Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Influence of Crystal Structure on the Chemical Bonding Nature and Photocatalytic Activity of Hexagonal and Cubic Perovskite Compounds

  • Lee, Sun-Hee (Center for Intelligent Nano-Bio Materials (CINBM), Division of Nano Sciences and Department of Chemistry, Ewha Womans University) ;
  • Kim, In-Young (Center for Intelligent Nano-Bio Materials (CINBM), Division of Nano Sciences and Department of Chemistry, Ewha Womans University) ;
  • Kim, Tae-Woo (Center for Intelligent Nano-Bio Materials (CINBM), Division of Nano Sciences and Department of Chemistry, Ewha Womans University) ;
  • Hwang, Seong-Ju (Center for Intelligent Nano-Bio Materials (CINBM), Division of Nano Sciences and Department of Chemistry, Ewha Womans University)
  • Published : 2008.04.20
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Abstract

We have investigated the influence of the crystal structure on the chemical bonding nature and photocatalytic activity of cubic and hexagonal perovskite A[$Cr_{1/2}Ta_{1/2}$]O3 (A = Sr, Ba) compounds. According to neutron diffraction and field emission-scanning electron microscopy, the crystal structure and particle size of these compounds are strongly dependent on the nature of A-site cations. Also, it was found that the face-shared octahedra in the hexagonal phase are exclusively occupied by chromium ions, suggesting the presence of metallic (Cr-Cr) bonds. X-ray absorption and diffuse UV-vis spectroscopic analyses clearly demonstrated that, in comparison with cubic Sr[$Cr_{1/2}Ta_{1/2}$]$O_3$ phase, hexagonal Ba[$Cr_{1/2}Ta_{1/2}$]$O_3$ phase shows a decrease of Cr oxidation state as well as remarkable changes in interband Cr d-d transitions, which can be interpreted as a result of metallic (Cr-Cr) interactions. According to the test of photocatalytic activity, the present semiconducting materials have a distinct activity against the photodegradation of 4-chlorophenol. Also the Srbased compound was found to show a higher photocatalytic activity than the Ba-based one, which is attributable to its smaller particle size and its stronger absorption in visible light region.

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