RESUMO
Rational nanostructure manipulation has been used to prepare nanocomposites in which multiwalled carbon nanotubes (MWCNTs) were embedded inside mesoporous layers of oxides (TiO(2), ZrO(2), or CeO(2)), which in turn contained dispersed metal nanoparticles (Pd or Pt). We show that the MWCNTs induce the crystallization of the oxide layer at room temperature and that the mesoporous oxide shell allows the particles to be accessible for catalytic reactions. In contrast to samples prepared in the absence of MWCNTs, both the activity and the stability of core-shell catalysts is largely enhanced, resulting in nanocomposites with remarkable performance for the water-gas-shift reaction, photocatalytic reforming of methanol, and Suzuki coupling. The modular approach shown here demonstrates that high-performance catalytic materials can be obtained through the precise organization of nanoscale building blocks.
RESUMO
A method, based on self assembly, for preparing core-shell nanostructures that are dispersible in organic solvents is demonstrated for Pd and Pt cores with CeO(2), TiO(2), and ZrO(2) shells. Transmission electron microscopy (TEM) of these nanostructures confirmed the formation of distinct metal cores, approximately 2 nm in diameter, surrounded by amorphous oxide shells. Functional catalysts were prepared by dispersing the nanostructures onto an Al(2)O(3) support; and vibrational spectra of adsorbed CO, together with adsorption uptakes, were used to demonstrate the accessibility of the metal core to CO and the porous nature of the oxide shell. Measurements of water-gas-shift (WGS) rates demonstrated that these catalysts exhibit activities similar to that of conventional supported catalysts despite having lower metal dispersions. Pd-based CeO(2) and TiO(2) core-shell catalysts exhibit significant transient deactivation, which is probably caused by a decrease in the exposed metal surface area due to the ease of reduction of the shells. Alternatively, Pt-based analogous core-shell catalysts do not exhibit such a transient decrease. Both Pd- and Pt-based ZrO(2) core-shell catalysts deactivate at a significantly lower rate due to the less reducible nature of the ZrO(2) shell.
