The deactivation issue arising from alkali poisoning over catalysts is still a challenge for the selective catalytic reduction of NOx by NH3. Herein, improved NOx reduction in the presence of alkaline metals over phosphate-modified Fe2O3/TiO2 catalysts has been originally demonstrated via tailoring the reaction paths by in situ creating alkali-poisoning sites. The introduction of phosphate results in the partial formation of iron phosphate species and makes the catalyst to mainly exhibit the characteristics of FePO4, which is responsible for the widened temperature window and enhanced alkali resistance. The tetrahedral [FeO4]/[PO4] structures in iron phosphate act as the Brønsted acid sites to increase the catalyst surface acidity. In addition, the formation of an Fe-O-P structure enhances the redox ability and increases surface adsorbed oxygen. Furthermore, the created phosphate groups (PO43-) serving as alkali-poisoning sites preferentially combine with potassium so that iron species on the active sites are protected. Therefore, the enhanced NH3 species adsorption capacity, improved redox ability, and active nitrate species remaining in the phosphate-modified Fe2O3/TiO2 catalyst ensure the de-NOx activity after being poisoned by alkali metals through the Langmuir-Hinshelwood reaction pathway. Hopefully, this novel strategy could provide an inspiration to design novel catalysts to control NOx emission with extraordinary resistance to alkaline metals.
Keywords: NOx; alkali resistance; iron-based catalysts; phosphate modification; selective catalytic reduction.