A series of CuSO 4 /TiO 2 catalysts were prepared using a wet impregnation method. The activity of each sample in the selective catalytic reduction of NO by NH 3 (NH 3 -SCR) was determined. The effects of SO 2 and H 2 O, and their combined effect, on the activity were examined at 340 °C for 24 h. The catalysts were characterized using N 2 adsorption-desorption, X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction of H 2 (H 2 -TPR), temperature-programmed desorption of NH 3 (NH 3 -TPD), and in situ diffuse-reflectance infrared Fourier-transform spectroscopy (DRIFTS). The CuSO 4 /TiO 2 catalysts had good activities, with low production of N 2 O above 340 °C. SO 2 or a combination of SO 2 and H 2 O had little effect on the activity, and H 2 O caused only a slight decrease in activity during the experimental period. The NH 3 -TPD and H 2 -TPR results showed that CuSO 4 increased the amounts of acid sites and adsorbed oxygen on the catalyst. In situ DRIFTS showed that the NH 3 -SCR reaction on the CuSO 4 /TiO 2 catalysts followed an Eley–Rideal mechanism. The reaction of gaseous NO with NH 3 adsorbed on Lewis acid sites to form N 2 and H 2 O could be the main reaction pathway, and oxygen adsorption might favor this process.
Anatase TiO 2 loaded with 0.1wt.% Pt catalyst (0.1Pt/TiO 2 -A) was prepared via the impregnation method, and its CO catalytic oxidation activity was investigated. Noteworthy, introduction of H 2 O into the reaction atmosphere apparently facilitated the catalytic oxidation of CO. Besides, introduction of SO 2 inhibited the catalytic oxidation of CO. In presence of H 2 O and SO 2 , 0.1Pt/TiO 2 -A showed outstanding catalytic stability, and X-ray photoelectron spectroscopy (XPS) and thermogravimetric (TG) characterizations suggested that the amount of sulfate species deposited on the 0.1Pt/TiO 2 -A treated at 230 °C did not increase with time extension, which might be an important reason for the high sulfur resistance of 0.1Pt/TiO 2 -A. XPS results also demonstrated that the dissociation of H 2 O led to considerably increase of hydroxyl groups over the catalyst surface. H 2 18 O isotope-labeling experiments unambiguously showed that C 16 O 18 O was the main product accounting for 88.9%, revealing that the other oxygen atom in the product CO 2 was mostly from H 2 O. Consequently, based on previous researches and our experimental results, the mechanism of H 2 O promoting CO oxidation on 0.1Pt/TiO 2 -A catalyst was proposed.
SO 2 in the sintering flue gas severely inhibits the CO oxidation performance of commercial Pt/Al 2 O 3 catalysts. However, the major poisoning mechanism of SO 2 on Pt/Al 2 O 3 in CO oxidation in the presence of H 2 O remains to be elucidated. Here, Pt/Al 2 O 3 was pretreated with different reducing atmospheres at high temperatures. Among these, the catalyst pretreated with a CO atmosphere at 600 °C (denoted as Pt/Al 2 O 3 -CO-600) exhibited superior CO oxidation performance and enhanced sulfur resistance in the presence of both H 2 O and SO 2 . The combination of XPS, HAADF-STEM, TG-MS, SO 2 oxidation test, and in-situ DRIFTS reveal that the Pt species on Pt/Al 2 O 3 -CO-600 transformed from Pt oxide clusters to metallic Pt nanoparticles. This transformation enhanced SO 2 adsorption and reactivity, leading to increased sulfate accumulation. Despite the high SO 2 reactivity and sulfate content, in-situ DRIFTS revealed that the CO reaction of Pt/Al 2 O 3 -CO-600 was less hindered by SO 2 and the sulfated Al 2 O 3 . This is attributed to the high ratio of the under-coordinated (UC) Pt sites in Pt/Al 2 O 3 -CO-600, which promotes the reaction intermediates spillover from Pt site to Al 2 O 3 compared to the Pt/Al 2 O 3 . This phenomenon was positively correlated with the sulfur resistance of reduced catalysts. Accordingly, the UC site contributes to the spillover of sulfate intermediate (H 2 SO 4 ), reducing the CO reactivity loss of Pt/Al 2 O 3 due to the intermediate coverage. This study elucidates that the primary poisoning pathway of Pt/Al 2 O 3 in the presence of H 2 O and SO 2 is the difficulty of sulfate intermediate spillover.
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