NOx storage and reduction pathways on zirconia and titania functionalized binary and ternary oxides as NOx storage and reduction (NSR) systems

Abstract

Binary and ternary oxide materials, ZrO2/TiO2 (ZT) and Al2O3/ZrO2/TiO2 (AZT), as well as their Ptfunctionalized counterparts were synthesized and characterized via XRD, Raman spectroscopy, BET, in situ FTIR and TPD techniques. In the ZT system, a strong interaction between TiO2 and ZrO2 domains at high temperatures (>973K) resulted in the formation of a low specific surface area (i.e. 26 m2/g at 973K) ZT material containing a highly ordered crystalline ZrTiO4 phase. Incorporation of Al2O3 in the AZT structure renders the material highly resilient toward crystallization and ordering. Alumina acts as a diffusion barrier in the AZT structure, preventing the formation of ZrTiO4 and leading to a high specific surface area (i.e. 264 m2/g at 973K). NOx adsorption on the AZT system was found to be significantly greater than that of ZT, due to almost ten-fold greater SSA of the former surface. While Pt incorporation did not alter the type of the adsorbed nitrate species, it significantly boosted the NOx adsorption on both Pt/ZT and Pt/AZT systems. Thermal stability of nitrates was higher on the AZT compared to ZT, most likely due to the defective structure and the presence of coordinatively unsaturated sites on the former surface. Pt sites also facilitate the decomposition of nitrates in the absence of an external reducing agent by shifting the decomposition temperatures to lower values. Presence of Pt also enhances partial/complete NOx reduction in the absence of an external reducing agent and the formation of N2 and N2O. In the presence of H2(g), reduction of surface nitrates was completed at 623K on ZT, while this was achieved at 723K for AZT. Nitrate reduction over Pt/ZT and Pt/AZT via H2(g) under mild conditions initially leads to conversion of bridging nitrates into monodentate nitrates/nitrites and the formation of surface OH and NHx functionalities. N2O(g) was also continuously generated during the reduction process as an intermediate/byproduct.