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Phosphorus is known to reduce effectiveness of the three-way catalysts (TWC) commonly used by automotive OEMs. This phenomenon is referred to as catalyst deactivation. The process occurs as zinc dialkyldithiophosphate (ZDDP) decomposes in an engine creating many phosphorus species, which eventually interact with the active sites of exhaust catalysts. This phosphorous comes from both oil consumption and volatilization. Novel low-volatility ZDDP is designed in such a way that the amounts of volatile phosphorus species are significantly reduced while their antiwear and antioxidant performances are maintained. A recent field trial conducted in New York City taxi cabs provided two sets of “aged” catalysts that had been exposed to GF-4-type formulations. The trial compared fluids formulated with conventional and low-volatility ZDDPs. Results of field test examination were reported in an earlier paper (1).

Catalyst durability is a major concern in automotive exhaust gas treatment, and can be affected by chemical and thermal history. In this work, applications of in situ UV and visible Raman spectroscopy to a variety of catalyst deactivation issues are demonstrated: a) identification and characterization of CePO4 in three-way catalysts. CePO4 forms from the interaction of phosphorus in engine oil additives with the catalyst washcoat. It affects oxygen storage and decreases catalyst conversion efficiency. b) thermal deactivation in Pd/ceria-zirconia catalysts. A compressive strain on palladium oxide as indicated by its Raman shift can serve as a diagnostic for a thermally-deactivated catalyst and thus the unavailability of the Pd for catalysis. c) sulfur poisoning, thermal deactivation and BaCO3 formation in lean NOx traps (LNT).