• ceria;
  • copper;
  • dimerization;
  • flame spray pyrolysis;
  • nanoparticles;
  • structure–property relationship


Rapid synthesis of Cu[BOND]CeO2 catalysts by flame spray pyrolysis produces highly active Cu dimer morphologies without the need for additional catalyst pretreatment. The active Cu component is enriched onto the CeO2 surface at concentrations higher than the nominal loading with no evidence of amorphous or crystalline CuO phase. Increasing the Cu content results in a morphological transition from isolated Cu monomers to oxygen-bridged dimers and an associated increase in oxygen vacancy concentration. Dimer-containing Cu[BOND]CeO2 catalysts display high levels of activity and selectivity in the low-temperature preferential oxidation of CO. Experimental measurements and simulations suggest that the geometry of the dimer presents a comparatively ionic Cu[BOND]O bond at the catalyst surface. Further studies indicate that these ionic dimer species promote preferential CO oxidation at lower temperatures than observed for monomeric Cu species. This is the first report to explicitly propose and demonstrate that the structural distortion associated with the formation of Cu dimers directly induces increased bond ionicity at the catalyst surface and that these changes are responsible for improved catalytic activity.