Hydrothermal Aging Alleviates the Phosphorus Poisoning of Cu-SSZ-39 Catalysts for NH3-SCR Reaction.

As a new type of catalyst with the potential for commercial application in NOx removal from diesel engine exhausts, Cu-SSZ-39 catalysts must have excellent resistance to complex and harsh conditions. In this paper, the effects of phosphorus on Cu-SSZ-39 catalysts before and after hydrothermal aging treatment were investigated. Compared with fresh Cu-SSZ-39 catalysts, phosphorus poisoning significantly decreased the low-temperature NH3-SCR catalytic activity. However, such activity loss was alleviated by further hydrothermal aging treatment. To reveal the reason for this interesting result, a variety of characterization techniques including NMR, H2-TPR, X-ray photoelectron spectroscopy, NH3-TPD, and in situ DRIFTS measurements were employed. It was found that Cu-P species produced by phosphorus poisoning decreased the redox ability of active copper species, resulting in the observed low-temperature deactivation. After hydrothermal aging treatment, however, Cu-P species partly decomposed with the formation of active CuOx species and a release of active copper species. As a result, the low-temperature NH3-SCR catalytic activity of Cu-SSZ-39 catalysts was recovered.

Nano-sized alumina supported palladium catalysts for methane combustion with excellent thermal stability.

Pd/Al2O3 catalysts supported on Al2O3 of different particle sizes were synthesized and applied in methane combustion. These catalysts were systematically characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), high resolution-transmission electron microscopy (HR-TEM), high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), H2-temperature-programmed reduction (H2-TPR), O2-temperature-programmed oxidation (O2-TPO), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure (XAFS). The characterization results indicated that nano-sized Al2O3 enabled the uniform dispersion of palladium nanoparticles, thus contributing to the excellent catalytic performance of these nano-sized Pd/Al2O3 catalysts. Among them, Pd/Al2O3-nano-10 (Pd/Al2O3 supported by alumina with an average particle size of 10 nm) showed superior catalytic activity and stability for methane oxidation under harsh practical conditions. It maintained excellent catalytic performance for methane oxidation for 50 hr and remained stable even after harsh hydrothermal aging in 10 vol.% steam at 800°C for 16 hr. Characterization results revealed that the strong metal-support interactions and physical barriers provided by Al2O3-nano-10 suppressed the coalescence ripening of palladium species, and thus contributed to the superior sintering resistance of the Pd/Al2O3-nano-10 catalyst.

Si/Al Ratio Determines the SCR Performance of Cu-SSZ-13 Catalysts in the Presence of NO2.

A comparative study was performed to investigate the NH3-selective catalytic reduction (SCR) reaction activity of Cu-SSZ-13 zeolites having Si/Al ratios (SARs) of 5, 18, and 30. Remarkably, the Cu-SSZ-13 zeolite catalysts exhibited completely opposite behaviors as a function of SAR under standard SCR (SSCR) and fast SCR (FSCR) reaction atmospheres. Under SSCR conditions, the NOx conversion increased as expected with the decreasing SAR. Under FSCR conditions, however, the NOx conversion decreased as the SAR decreased, contrary to expectations. In this study, based on characterization of the catalysts by X-ray diffraction, transmission electron microscopy, electron paramagnetic resonance, H2-temperature-programmed reduction, temperature-programmed desorption, and diffuse reflectance infrared Fourier transform spectroscopy, together with theoretical calculations, the authors found that the amount of Brønsted acid sites goes up while the SAR goes down, leading to an increase in the accumulation of NH4NO3 under FSCR reaction conditions. Moreover, the accumulated NH4NO3 is of greater stability for those low SAR Cu-SSZ-13 catalysts. These two reasons cause the FSCR performance of Cu-SSZ-13 to decrease with a decrease in SAR. As a result, the NO2 effect on SCR activity changes from promotion to inhibition as the SAR decreases.