A Study of Different Doped Metal Cations on the Physicochemical Properties and Catalytic Activities of Ce20 M1 Ox (M=Zr, Cr, Mn, Fe, Co, Sn) Composite Oxides for Nitric Oxide Reduction by Carbon Monoxide.

This work is mainly focused on investigating the effects of different doped metal cations on the formation of Ce20 M1 Ox (M=Zr, Cr, Mn, Fe, Co, Sn) composite oxides and their physicochemical and catalytic properties for NO reduction by CO as a model reaction. The obtained samples were characterized by using N2 physisorption, X-ray diffraction, laser Raman spectroscopy, UV/Vis diffuse reflectance spectroscopy, inductively coupled plasma atomic emission spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction by hydrogen and by oxygen (H2 -TPR and O2 -TPD), in situ diffuse reflectance infrared Fourier transform spectroscopy, and the NO+CO model reaction. The results imply that the introduction of M(x+) into the lattice of CeO2 increases the specific surface area and pore volume, especially for variable valence metal cations, and enhances the catalytic performance to a great extent. In this regard, increases in the oxygen vacancies, reduction properties, and chemisorbed O2 (-) (and/or O(-) ) species of these Ce20 M1 Ox composite oxides (M refers to variable valence metals) play significant roles in this reaction. Among the samples, Ce20 Cr1 Ox exhibited the best catalytic performance, mainly because it has the best reducibility and more chemisorbed oxygen, and significant reasons for these attributes may be closely related to favorable synergistic interactions of the vacancies and near-surface Ce(3+) and Cr(3+) . Finally, a possible reaction mechanism was tentatively proposed to understand the reactions.

The effect of positioning cations on acidity and stability of the framework structure of Y zeolite.

The investigation on the modification of NaY zeolite on LaHY and AEHY (AE refers Ca and Sr and the molar ratio of Ca and Sr is 1:1) zeolites was proformed by XRD, N2-physisorption (BET), XRF, XPS, NH3-TPD, Py-IR, hydrothermal stability, and catalytic cracking test. These results indicate that HY zeolite with ultra low content Na can be obtained from NaY zeolite through four exchange four calcination method. The positioning capability of La(3+) in sodalite cage is much better than that of AE(2+) and about 12 La(3+) can be well coordinated in sodalite cages of one unit cell of Y zeolite. Appropriate acid amount and strength favor the formation of propylene and La(3+) is more suitable for the catalytic cracking of cyclohexane than that of AE(2+). Our results not only elaborate the variation of the strong and weak acid sites as well as the Brönsted and Lewis acid sites with the change of exchanged ion content but also explore the influence of hydrothermal aging of LaHY and AEHY zeolites and find the optimum ion exchange content for the most reserved acid sites. At last, the coordination state and stabilization of ion exchanged Y zeolites were discussed in detail.

NO reduction by CO over CuO supported on CeO2-doped TiO2: the effect of the amount of a few CeO2.

This work is mainly focused on the investigation of the influence of the amount of a few CeO2 on the physicochemical and catalytic properties of CeO2-doped TiO2 catalysts for NO reduction by a CO model reaction. The obtained samples were characterized by means of XRD, N2-physisorption (BET), LRS, UV-vis DRS, XPS, (O2, CO, and NO)-TPD, H2-TPR, in situ FT-IR, and a NO + CO model reaction. These results indicate that a small quantity of CeO2 doping into the TiO2 support will cause an obvious change in the properties of the catalyst and the TC-60 : 1 (the TiO2/CeO2 molar ratio is 60 : 1) support exhibits the most extent of lattice expansion, which indicates that the band lengths of Ce-O-Ti are longer than other TC (the solid solution of TiO2 and CeO2) samples, probably contributing to larger structural distortion and disorder, more defects and oxygen vacancies. Copper oxide species supported on TC supports are much easier to be reduced than those supported on the pure TiO2 and CeO2 surface-modified TiO2 supports. Furthermore, the Cu/TC-60 : 1 catalyst shows the highest activity and selectivity due to more oxygen vacancies, higher mobility of surface and lattice oxygen at lower temperature (which contributes to the regeneration of oxygen vacancies, and the best reducing ability), the most content of Cu(+), and the strongest synergistic effect between Ti(3+), Ce(3+) and Cu(+). On the other hand, the CeO2 doping into TiO2 promotes the formation of a Cu(+)/Cu(0) redox cycle at high temperatures, which has a crucial effect on N2O reduction. Finally, in order to further understand the nature of the catalytic performances of these samples, taking the Cu/TC-60 : 1 catalyst as an example, a possible reaction mechanism is tentatively proposed.