Scale-Activity Relationship of MnO-FeO Nanocage Catalysts Derived from Prussian Blue Analogues for Low-Temperature NO Reduction: Experimental and DFT Studies.

Size effects have been recognized to promote the catalytic activity and selectivity of metal oxide particles. So far, limited works and studies are conducted to investigate the size effect of metal oxide with the tailored shape in the selective catalytic reduction of NO with NH (NH-SCR). Herein, the MnO-FeO nanocage catalysts with varied scales (0.25, 0.5, 1, and 2 μm) were synthesized via a Prussian blue analogue (PBA)-derived method and used for NH-SCR of NO. By preforming a series of the activity tests over the nanocages with different scales, the NH-SCR activity of 0.5 μm MnO-FeO nanocage catalysts exhibits the highest deNO activity in the temperature range of 80-200 °C owing to more preferable physical and chemical properties. It has been demonstrated that there is a strong interaction among Mn and Fe cations in the 0.5 μm MnO-FeO nanocages. Moreover, the H-TPR and XPS analysis prove 0.5 μm nanocages exhibit excellent redox properties, which contribute to the higher conservation of NO. Through the DFT studies, it is also demonstrated that the 0.5 μm MnO-FeO nanocage catalysts could provide more preferable electronic charge, which gives rise to the varied adsorption behavior of the NH species and NO species compared to the nanocages with other scales. The in situ DRIFTs were also employed to evaluate the adsorption status of NH with NO species over MnO-FeO nanocage catalysts with varied scales. Finally, the scale-activity relationship of the MnO-FeO nanocage catalysts and their corresponding activities are also established. The deep insight into the scale-activity relationship of the PBA-derived MnO-FeO nanocage catalyst paves the way for developing and designing highly efficient Mn-based catalyst at lower temperature.