Abstract
We have investigated the influence of the crystal structure on the chemical bonding nature and photocatalytic activity of cubic and hexagonal perovskite A[<TEX>$Cr_{1/2}Ta_{1/2}$</TEX>]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[<TEX>$Cr_{1/2}Ta_{1/2}$</TEX>]<TEX>$O_3$</TEX> phase, hexagonal Ba[<TEX>$Cr_{1/2}Ta_{1/2}$</TEX>]<TEX>$O_3$</TEX> 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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