| Abstract: | Nitric oxide(NO_x), as one of the main pollutants, can contribute to a series of environmental problems, and to date the selective catalytic reduction(SCR) of NO_x with NH_3 in the presence of excess of O_2 over the catalysts has served as one of the most effective methods, in which Mn-based catalysts have been widely studied owing to their excellent low-temperature activity toward NH3-SCR. However, the related structure-activity relation was not satisfactorily explored at the atomic level. By virtue of DFT+U calculations together with microkinetic analysis, we systemically investigate the selective catalytic reduction process of NO with NH_3 over Mn_3 O_4(110), and identify the crucial thermodynamic and kinetic factors that limit the catalytic activity and selectivity.It is found that NH3 prefers to adsorb on the Lewis acid site and then dehydrogenates into NH_2~* assisted by either the two-or three-fold lattice oxygen; NH_2~* would then react with the gaseous NO to form an important intermediate NH_2 NO that prefers to convert into N_2 O rather than N_2 after the sequential dehydrogenation, while the residual H atoms interact with O_2 and left the surface in the form of H_2 O. The rate-determining step is proposed to be the coupling reaction between NH_2~* and gaseous NO.Regarding the complex surface structure of Mn_3 O_4(110),the main active sites are quantitatively revealed to be O_(3 c) and Mn_(4 c). |
