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Specific Surface Area and Three-Dimensional Nanostructure Measurements of Porous Titania Photocatalysts by Electron Tomography and Their Relation to Photocatalytic Activity

Published online by Cambridge University Press:  09 March 2011

Kenta Yoshida*
Affiliation:
Department of Chemistry, The University of York, Heslington, York TO10 5BR, UK Nanostructures Research Laboratory, Japan Fine Ceramics Center, 2-4-1 Mutsuno, Atsuta-ku, Nagoya 456-8587, Japan
Masaki Makihara
Affiliation:
Department of Crystalline Materials Science and Ecotopia Science Institute, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
Nobuo Tanaka
Affiliation:
Department of Crystalline Materials Science and Ecotopia Science Institute, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
Shinobu Aoyagi
Affiliation:
Department of Applied Physics, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
Eiji Nishibori
Affiliation:
Department of Applied Physics, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
Makoto Sakata
Affiliation:
SPring-8/JASRI, Kouto, Sayo, Hyogo 679-5198, Japan
Edward D. Boyes
Affiliation:
Department of Physics, The University of York, Heslington, York TO10 5BR, UK The York JEOL Nanocentre, The University of York, Heslington, York TO10 5BR, UK
Pratibha L. Gai
Affiliation:
Department of Chemistry, The University of York, Heslington, York TO10 5BR, UK Department of Physics, The University of York, Heslington, York TO10 5BR, UK The York JEOL Nanocentre, The University of York, Heslington, York TO10 5BR, UK
*
Corresponding author. E-mail: ky512@york.ac.uk
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Abstract

Various porous titania photocatalysts are analyzed three-dimensionally in real space by electron tomography. Shapes and three-dimensional (3D) distributions of fine pores and silver (Ag) particles (2 nm in diameter) within the pores are successfully reconstructed from the 3D data. Electron tomography is applied for measuring the specific surface area of the porous structures including open and closed porosity. Calculated specific surface areas of 22.8 m2/g for a conventional sol-gel TiO2 sample and 366 m2/g for a highly porous TiO2 sample prepared using the Pluronic P-123 self-assembly process are compared with those measured by the general BET method. The real-space surface measurement indicates that the highly porous TiO2 produced by the present method using block copolymers has a greater number of effective reaction sites for the degradation of methylene blue. Electron tomography shows a great potential to contribute considerably to the nanostructural analysis and design of such catalyst materials for photocatalysis.

Type
Material Applications
Copyright
Copyright © Microscopy Society of America 2011

