Catalyst degradation redistribution

The parameters that affect the degradation of supported platinum and palladium automotive exhaust catalysts are investigated. The study includes the effects of temperature, poison concentration, and hed volume on the lifetime of the catalyst. Thermal damage primarily affects noble metal surface area. Measurements of specific metal area and catalytic activity reveal that supported palladium is more thermally stable than platinum. On the other hand, platinum is more resistant to poisoning than palladium. Electron microprobe examinations of poisoned catalyst pellets reveal that the contaminants accumulate almost exclusively near the skin of the pellet as lead sulfate and lead phosphate. It is possible to regenerate these poisoned catalysts by redistributing the contaminants throughout the pellet. 

As depicted in Fig. 10.9, Pt dissolution and redistribution are other major reasons for catalyst degradation during long-term operation and high-potential cycling tests [91,92]. In the case of Pt dissolution, two parallel paths have been discerned (1) the electrochemical dissolution of Pt to Pt +, according to the reaction Pt—>Pt + + 2e and (2) the formation of Pt oxide, followed by dissolution according to Reactions (lO.I) and (lO.II) ... 

Asymmetric epoxidation of unfunctionalized aUcenes catalyzed by chiral Mn(III)(salen) complexes has proven to be a useful solution-phase reaction [88]. To simplify product isolation and to avoid degradation of the Mn(salen) complex through formation of i-oxo-manganese(lV) dimers by spatial redistribution, the polymer-supported catalyst 112 was prepared by co-polymerization of complex 113, styrene 58, and divinylbenzene as a cross-linker (Scheme 20) [89]. As a stoichiometric oxidant, a combination of meta-chlor-operbenzoic acid (mCPBA) and N-methyl-morpholine N-oxide (NMO) in acetonitrile was used. Yields and rates of conversion were satisfactory for the epoxidation of styrene 58 and of methyl styrene, but only low enantioselectivities were obtained. Nevertheless, the catalyst retained its efficiency in terms of yields and enantioselectivities after repetitive use. Similar results have been described by other researchers [90]. 

---