Abstract:In this paper, mechanistic aspects involved in the formation of N 2 O over Pt-BaO/Al 2 O 3 and Rh-BaO/Al 2 O 3 model NO x Storage-Reduction (NSR) catalysts are discussed. The reactivity of both gas-phase NO and stored nitrates was investigated by using H 2 and NH 3 as reductants. It was found that N 2 O formation involves the presence of gas-phase NO, since no N 2 O is observed upon the reduction of nitrates stored over both Pt-and Rh-BaO/Al 2 O 3 catalyst samples. In particular, N 2 O formation involves the coupling of undissociated NO molecules with N-adspecies formed upon NO dissociation onto reduced Platinum-Group-Metal (PGM) sites. Accordingly, N 2 O formation is observed at low temperatures, when PGM sites start to be reduced, and disappears at high temperatures where PGM sites are fully reduced and complete NO dissociation takes place. Besides, N 2 O formation is observed at lower temperatures with H 2 than with NH 3 in view of the higher reactivity of hydrogen in the reduction of the PGM sites and onto Pt-containing catalyst due to the higher reducibility of Pt vs. Rh.