Revealing the crystal facet effect on N₂O formation during the NH₃-SCR over α-MnO₂ catalysts

The detailed atomic-level mechanism of the effect induced by engineering the crystal facet of α-MnO₂ catalysts on N₂O formation during ammonia-selective catalytic reduction (NH₃-SCR) was ascertained by combining density functional theory (DFT) calculations and thermodynamics/kinetic analysis. The surface energies of α-MnO₂ with specific (100), (110), and (310) exposed planes were calculated, and the adsorptions of NH₃, NO, and O₂ on three surfaces were analyzed. The adsorption energies showed that NH₃ and NO molecules could be strongly adsorbed on the surface of the α-MnO₂ catalyst, while the adsorption of O₂ was weak. Moreover, the key steps in the oxidative dehydrogenation of NH₃ and the formation of NH₂NO as well as dissociation of NH₂ were studied to evaluate the catalytic ability of NH₃-SCR reaction and N₂ selectivity. The results revealed that the α-MnO₂ catalyst exposed with the (310) plane exhibited the best NH₃-SCR catalytic performance and highest N₂ selectivity, mainly due to its low energy barriers in NH₃ dehydrogenation and NH₂NO generation, and difficulty in NH₂ dissociation. This study deepens the comprehension of the facet-engineering of α-MnO₂ on inhibiting N₂O formation during the NH₃-SCR, and points out a strategy to improve their catalytic ability and N₂ selectivity for the low-temperature NH₃-SCR process.