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(Ce6O6 or Zr6O6).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 Ce6 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 Pdδ+,which not only enhances the adsorption of H2 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
Due to the paramagnetic property of liquid oxygen,the Kelvin force can be induced in liquid oxygen under non-uniform magnetic field.Based on the volume of fluid(VOF)model,the positioning effect of the force in liquid ...Due to the paramagnetic property of liquid oxygen,the Kelvin force can be induced in liquid oxygen under non-uniform magnetic field.Based on the volume of fluid(VOF)model,the positioning effect of the force in liquid oxygen tanks is analyzed under various Bond numbers(Bo)and magnetic Bond numbers(Bom).The results show that the magnetic field has the effect of repositioning the liquid oxygen in the tank when the gravity field is not enough or absent.Additionally,the gas-liquid interface has a periodic fluctuation during the process due to the inhomogeneous Kelvin force distribution,and more effective suppression of fluctuation can be achieved under the condition of a larger Bom.The new method of controlling gas-liquid interface of liquid oxygen tank under micro gravity condition is hoped to be developed in the future.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(Ce6O6 or Zr6O6).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 Ce6 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 Pdδ+,which not only enhances the adsorption of H2 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supported by the Natural Science Foundation of China(No.51706190)the State Scholarship Fund of China Scholarship Council。
文摘Due to the paramagnetic property of liquid oxygen,the Kelvin force can be induced in liquid oxygen under non-uniform magnetic field.Based on the volume of fluid(VOF)model,the positioning effect of the force in liquid oxygen tanks is analyzed under various Bond numbers(Bo)and magnetic Bond numbers(Bom).The results show that the magnetic field has the effect of repositioning the liquid oxygen in the tank when the gravity field is not enough or absent.Additionally,the gas-liquid interface has a periodic fluctuation during the process due to the inhomogeneous Kelvin force distribution,and more effective suppression of fluctuation can be achieved under the condition of a larger Bom.The new method of controlling gas-liquid interface of liquid oxygen tank under micro gravity condition is hoped to be developed in the future.
