The catalytic activity of cobalt-exchanged mordenites for the abatement of NO with CH4 in the presence of excess O2

The abatement of NO with methane in the presence of oxygen was studied on various commercial MOR in the Na-form (Na-MOR) and H-form (H-MOR), or exchanged to various extents with cobalt (Co-MOR). The sodium and cobalt contents were determined by atomic absorption. Samples were characterized by FTIR and volumetric measurements of CO adsorption. Chemical analysis indicated that one cobalt species replaced two Brønsted acid sites in H-MOR and two Na+ ions in Na-MOR. The IR analysis of the OH stretching region, evidencing an unexpected presence of Brønsted acid sites (band at 3610 cm-1) in Co-MOR, indicated that the exchange process had a more complex stoichiometry. The adsorption of CO at RT on Co-MOR, in addition to the bands of the corresponding H-MOR and Na-MOR matrices, yielded two types of CoII-carbonyls, the first type occupied the mordenite main channels, and the second one the mordenite smaller channels. Brønsted acid sites in mordenites were active for the selective catalytic reduction of NO with CH4. Co-MOR samples were far more active than Na-MOR and H-MOR samples, showing that acid protons play a negligible role when Co is present. Co-MOR catalysts showing the highest activity had the largest amount of CoII-carbonyls in the main channels. This result strongly suggests that CoII in the main channels of MOR are the active sites for the CH4+NO+O2 reaction.