Comparative study of HSO_A^-/SO_A^2- versus H_3−BPO₄^B- functionalities anchored on TiO₂-supported antimony oxide-vanadium oxide-cerium oxide composites for low-temperature NO_X activation

TiO₂-supported antimony oxide-vanadium oxide-cerium oxide (SVC) imparts Lewis acidic (L)/Brönsted acidic (B) sites, labile (O_α)/mobile oxygens (O_M), and oxygen vacancies (O_V) for selective catalytic NO_X reduction (SCR). However, these species are harmonious occasionally, readily poisoned by H₂O/sulfur/phosphorus/carbon, thus limiting SCR performance of SVC. Herein, a synthetic means is reported for immobilizing HSO_A^-/SO_A^2- (A= 3–4) or H_3−BPO₄^B- (B= 1–3) on the L sites of SVC to form SVC-S and SVC-P. HSO_A^-/SO_A^2-/H_3−BPO₄^B- acted as additional B sites with distinct characteristics, altered the properties of O_α/O_M/O_V species, thereby affecting the SCR activities and performance of SVC-S and SVC-P. SVC-P activated Langmuir-Hinshelwood-typed SCR better than SVC-S, as demonstrated by a greater O_α-directed pre-factor and smaller binding energy between O_α and NO. Meanwhile, SVC-S provided a larger B-directed pre-factor, thereby outperforming SVC-P in activating Eley-Rideal-typed SCR that dictated the overall SCR activities. Compared with SVC-S, SVC-P contained fewer O_V species, yet, had higher O_M mobility, thus enhancing the overall redox cycling feature, while providing greater Brönsted acidity. Consequently, the resistance of SVC-P to H₂O or soot were greater than or similar to that of SVC-S. Conversely, SVC-S revealed greater tolerance to hydro-thermal aging and SO₂ than SVC-P. This study highlights the pros and cons of HSO_A^-/SO_A^2-/H_3−BPO₄^B- functionalities in tailoring the properties of metal oxides in use as SCR catalysts.