Al 2O 3-SiO 2-TiO 2-ZrO 2 supported membranes were prepar ed by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al 2O 3, TiO 2(a nat...Al 2O 3-SiO 2-TiO 2-ZrO 2 supported membranes were prepar ed by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al 2O 3, TiO 2(a natase), Al 2SiO 5, and ZrO 2 in these membranes. Changing the molar ratio of Al∶Si∶Ti∶Zr,the kinds and content of crystal phases of composite membranes could be different, which may lead to a variety of microstructure of membranes. The surface nanoscale topography and microstructure of membranes were investiga ted by XRD,SEM,AFM,EPMA. The effects of additives and heat treatments on the sur face nanoscale topography and microstructure of composite ceramic membranes were also analyzed.展开更多
Cu/ZrO2/SiO2 are efficient catalysts for the selective hydrogenation of CO2 to CH3OH. In order to understand the role of ZrO2 in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carri...Cu/ZrO2/SiO2 are efficient catalysts for the selective hydrogenation of CO2 to CH3OH. In order to understand the role of ZrO2 in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carried out on the Cu and Zr K-edge. Under reaction conditions, Cu remains metallic, while Zr is present in three types of coordination environment associated with 1) bulk ZrO2, 2) coordinatively saturated and 3) unsaturated Zr(Ⅳ) surface sites. The amount of coordinatively unsaturated Zr surface sites can be quantified by linear combination fit of reference X-Ray absorption near edge structure (XANES) spectra and its amount correlates with CH3OH formation rates, thus indicating the importance of Zr(Ⅳ) Lewis acid surface sites in driving the selectivity toward CH3OH. This finding is consistent with the proposed mechanism, where CO2 is hydrogenated at the interface between the Cu nanoparticles that split H2 and Zr(Ⅳ) surface sites that stabilizes reaction intermediates.展开更多
摘要Al 2O 3-SiO 2-TiO 2-ZrO 2 supported membranes were prepar ed by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al 2O 3, TiO 2(a natase), Al 2SiO 5, and ZrO 2 in these membranes. Changing the molar ratio of Al∶Si∶Ti∶Zr,the kinds and content of crystal phases of composite membranes could be different, which may lead to a variety of microstructure of membranes. The surface nanoscale topography and microstructure of membranes were investiga ted by XRD,SEM,AFM,EPMA. The effects of additives and heat treatments on the sur face nanoscale topography and microstructure of composite ceramic membranes were also analyzed.
基金E.L.,K.L.,P.W.,and S.T.are supported by the SCCER-Heat and Energy Storage program
摘要Cu/ZrO2/SiO2 are efficient catalysts for the selective hydrogenation of CO2 to CH3OH. In order to understand the role of ZrO2 in these mixed-oxides based catalysts, in situ X-ray absorption spectroscopy has been carried out on the Cu and Zr K-edge. Under reaction conditions, Cu remains metallic, while Zr is present in three types of coordination environment associated with 1) bulk ZrO2, 2) coordinatively saturated and 3) unsaturated Zr(Ⅳ) surface sites. The amount of coordinatively unsaturated Zr surface sites can be quantified by linear combination fit of reference X-Ray absorption near edge structure (XANES) spectra and its amount correlates with CH3OH formation rates, thus indicating the importance of Zr(Ⅳ) Lewis acid surface sites in driving the selectivity toward CH3OH. This finding is consistent with the proposed mechanism, where CO2 is hydrogenated at the interface between the Cu nanoparticles that split H2 and Zr(Ⅳ) surface sites that stabilizes reaction intermediates.