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References

REFERENCES

Alexandridis, P., Olsson, U. & Lindman, B. (1998). A record nine different phases (four cubic, two hexagonal, and one lamellar lyotropic liquid crystalline and two micellar solutions) in a ternary isothermal system of an amphiphilic block copolymer and selective solvents (water and oil). Langmuir 14(10), 26272638.Google Scholar
Aoyagi, S., Kuroiwa, Y., Sawada, A., Kawaji, H. & Atake, T. (2005). Size effect on crystal structure and chemical bonding nature in BaTiO3 nanopowder. J Therm Anal Cal 81(3), 627630.CrossRefGoogle Scholar
Aoyagi, S., Kuroiwa, Y., Sawada, A., Yamashita, I. & Atake, T. (2002). Composite structure of BaTiO3 nanoparticle investigated by SR X-ray diffraction. J Phys Soc Jpn 71, 12181221.Google Scholar
Asahi, R., Morikawa, T., Ohwaki, T., Aoki, K. & Takagi, Y. (2001). Visible-light photocatalysis in nitrogen-doped titanium oxides. Science 293(5528), 269271.Google Scholar
Avnir, D., Farin, D. & Pfeifer, P. (1984). Molecular fractal surfaces. Nature 308, 261263.CrossRefGoogle Scholar
Brunauer, S., Emmett, P.H. & Teller, E. (1938). Adsorption of gases in multimolecular layers. J Am Chem Soc 60, 309319.CrossRefGoogle Scholar
Fahrenkamp-Uppenbrink, J. (2009). Gold needles in a haystack. Science 325(10), 5937.Google Scholar
Frank, J. (1992). Electron Tomography: Three Dimensional Imaging with the Transmission Electron Microscope. New York, London: Plenum.Google Scholar
Fujishima, A. & Honda, K. (1972). Electrochemical photolysis of water at a semiconductor electrode. Nature 238, 3738.CrossRefGoogle Scholar
Gonzáles, J.C., Hernandez, J.C., Lopez, M., Rio, E.D., Delgado, J.J., Hungria, A.B., Trasobares, S., Bernal, S., Midgley, P.A. & Calvino, J.J. (2009). 3D characterization of gold nanoparticles supported on heavy metal oxide catalysts by HAADF-STEM electron tomography. Angew Chem 48(29), 53135315.CrossRefGoogle Scholar
Haruta, M. (1997). Size- and support-dependency in the catalysis of gold. Catalysis Today 36(1), 153166.Google Scholar
Holmqvist, P., Alexandridis, P. & Lindman, B. (1997). Modification of the microstructure in poloxamer block copolymer–water–“oil” systems by varying the “oil” type. Macromolecules 30(22), 67886797.CrossRefGoogle Scholar
Horn, M., Schwerdtfeger, C.F. & Meagher, E.P. (1972). Refinement of the structure of anatase at several temperatures. Z Kristallogr 136, 273281.Google Scholar
Howie, A. (1979). Electron microscope image contrast and localized signal selection techniques. J Microsc 117(1), 1123.Google Scholar
Jelinek, L. & Kováts, E. (1994). True surface areas from nitrogen adsorption experiments. Langmuir 10(11), 42254231.CrossRefGoogle Scholar
Kaneko, K., Inoke, K., Freitag, B., Hungria, A.B., Midgley, P.A., Hansen, T.W., Zhang, J., Ohara, S. & Adschiri, T. (2007). Structural and morphological characterization of cerium oxide nanocrystals prepared by hydrothermal synthesis. Nano Lett 7(27), 421425.CrossRefGoogle ScholarPubMed
Kremer, J.R., Mastronarde, D.N. & McIntosh, J.R. (1996). Computer visualization of three-dimensional image data using IMOD. J Struct Biol 116(1), 7176.Google Scholar
Kumar, K.N.P., Keizer, K., Burggraaf, A.J., Okubo, T., Nagamoto, H. & Morooka, S. (1992). Densification of nanostructured titania assisted by a phase transformation. Nature 358(6381), 4851.Google Scholar
Mastronarde, D.N. (1997). Dual-axis tomography: An approach with alignment methods that preserve resolution. J Struct Biol 120(3), 343352.Google Scholar
Midgley, P.A. & Weyland, M. (2003). 3D electron microscopy in the physical sciences: The development of Z-contrast and EFTEM tomography. Ultramicroscopy 96(3-4), 413431.CrossRefGoogle ScholarPubMed
Musić, S., Gotić, M., Ivanda, M., Popović, S., Turković, A., Trojko, R., Sekulić, A. & Furić, K. (1997). Chemical and micro structural properties of TiO2 synthesized by sol-gel procedure. Mater Sci Eng 47(1), 3340.CrossRefGoogle Scholar
Nambara, T., Yoshida, K., Miao, L., Tanemura, S. & Tanaka, N. (2007). Preparation of strain-included rutile titanium oxide thin films and influence of the strain upon optical properties. Thin Solid Films 515(5), 30963101.Google Scholar
Nishibori, E., Takata, M., Kato, K., Sakata, M., Kubota, Y., Aoyagi, S., Kuroiwa, Y., Yamakata, M. & Ikeda, N. (2001). The large Debye-Scherrer camera installed at SPring-8 BL02B2 for charge density studies. Nucl Instrum Methods Phys Res A 467&468, 10451048.Google Scholar
Pfeifer, P. & Avnir, D. (1983). Chemistry in noninteger dimensions between two and three. I. Fractal theory of heterogeneous surfaces. J Chem Phys 79, 35583565.Google Scholar
Sueda, S., Yoshida, K. & Tanaka, N. (2010). Quantification of metallic nanoparticle morphology on TiO2 using HAADF-STEM tomography. Ultramicroscopy 110(9), 11201127.Google Scholar
Tanaka, N., Cho, S.P., Shklyaev, A.A., Yamasaki, J., Okunishi, E. & Ichikawa, M. (2008). Spherical aberration corrected STEM studies of Ge nanodots grown on Si(0 0 1) surfaces with an ultrathin SiO2 coverage. Appl Surf Sci 254(23), 75697572.CrossRefGoogle Scholar
Yamasaki, J., Tanaka, N., Baba, N., Kakibayashi, H. & Terasaki, O. (2004). Three-dimensional analysis of platinum supercrystals by transmission electron microscopy and high-angle annular dark-field scanning transmission electron microscopy observations. Philos Mag 84(25-26), 28192828.Google Scholar
Yoshida, K., Ikuhara, Y.H., Takahashi, S., Hirayama, T., Saito, T., Sueda, S., Tanaka, N. & Gai, P.L. (2009). The three-dimensional morphology of nickel nanodots in amorphous silica and their role in high-temperature permselectivity for hydrogen separation. Nanotech 20, 315703.Google Scholar
Yoshida, K., Kawai, T., Nanbara, T., Tanemura, S., Saitoh, K. & Tanaka, N. (2006a). Direct observation of oxygen atoms in rutile titanium dioxide by spherical aberration corrected high-resolution transmission electron microscopy. Nanotech 17(15), 39443950.CrossRefGoogle Scholar
Yoshida, K., Yamasaki, J. & Tanaka, N. (2006b). Oxygen release and structural changes in TiO2 films during photocatalytic oxidation. J Appl Phys 99(8), 084908.Google Scholar
Zemlin, F., Weiss, K., Schiske, P., Kunath, W. & Hermann, K.H. (1978). Coma-free alignment of high resolution electron microscopes with the aid of optical diffractograms. Ultramicroscopy 3, 4960.Google Scholar
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