Exceptionally high and reversible NOx uptake by hollow Mn–Fe composite nanocubes derived from Prussian blue analogues

Abstract

Noble metal-based catalysts are widely used as passive NO_x adsorbers (PNA) for cold-start NO_x emissions; however, efficient porous materials as an alternative have great development potential. Herein, porous Mn–Fe composites with hollow nanocubes derived from Prussian blue analogue (PBA) precursors were used as PNA. The effects of O₂, the molar ratio of Mn/Fe, calcination temperature and reaction temperature on their adsorption capacity were explored. The physicochemical properties of the obtained catalysts were systematically characterized by XRD, SEM, BET surface area, TGA, XPS and DRIFT techniques. The developed Mn₁Fe₂-450 presented excellent NO_x uptake (more than 2.16 mmol g⁻¹ at 200 °C). Moreover, a high NO_x adsorption performance was also retained in the presence of 10% water vapor. The existing Mn³⁺ and Fe²⁺ species could contribute to the NO_x adsorption and gaseous O₂ can accelerate NO activation to form more easily adsorbed NO₂. Surface NO₂ is further diffused and stored into the bulk of the Mn–Fe composite in the form of nitrite and nitrate. This work revealed a novel candidate for PNA catalysts, which might provide inspiration for the design of new adsorbent materials.