Gold stabilized by nanostructured ceria supports: Nature of the active sites and catalytic performance

The interaction of gold atoms with CeO₂ nanocrystals having rod and cube shapes has been examined by cyanide leaching, TEM, TPR, CO IR and X-ray absorption spectroscopy. After deposition-precipitation and calcination of gold, these surfaces contain gold nanoparticles in the range 2-6 nm. For the ceria nanorods, a substantial amount of gold is present as cations that replace Ce ions in the surface as follows from their first and second coordination shells of oxygen and cerium by EXAFS analysis. These cations are stable against cyanide leaching in contrast to gold nanoparticles. Upon reduction the isolated Au atoms form finely dispersed metal clusters with a high activity in CO oxidation, the WGS reaction and 1,3-butadiene hydrogenation. By analogy with the very low activity of reduced gold nanoparticles on ceria nanocubes exposing the {100} surface plane, it is inferred that the gold nanoparticles on the ceria nanorod surface also have a low activity in such reactions. Although the finely dispersed Au clusters are thermally stable up to quite high temperature in line with earlier findings (Y. Guan and E. J. M. Hensen, Phys Chem Chem Phys 11:9578, 2009), the presence of gold nanoparticles results in their more facile agglomeration, especially in the presence of water (e.g., WGS conditions). For liquid phase alcohol oxidation, metallic gold nanoparticles are the active sites. In the absence of a base, the O-H bond cleavage appears to be rate limiting, while this shifts to C-H bond activation after addition of NaOH. In the latter case, the gold nanoparticles on the surface of ceria nanocubes are much more active than those on the surface of nanorod ceria.