The effect of the mixing ways of Ce0.7Zr0.3O2-Al2O3 mixed oxides on the partial oxidations of methane (POM) was investigated over Pd/Ce0.7Zr0.3O2-Al2O3 catalysts, the mixing ways including salt precursor mixing (ATOM), precipitator mixing (MOL), and powder mechanically mixing (MECH), respectively. The test results indicated that among the three samples, Pd/ATOM had the best catalytic activity while Pd/MOL had the best stability in the stability test. Both the activity sequences of the fresh and used samples were consistent with the order of Pd dispersion. According to the X-ray diffraction (XRD) and BET characterization, the interaction of Ce^4+, Zr^4+, and Al^3+ in the ATOM mixed oxide was in favor of performing higher catalytic activity and thermal stability. The stability test indicated that Pd/MOL had the highest Pd dispersion and least coke formation on the active sites calculated by the Hz-chemisorption and TG results, which was considered to relate to its superior activity of POM to other catalysts.
Mn0.1Ce0.9Ox and Mn0.1Ce0.6Zr0.30x samples synthesized by sol-gel method were tested for redox properties through the dynamic oxygen storage measurement and characterized using X-ray diffraction, BET, electron paramagnetic resonance, and X-ray photoelectron spectroscopy. The results showed that redox performances of ceria-based materials could be enhanced by synergetic effects between Mn-O and Ce-O. Fresh and aged samples were characterized with the fluorite-type cubic structure similar to CeO2, and furthermore, the thermal stability of Mn0.1Ce0.9Ox materials was improved by the introduction of some Zr atoms. From XPS, it could be concluded that Mn^2+/Mn^3+ redox couples existed on the surface of Mn0.1Ce0.9Ox and Mn0.1Ce0.6Zr0.3Ox samples. Electron paramagnetic resonance researches revealed that there were three types of Mn^2+ species: isolated Mn^2+ substituting for Ce^4+ ions in the lattice with a cubic symmetry, ones in defect with a noncubic symmetry, and at the surface of samples.
The influences of CeO2-ZrO2 and γ-Al2O3 mixing methods on the catalytic activity and stability of partial oxidation of methane (POM) were investigated over Ni/Ce0.7Zr0.3O2-Al2O3 catalysts. The catalysts were characterized by XRD, TPR, H2-chemsorption, and TG-DTA. For fresh catalysts, the results showed that the salt precursor mixing catalyst (ATOM) presented better performance than the catalysts prepared by the precipitator mixing method (MOL) and the powder mechanically mixing method (MECH). The result of XRD suggested that the interaction between CeO2-ZrO2 and Al2O3 in ATOM sample was stronger than the others, which led to more lattice defects and thereby better initial activity. Moreover, the MECH sample had the best stability and the least coke deposition in 24 h stability tests. The results of TPR and H2-chemsorption indicated that the intimate contact of Ni-Al in MECH sample enhanced the ability of resisting coke deposition and metal sintering.