe, H. Hidaka, and P. Pichat: Photocatalytic degradation mechanism for heterocyclic derivatives of triazolidine and triazole. J. Photochem. Photobiol. Chem. 149, 155 (2002).

    Article  CAS  Google Scholar 

  3. J.M. Coronado, M.E. Zorn, I. Tejedor-Tejedor, and M.A. Anderson: Photocatalytic oxidation of ketones in the gas phase over TiO2 thin films: A kinetic study on the influence of water vapor. Appl. Catal., B 43, 329 (2003).

    Article  CAS  Google Scholar 

  4. N. Doucet, O. Zahraa, and M. Bouchy: Kinetics of the photocatalytic degradation of benzene. Catal. Today 122, 168 (2007).

    Article  CAS  Google Scholar 

  5. K. Zakrzewska: Gas sensing mechanism of TiO2-based thin films. Vacuum 74, 335 (2004).

    Article  CAS  Google Scholar 

  6. Y. Matsumoto, M. Murakami, T. Shono, T. Hasegawa, T. Fukumura, M. Kawasaki, P. Ahmet, T. Chikyow, S. Koshihara, and H. Koinuma: Room-temperature ferromagnetism in transparent transition metal-doped titanium dioxide. Science 291, 854 (2001).

    Article  CAS  Google Scholar 

  7. W.K. Park, R.J. Ortega-Hertogs, J.S. Moodera, A. Punnoose, and M.S. Seehra: Semiconducting and ferromagnetic behavior of sputtered Co-doped TiO2 thin films above room temperature. J. Appl. Phys. 91, 8093 (2002).

    Article  CAS  Google Scholar 

  8. P. Kluson, S. Kment, H. Bartkova, and Z. Hubicka: Thin functional films of photoactive TiO2 nanoparticles, in New Research on Thin Solid Films, edited by M.G. Benjamin (Nova Science, New York, 2007) p. 65.

    Google Scholar 

  9. H. Tang, K. Prasad, R. Sanjines, P.E. Schmid, and F. Levy: Electrical and optical properties of TiO2 anatase thin films. J. Appl. Phys. 75, 2042 (1994).

    Article  CAS  Google Scholar 

  10. T. Tong, J. Zhang, B. Tian, F. Chen, and D. He: Preparation of Fe doped TiO2 catalysts by controlled hydrolysis of titanium alkoxide and study on their photocatalytic activity for methyl orange degradation. J. Hazard. Mater. 155, 572 (2008).

    Article  CAS  Google Scholar 

  11. A. Fujishima, X. Zhang, and D.A. Tryk: Photocatalysis and related surface phenomena. Surf. Sci. Rep. 63, 515 (2008).

    Article  CAS  Google Scholar 

  12. W.Y. Choi, A. Termin, and M.R. Hoffmann: The role of metal ion dopants in quantum-sized TiO2: Correlation between photoreactivity and charge carrier recombination dynamics. J. Phys. Chem. 84, 13669 (1994).

    Article  Google Scholar 

  13. N.H. Hong, W. Preltier, J. Sakai, and A. Hassini: Fe- and Ni-doped TiO2 thin films grown on LaAlO3 and SrTiO3 substrates by laser ablation. Appl. Phys. Lett. 84, 2850 (2004).

    Article  CAS  Google Scholar 

  14. J.P. Xu, Y.B. Lin, Z.H. Lu, X.C. Liu, Z.L. Lu, J.F. Wamg, W.Q. Zou, L.Y. Lv, F.M. Zhang, and Y.W. Du: Enhanced ferromagnetism in Mn-doped TiO2 films during the structural phase transition. Solid State Commun. 140, 514 (2006).

    Article  CAS  Google Scholar 

  15. Z.J. Wang, J.K. Tang, H.G. Zhang, V. Golub, L. Spinu, and L.D. Tung: Ferromagnetism in chromium-doped reduced-rutile titanium dioxide thin films. J. Appl. Phys. 95, 7381 (2004).

