Preparation of anatase TiO2 nanorods from solutions in the absence of surfactants or templates has rarely been reported. The present work has found that hydrothermal treatment of titanate nanotube suspensions under an acidic environment resulted in the formation of single-crystalline anatase nanorods with a specific crystal-elongation direction. The nanotube suspensions were prepared by treatment of TiO2 in NaOH, followed by mixing with HNO3 to different pH values. The crystal size of the anatase nanoparticles obtained from the hydrothermal treatment increased with the pH of the suspensions, and nanorods with an aspect ratio up to 6 and a long axis along the anatase [001] were obtained at a pH slightly less than 7. A mechanism for the tube-to-rod transformation has been proposed on the basis of the crystalline structures of the tubes and rods. The local shrinkage of the tube walls to form anatase crystallites and the subsequent oriented attachment of the crystallites have been suggested to be the key steps involved in the nanorod formation.
Copper oxide was deposited on tubular TiO2 via Cu2+ introduction into a titanate nanotube aggregate followed by calcination. The titanate has a layered structure allowing Cu intercalation and can readily transform into anatase TiO2 via calcination for condensation of the constituting layers. The activity of the tubular catalysts, with a Cu content of 2 wt %, in selective NO reduction with NH3 was compared with those of other 2 wt % Cu/TiO2 catalysts using TiO2 nanoparticles as the support. The Cu species supported on the nanotubes showed a higher activity than those supported on the nanoparticles. X-ray absorption near-edge structure (XANES) analysis showed that the Cu species on all the TiO2 supports are in the +2 state. Extended X-ray absorption fine structure (EXAFS) investigations of these catalysts reflected higher degrees of CuO dispersion and Cu2+ dissolution into the TiO2 lattice for the tubular Cu/TiO2 catalysts. Absence of CuO bulk detection by a temperature-programmed reduction analysis for the tubular catalysts confirmed the high CuO-dispersion feature of the tubular catalysts. The dissolution of Cu2+ to form a CuxTi1-xO2 type of solid solution was improved by using an in-situ ion-intercalation method for Cu deposition on the nanotubes. A fraction as high as 40% for Cu2+ dissolution was obtained for the tubular catalysts while only 20% was obtained for the particulate catalysts. The CuxTi1-xO2 species were considered one form of the active sites on the Cu/TiO2 catalysts.
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