Silver-alumina catalysts for selective reduction of NO by higher hydrocarbons: structure of active sites and reaction mechanism

Abstract

Silver-alumina catalysts prepared by sol–gel method (Ag-Al2O3) and impregnation method (Ag/Al2O3) were studied for the selective catalytic reduction (SCR) of NO by higher alkanes (n-hexane and n-octane). UV–VIS and Ag K-edge XAFS results established the structure of the catalysts; below 2wt.%, highly dispersed Ag+ ions are predominant Ag species, while at higher Ag loading, Agn clusters are predominant. A relationship between the structure of Ag species and their catalytic function for SCR by n-octane was clarified. Ag+ ions are responsible for the selective reduction of NO to N2, while the Agn clusters are responsible for the hydrocarbon combustion and N2O formation. The mechanism of SCR by n-hexane on Ag-Al2O3, which mainly consists of Ag+ ions, were investigated by in situ FTIR spectroscopy. During NO+n-hexane+O2 reaction, the acetate produced via the partial oxidation of n-hexane and the nitrates produced via the oxidation of NO were main adspecies in the steady-state condition at 473–623K. The acetate, which was stable in O2 or NO, was reactive in NO+O2. Nitrates, which were relatively stable in n-hexane, were quite reactive toward n-hexane+O2. The rate of nitrates reaction in n-hexane+O2 was close to the steady-state rate of NO reduction over wide range of temperature, indicating that the nitrate is a possible intermediate in the SCR. A proposed mechanism, suggesting the reaction of nitrates with partially oxidized hydrocarbon species as a crucial step, explains the steady-state kinetic results. At relatively high NO concentration or at low temperature, nitrates should inhibit the reaction by strongly adsorbing on the catalyst surface.