    Article  CAS  Google Scholar 

  16. A. Henglein: Small-particle research: Physicochemical properties of extremely small colloidal metal and semiconductor particles. Chem. Rev. 89, 1861 (1989).

    Article  CAS  Google Scholar 

  17. M.M.J. Treacy, S.B. Rice, A.J. Jacobson, and T. Lewandowski: An electron microscopy study of delamination in dispersions of the perovskite-related layered phases K[Ca2Nan-3NbnO3n-1]: Evidence for single layer formation. Chem. Mater. 2, 279 (1990).

    Article  CAS  Google Scholar 

  18. T. Sasaki, M. Watanabe, H. Hashizume, H. Yamada, and H. Nakazawa: Macromolecule-like aspects for a colloidal suspension of an exfoliated titanate. Pairwise association of nanosheets and dynamic reassembling process initiated from it. J. Am. Chem. Soc. 118, 8329 (1996).

    Article  CAS  Google Scholar 

  19. T. Sasaki and M. Watanabe: Osmotic swelling to exfoliation. Exceptionally high degrees of hydration of a layered titanate. J. Am. Chem. Soc. 120, 4682 (1998).

    Article  CAS  Google Scholar 

  20. R. Abe, K. Shinohara, A. Tanaka, M. Hara, J.N. Kondo, and K. Domen: Preparation of porous niobium oxide by the exfoliation of K4Nb6O17 and its photocatalytic activity. J. Mater. Res. 13, 861 (1998).

    Article  CAS  Google Scholar 

  21. Z.H. Liu, K. Ooi, H. Kanoh, W.P. Tang, and T. Tomida: Swelling and delamination behaviors of birnessite-type manganese oxide by intercalation of tetraalkylammonium ions. Langmuir 16, 4154 (2000).

    Article  CAS  Google Scholar 

  22. Y. Omomo, T. Sasaki, L. Wang, and M. Watanabe: Redoxable nanosheet crystallites of MnO2 derived via delamination of a layered manganese oxide. J. Am. Chem. Soc. 125, 3568 (2003).

    Article  CAS  Google Scholar 

  23. K. Fukuda, I. Nakai, Y. Ebina, R. Ma, and T. Sasaki: Colloidal unilamellar layers of tantalum oxide with open channels. Inorg. Chem. 46, 4787 (2007).

    Article  CAS  Google Scholar 

  24. K. Fukuda, K. Akatsuka, Y. Ebina, R. Ma, K. Takada, I. Nakai, and T. Sasaki: Exfoliated nanosheet crystallite of cesium tungstate with 2D pyrochlore structure: Synthesis, characterization, and photochromic properties. ACS Nano 2, 1689 (2008).

    Article  CAS  Google Scholar 

  25. N. Sakai, Y. Ebina, K. Takada, and T. Sasaki: Electronic band structure of titania semiconductor nanosheets revealed by electrochemical and photoelectrochemical studies. J. Am. Chem. Soc. 126, 5851 (2004).

    Article  CAS  Google Scholar 

  26. T. Sasaki, Y. Ebina, T. Tanaka, M. Harada, and M. Watanabe: Layer-by-layer assembly of titania nanosheet/polycation composite films. Chem. Mater. 13, 4661 (2001).

    Article  CAS  Google Scholar 

  27. M. Harada, T. Sasaki, Y. Ebina, and M. Watanabe: Preparation and characterizations of Fe- or Ni-substituted titania nanosheets as photocatalysts. J. Photochem. Photobiol. Chem. 148, 273 (2002).

    Article  CAS  Google Scholar 

  28. M. Osada, Y. Ebina, K. Takada, and T. Sasaki: Gigantic magneto-optical effects in multilayer assemblies of two-dimensional titania nanosheets. Adv. Mater. 18, 295 (2006).

    Article  CAS  Google Scholar 

  29. M. Osada, Y. Ebina, K. Fukuda, K. Ono, K. Takada, K. Yamaura, E. Takayama-Muromachi, and T. Sasaki: Ferromagnetism in two-dimensional Ti0.8Co0.2O2 nanosheets. Phys. Rev. B 73, 153301 (2006).

