Support-induced promotional effects on the activity of automotive exhaust catalysts: 1. The case of oxidation of light hydrocarbons (C 2H 4)

Abstract

The kinetics of oxidation of a light hydrocarbon (C 2H 4) were studied on catalysts comprising of combinations of one of three metals, Pt, Pd or Rh supported on five different supports, that is, SiO 2, γ-Al 2O 3, ZrO 2 (8% Y 2O 3), TiO 2 or TiO 2 (W 6+). Significant variation of turnover frequency with the carrier was observed, which cannot be explained by structure sensitivity considerations and is attributed to interactions between the metal crystallites and the carrier. The catalytic activity of these metal-support combinations was investigated over a wide range of partial pressures of ethylene and oxygen. In a separate set of experiments, the kinetics of C 2H 4 oxidation were also investigated on polycrystalline Rh films interfaced with ZrO 2 (8 mol% Y 2O 3) solid electrolyte in a galvanic cell of the type: C 2H 4, O 2, Rh/YSZ/Pt, air, during regular open-circuit conditions as well as under Non-Faradic Electrochemical Modification of Catalytic Activity (NEMCA), that is, closed-circuit conditions. Up to 100-fold increase in catalytic activity was observed by supplying O 2− ions to the catalyst surface via positive potential application to the catalyst. The observed kinetic behavior upon increasing catalyst potential parallels qualitatively the observed alteration of turnover frequency with variation of the support of the Rh crystallites.