A series of CexZr0.50-xAl0.50O1.75(0.05≤x≤0.45) mixed oxides with different Ce/Zr ratio were prepared by co-precipitation method and characterized by means of X-ray diffraction(XRD),Brunauer-Emmet Teller method(BET),temperature-programmed reduction(H2-TPR) and oxygen pulsing technique.The XRD results showed that all samples kept the single CeO2 cubic fluorite structure after calcination at 600 and 1000 oC for 5 h.The results of BET revealed that CexZr0.50-xAl0.50O1.75 with Ce/Zr molar ratio 1/1 exhibited higher specific surface area(212 m2/g) and larger pore volume(0.40 ml/g).For all aged samples,CZA with Ce/Zr molar ratio 3/7 presented the highest specific surface area(104 m2/g) and pore volume(0.34 ml/g).The compounds could still keep prominent structural and textural stability with excellent redox properties even calcined at 1000 oC.
The catalytic behaviors of Pd (1.4 wt.%) catalysts supported on CeO2-ZrO2 promoted with La2O3 were investigated for methanol decomposition. The measurements of inductively coupled plasma emission spectroscopy (ICP), N2 adsorption-desorption (BET), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR) and oxygen storage capacity (OSC) were used to characterize the properties of catalysts. The catalysts' activities were tested in a fixed bed continuous flow reactor operating under atmospheric pressure. The Pd/Ce0.8Zr0.2O2-5 wt.%La2O3 catalyst exhibited the best activity. The reasons for this were twofold: (1) doping of La improved effectively textural properties of CeO2-ZrO2 oxygen storage materials, and (2) Pd/Ce0.8Zr0.2O2-5 wt.%La2O3 possessed super oxygen storage property and reducibility due to the existence of lattice defect oxygen or mobile oxygen, which helped to re-oxidize zerovalent Pd0 to a partly oxidized Pdδ+. By introducing 5 wt.%La2O3, the specific surface area of the sample increased, but declined if further increasing the content of La2O3 to 10 wt.%.
Composite supports CeO2-ZrO2-Al2O3 (CZA) and CeO2-ZrO2-Al2O3-La2O3 (CZALa) were prepared by co-precipitation method. Palladium catalysts were prepared by impregnation and their purification ability for CH4, CO and NOx in the mixture gas simulated the exhaust from natural gas vehicles (NGVs) operated under stoichiometric condition was investigated. The effect of La2O3 on the physicochemical properties of supports and catalysts was characterized by various techniques. The characterizations with X-ray diffraction (XRD) and Raman spectroscopy revealed that the doping of La2O3 restrained effectively the sintering of crystallite particles, maintained the crystallite particles in nanoscale and stabilized the crystal phase after calcination at 1000℃. The results of N2-adsorption, H2-temperature-programmed reduction (H2-TPR) and oxygen storage capacity (OSC) measurements indicated that La2O3 improved the textural properties, reducibility and OSC of composite supports. Activity testing results showed that the catalysts exhibit excellent activities for the simultaneous removal of methane, CO and NOx in the simulated exhaust gas. The catalysts supported on CZALa showed remarkable thermal stability and catalytic activity for the three pollutants, especially for NOx. The prepared palladium catalysts have high ability to remove NOx, CH4 and CO, and they can be used as excellent catalysts for the purification of exhaust from NGVs operated under stoichiometric condition. The catalysts reported in this work also have significant potential in industrial application because of their high performance and low cost.
