The role of rare-earth dopants in nanophase zirconia catalysts for automotive emission control.

Rare earth (RE) modification of automotive catalysts (e.g., ZrO{sub 2}) for exhaust gas treatment results in outstanding improvement of the structural stability, catalytic functions and resistance to sintering at high temperatures. Owing to the low redox potential of nonstoichiometric CeO{sub 2}, oxygen release and intake associated with the conversion between the 3+ and 4+ oxidation states of the Ce ions in Ce-doped ZrO{sub 2} provide the oxygen storage capacity that is essentially to effective catalytic functions under dynamic air-to-fuel ratio cycling. Doping tripositive RE ions such as La and Nd in ZrO{sub 2}, on the other hand, introduces oxygen vacancies that affect the electronic and ionic conductivity. These effects, in conjunction with the nanostructure and surface reactivity of the fine powders, present a challenging problem in the development of better ZrO{sub 2}-containing three-way catalysts. We have carried out in-situ small-to-wide angle neutron diffraction at high temperatures and under controlled atmospheres to study the structural phase transitions, sintering behavior, and Ce{sup 3+} {leftrightarrow} Ce{sup 4+} redox process. We found substantial effects due to RE doping on the nature of aggregation of nanoparticles, defect formation, crystal phase transformation, and metal-support interaction in ZrO{sub 2} catalysts for automotive emission control