Activity and thermal stability of Rh-based catalytic system for an advanced modern TWC

Abstract

The catalytic activity and thermal durability of Rh supported on a variety of metal oxides for removing NO in the three-way catalyst (TWC) converter have been investigated under realistic gasoline engine exhaust conditions. Among the Rh/metal oxide catalysts examined, the Rh/ZrO2 catalyst has the best thermal durability. The catalytic activity and thermal stability of the Rh/ZrO2 catalysts have shown strong dependence on the ZrO2 support employed, with the ZrO2 prepared by the sol-gel (SG) and precipitation (P) methods exhibiting the most favorable catalytic performance. The improved TWC performance and thermal stability of the Rh/ZrO2 (SG and P) catalysts compared to other Rh/ZrO2 catalysts are mainly due to the structural difference in the underlying ZrO2 supports. Both ZrO2 (P) and ZrO2 (SG) contain the tetragonal as well as the monoclinic phase of ZrO2, whereas the others are primarily in the monoclinic phase. Deactivation of the Rh/ZrO2 upon thermal aging is mainly caused by the loss of the active metal surface area of Rh due to sintering and/or burial of Rh into the sublattice of ZrO2. The strong interaction of Rh with the tetragonal phase of ZrO2 appears to prevent the burial of Rh into ZrO2 lattice during the thermal aging. A series of comparative kinetic experiments revealed that the Rh/ZrO2 (SG and P) catalysts among other Rh/metal oxide catalysts produce the least amount of harmful NH3, which can be subsequently oxidized to hazardous NOx over the Pd-based oxidation catalyst co-existing in the TWC converter. A dual-brick monolith system washcoated with Rh/ZrO2 (P) and Pd/Al2O3 in the front and the rear bricks, respectively, has shown superior thermal durability over monolith configurations investigated in the present study. (c) 2012 Elsevier B.V. All rights reserved.