SO2-4–Mo O3–Zr O2–Nd2O3/Si O2（SMZN/Si O2） catalysts for the production of biodiesel via both esterification and transesterification were prepared and characterized by N2adsorption-desorption isotherms,X-ray diffr...SO2-4–Mo O3–Zr O2–Nd2O3/Si O2（SMZN/Si O2） catalysts for the production of biodiesel via both esterification and transesterification were prepared and characterized by N2adsorption-desorption isotherms,X-ray diffraction（XRD）,scanning electron microscopy（SEM）,thermogravimetry analysis（TGA）,ammonia adsorption Fourier transform infrared spectra（NH3-FTIR）,and ammonia adsorption temperature programmed desorption（NH3-TPD） to reveal the dependence of the stable catalytic activity on calcination time. The reason for catalyst deactivation was also studied. The calcination time remarkably affected the types of active centers on SMZN/Si O2-2,and 4 h was found to be the optimal calcination time. SO4 species bonded with small size Zr O2 were found to be the stable active centers,where the leaching of SO2-4and the deposition of coke were inhibited. The deposition of coke was easier on large size Zr O2 than on small size ones. Calcination in air flow could eliminate the deposited coke to recover the deactivated catalysts.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
基金supported by the National Nature Science Foundation of China (no.21106089)
文摘SO2-4–Mo O3–Zr O2–Nd2O3/Si O2（SMZN/Si O2） catalysts for the production of biodiesel via both esterification and transesterification were prepared and characterized by N2adsorption-desorption isotherms,X-ray diffraction（XRD）,scanning electron microscopy（SEM）,thermogravimetry analysis（TGA）,ammonia adsorption Fourier transform infrared spectra（NH3-FTIR）,and ammonia adsorption temperature programmed desorption（NH3-TPD） to reveal the dependence of the stable catalytic activity on calcination time. The reason for catalyst deactivation was also studied. The calcination time remarkably affected the types of active centers on SMZN/Si O2-2,and 4 h was found to be the optimal calcination time. SO4 species bonded with small size Zr O2 were found to be the stable active centers,where the leaching of SO2-4and the deposition of coke were inhibited. The deposition of coke was easier on large size Zr O2 than on small size ones. Calcination in air flow could eliminate the deposited coke to recover the deactivated catalysts.
基金E.L.,K.L.,P.W.,and S.T.are supported by the SCCER-Heat and Energy Storage program
文摘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.
