Precise control of the local environment and electronic state of the guest is an important method of controlling catalytic activity and reaction pathways.In this paper,guest Pd NPs were introduced into a series of hos...Precise control of the local environment and electronic state of the guest is an important method of controlling catalytic activity and reaction pathways.In this paper,guest Pd NPs were introduced into a series of host UiO-67 MOFs with different functional ligands and metal nodes,the microenvironment and local electronic structure of Pd is modulated by introducing bipyridine groups and changing metal nodes(Ce_(6)O_(6) or Zr_(6)O_(6)).The bipyridine groups not only promoted the dispersion Pd NPs,but also facilitated electron transfer between Pd and UiO-67 MOFs through the formation of Pd-N bridges.Compared with Zr6 clusters,the tunability and orbital hybridisation of the 4f electronic structure in the Ce_(6) clusters modulate the electronic structure of Pd through the construction of the Ce-O-Pd interfaces.The optimal catalyst Pd/UiO-67(Ce)-bpy presented excellent low-temperature activity towards dicyclopentadiene hydrogenation with a conversion of>99% and a selectivity of>99%(50℃,10 bar).The results show that the synergy of Ce-O-Pd and Pd-N promotes the formation of active Pd^(δ+),which not only enhances the adsorption of H_(2) and electron-rich C=C bonds,but also contributes to the reduction of proton migration distance and improves proton utilization efficiency.These results provide valuable insights for investigating the regulatory role of the host MOFs,the nature of host-guest interactions,and their correlation with catalytic performance.展开更多
Ce0.8Sm0.2O1.9-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ（SDC-LSGM）is prepared by the glycine-nitrate process（GNP）.SDC-LSGM composite electrolyte samples with different weight ratios are prepared by the co-combustion method so ...Ce0.8Sm0.2O1.9-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ（SDC-LSGM）is prepared by the glycine-nitrate process（GNP）.SDC-LSGM composite electrolyte samples with different weight ratios are prepared by the co-combustion method so as to obtain homogeneous nano-sized precursor powders. The X-ray diffraction （XRD） and the scan electron microscope （SEM） are used to investigate the phases and microstructures. The measurements and analyses of oxygen ionic conductivity of SDC-LSGM are carried out through the four-terminal direct current （DC） method and the electrochemical impendence spectroscopy, respectively. The optimum weight ratio of SDC-LSGM is 8∶2, of which the ionic conductivity is 0.113 S/cm at 800℃ and the conductivity activation energy is 0.620 eV. The impendence spectra shows that the grain boundary resistance becomes the main barrier for the ionic conductivity of electrolyte at lower temperatures. The appropriate introduction of LSGM to the electrolyte SDC can not only decrease the electronic conductivity but also improve the conditions of the grain and grain boundary, which is advantageous to cause an increase in oxygen ionic conductivity.展开更多
文摘Precise control of the local environment and electronic state of the guest is an important method of controlling catalytic activity and reaction pathways.In this paper,guest Pd NPs were introduced into a series of host UiO-67 MOFs with different functional ligands and metal nodes,the microenvironment and local electronic structure of Pd is modulated by introducing bipyridine groups and changing metal nodes(Ce_(6)O_(6) or Zr_(6)O_(6)).The bipyridine groups not only promoted the dispersion Pd NPs,but also facilitated electron transfer between Pd and UiO-67 MOFs through the formation of Pd-N bridges.Compared with Zr6 clusters,the tunability and orbital hybridisation of the 4f electronic structure in the Ce_(6) clusters modulate the electronic structure of Pd through the construction of the Ce-O-Pd interfaces.The optimal catalyst Pd/UiO-67(Ce)-bpy presented excellent low-temperature activity towards dicyclopentadiene hydrogenation with a conversion of>99% and a selectivity of>99%(50℃,10 bar).The results show that the synergy of Ce-O-Pd and Pd-N promotes the formation of active Pd^(δ+),which not only enhances the adsorption of H_(2) and electron-rich C=C bonds,but also contributes to the reduction of proton migration distance and improves proton utilization efficiency.These results provide valuable insights for investigating the regulatory role of the host MOFs,the nature of host-guest interactions,and their correlation with catalytic performance.
基金The National Basic Research Program of China (973 Program) (No.2007CB936300)the Natural Science Foundation of Jiangsu Province (No.BK2009293)
文摘Ce0.8Sm0.2O1.9-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ（SDC-LSGM）is prepared by the glycine-nitrate process（GNP）.SDC-LSGM composite electrolyte samples with different weight ratios are prepared by the co-combustion method so as to obtain homogeneous nano-sized precursor powders. The X-ray diffraction （XRD） and the scan electron microscope （SEM） are used to investigate the phases and microstructures. The measurements and analyses of oxygen ionic conductivity of SDC-LSGM are carried out through the four-terminal direct current （DC） method and the electrochemical impendence spectroscopy, respectively. The optimum weight ratio of SDC-LSGM is 8∶2, of which the ionic conductivity is 0.113 S/cm at 800℃ and the conductivity activation energy is 0.620 eV. The impendence spectra shows that the grain boundary resistance becomes the main barrier for the ionic conductivity of electrolyte at lower temperatures. The appropriate introduction of LSGM to the electrolyte SDC can not only decrease the electronic conductivity but also improve the conditions of the grain and grain boundary, which is advantageous to cause an increase in oxygen ionic conductivity.
