Effect of the location of cobalt species on NO adsorption and NOx-SCR over Co-mordenite

Abstract

A thorough characterization of Co-mordenite was carried out using NO-TPD, H2-TPR, Raman, DRX and FTIR with NO as probe molecule. Different cobalt-loading catalysts (8.85, 5.70, 2.91, 2.45 and 1.15 wt.%) were prepared by ion exchange over NH4-mordenite and treated with different procedures (heated on He, O2 and H2). The effect of adding water to the reaction stream at 500 °C on the location of the cobalt species was also analyzed. All catalysts were evaluated for the SCR of NOx with methane as a test reaction both under dry and wet conditions. The NO adsorption capacity depended not only on the Co/Al ratio and pretreatments but also on the presence of Co oxides. In fact, for similar Co/Al ratios, Co2.91MOR showed a lower NO/Co ratio than Co2.45MOR due to the higher Co3O4 concentration in the former. These species probably blocked the main mordenite channels and/or produced the formation of some Co island on the zeolite surface, lowering the amount of surface Co. The main NO surface species detected were dinitrosyl and mononitrosyl. Their stability and relative amount depended on the cobalt species and the pretreatments. Heating in He or H2 induced the stabilization of part of the exchanged Co in less gas-accessible sites, whereas the calcination with O2 involved the mobilization of Co to more external sites. However, those effects were less significant for samples containing Co oxides suggesting that the spinel hinders the Co migration. During the wet reaction treatment, the cobalt mobilization to hidden positions occurred along with the formation of Co-oxides, which negatively affected both the catalytic activity and the NO adsorption capacity.