Gradual coarsening of the catalytically-active metal particles in a catalyst is one of the fundamental reasons for loss of activity over time. For three-way automotive exhaust-gas catalysts, a recent phenomenon, the redox-induced cyclical re-dispersion of the metal in novel precious-metal-doped-perovskite formulations has been proposed as a possible means of reducing this problem. Recent work showing that this phenomenon occurs over distances of only a few nanometers in these systems suggests that a practical perovskite-based catalyst will likely involve ultra-thin perovskite films or coatings. In an effort to assess the viability of such a catalyst, this GOALI award covers a carefully designed combination of electron microscopy and catalytic measurements on model planar and high-surface-area powder catalysts to be conducted at University of Michigan and Ford Research and Innovation Center under the supervision of Profs. Xiaoqing Pan and George Graham and of Dr. Robert McCabe, respectively. Specific objectives include the observation of self-stabilizing or self-regenerative catalyst behavior in ultra-thin perovskite films on planar supports, the production of perovskite-coated high-surface-area powders, the measurement of kinetics and detailed chemical potential dependence of structural transformations in model powder catalyst systems, the catalytic characterization of perovskite-based precious-metal catalysts using simple reactions to probe three-way catalytic activity, and ultimately the durability assessment of perovskite-based precious-metal powder catalysts under realistic conditions. An important aspect of the structure-property relationship testing will be to clearly assign catalytic activity to either supported metal particles or metal-doped perovskite.
Broader Significance and Importance:
Automotive exhaust-gas catalysts currently account for 30-50% of the world-wide demand for Pt and Pd, and the corresponding demand for Rh is even higher, ~80%. Since the utilization of these metals in this application has historically never exceeded a few percent by end of life, due primarily to particle coarsening, the attainment of even a modest increase in efficiency would be of tremendous significance, both commercially as well as scientifically. The proposed work affords the opportunity for graduate and undergraduate students at University of Michigan to collaborate closely with catalyst researchers at Ford Motor Company and their suppliers in the pursuit of this goal, which is to improve metal utilization efficiency through the development of a practical perovskite-based three-way catalyst.