    Article  Google Scholar 

  30. M. Osada, M. Itose, Y. Ebina, K. Ono, S. Ueda, K. Kobayashi, and T. Sasaki: Gigantic magneto-optical effects induced by (Fe/Co)-cosubstitution in titania nanosheets. Appl. Phys. Lett. 92, 253110 (2008).

    Article  Google Scholar 

  31. X. Dong, M. Osada, H. Ueda, Y. Ebina, Y. Kotani, K. Ono, S. Ueda, K. Kobayashi, K. Takada, and T. Sasaki: Synthesis of Mn-substituted titania nanosheets and ferromagnetic thin films with controlled doping. Chem. Mater. 21, 4366 (2009).

    Article  CAS  Google Scholar 

  32. T. Sasaki, F. Kooli, M. Iida, Y. Michiue, S. Takenouchi, Y. Yajima, F. Izumi, B.C. Chakoumakos, and M. Watanabe: A mixed alkali metal titanate with the lepidocrocite-like layered structure. Preparation, crystal structure, protonic form, and acid-base intercalation properties. Chem. Mater. 10, 4123 (1998).

    Article  CAS  Google Scholar 

  33. T. Sasaki and M. Watanabe: Semiconductor nanosheet crystallites of quasi-TiO2 and their optical properties. J. Phys. Chem. B 101, 10159 (1997).

    Article  CAS  Google Scholar 

  34. K. Fukuda, I. Nakai, C. Oishi, M. Nomura, M. Harada, Y. Ebina, and T. Sasaki: Nanoarchitecture of semiconductor titania nanosheets revealed by polarization-dependent total reflection fluorescence X-ray absorption fine structure. J. Phys. Chem. B 108, 13088 (2004).

    Article  CAS  Google Scholar 

  35. L. Li, R. Ma, Y. Ebina, N. Iyi, and T. Sasaki: Positively charged nanosheets derived via total delamination of layered double hydroxides. Chem. Mater. 17, 4386 (2005).

    Article  CAS  Google Scholar 

  36. Z. Liu, R. Ma, M. Osada, N. Iyi, Y. Ebina, K. Takada, and T. Sasaki: Synthesis, anion exchange, and delamination of Co–Al layered double hydroxide: Assembly of the exfoliated nanosheet/polyanion composite films and magneto-optical studies. J. Am. Chem. Soc. 128, 4872 (2006).

    Article  CAS  Google Scholar 

  37. R. Ma, Z. Liu, K. Takada, N. Iyi, Y. Bando, and T. Sasaki: Synthesis and exfoliation of Co2+-Fe3+ layered double hydroxides: An innovative topochemical approach. J. Am. Chem. Soc. 129, 5257 (2007).

    Article  CAS  Google Scholar 

  38. R. Ma, K. Takada, K. Fukuda, N. Iyi, Y. Bando, and T. Sasaki: Topochemical synthesis of monometallic (Co2+-Co3+) layered double hydroxide and its exfoliation into positively charged Co(OH)2 nanosheets. Angew. Chem. Int. Ed. 47, 86 (2008).

    Article  CAS  Google Scholar 

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ACKNOWLEDGMENTS

The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (21001093, 20805043), the Zhejiang Provincial Natural Science Foundation of China (Y4090285), and the Science Foundation of Zhejiang Sci-Tech University (0913840-Y).

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  1. Department of Chemistry, School of Sciences, Zhejiang Sci-Tech University, Xiasha Higher Education Zone, Hangzhou, Zhejiang, China

    Xiaoping Dong, Jie Fu & Fengna Xi

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  1. Xiaoping Dong
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Correspondence to Xiaoping Dong.

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Dong, X., Fu, J. & Xi, F. Synthesis and layer-by-layer self-assembly of titania nanosheets controllably doped with binary transition metal ions. Journal of Materials Research 26, 1285–1291 (2011). https://doi.org/10.1557/jmr.2011.101

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