Influence of ceria on the NOx reduction performance of NOx storage reduction catalysts

• Published in: Applied catalysis. B, Environmental Vol. 142-143; pp. 89 - 100
• Main Authors: Say, Zafer, Vovk, Evgeny I., Bukhtiyarov, Valerii I., Ozensoy, Emrah
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.10.2013
• Subjects: BaO; CeO2; NSR; Pt, NOx; BaO; CeO2; NSR; Pt, NOx
• ISSN: 0926-3373; 1873-3883
• DOI: 10.1016/j.apcatb.2013.04.075

•Influence of ceria on the NOx storage and reduction processes investigated in detail.•Spectroscopic evidence for presence of SMSI, ceria reduction, BaO2, and novel Pt–O–Ce interfacial sites are reported.•NOx reduction starts with formation of –OH, –NHx, N2O and proceeds with loss of –OH and –NHx groups and conversion of N2O into N2.•Ceria promotion has a significantly positive impact on the NOx reduction via H2. Influence of ceria on the NOx storage and reduction behavior of NSR catalysts was investigated in a systematic manner over γ-Al2O3, Ba/Al, Ce/Al, Ba/Ce/Al, Pt/Al, Pt/Ce/Al and Ba/Pt/Ce/Al systems using BET, XRD, Raman spectroscopy and in situ FTIR. Although ceria promotion does not seem to have a substantial influence on the overall NOx storage capacity, it does have a clearly positive effect on the NOx reduction via H2(g) during catalytic regeneration under rich conditions which is associated with the enhancement in the total amount of activated hydrogen on the catalyst surface and lowering of the thermal threshold for hydrogen activation. A strong metal support interaction (SMSI) between Pt sites and the BaOx/CeOx domains leads to a complex redox interplay including oxidation of the precious metal sites, reduction of ceria, formation of BaO2 species as well as the formation of Pt–O–Ce interfacial sites on the Ba/Pt/Ce/Al surface. Ceria domains also act as anchoring sites for Pt species, limit their surface diffusion, enhance dispersion and hinder sintering at elevated temperatures. On the Ba/Pt/Ce/Al catalyst surface, reduction of the stored nitrates under relatively mild conditions via H2(g) initially leads to the formation of surface –OH and –NHx species and gas phase N2O, as well as the destruction of surface nitrate species, leaving bulk nitrates mostly intact. Reduction proceeds with the conversion of N2O(g) into N2(g) along with the partial loss of surface –OH and –NHx groups, dehydration and the loss of bulk nitrates.