Structural feature and catalytic performance of Cu species distributed over TiO2 nanotubes.

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.