The oxidative carbonylation of phenol to diphenyl carbonate catalyzed by Pd Co, Pd Cu and Pd Mn catalyst systems has been studied with the addition of other components such as benzoquinone, Bu 2NBr and molecular sieve...The oxidative carbonylation of phenol to diphenyl carbonate catalyzed by Pd Co, Pd Cu and Pd Mn catalyst systems has been studied with the addition of other components such as benzoquinone, Bu 2NBr and molecular sieve. The results show that Bu 2NBr plays a very important role and Pd Mn catalyst has the highest activity among the three kinds of the catalysts studied. When the reaction is catalyzed by Pd Mn catalyst at n (PdCl 2)∶ n (Mn(OAc) 2)∶ n (Bu 4NBr)∶ n (benzoquinone)=1∶1∶ 10∶ 25, t =100 ℃, P =2 5 MPa( P CO / P O 2 =4∶1), reaction time 8 h, the yield of DPC is 7 23%. The yield of DPC is found to be increased with increase in total pressure of reactor and could be reached to 10 20% at total pressure of 3 5 MPa.展开更多
Mg-25 wt% Mg2Ni composite was prepared by sintered method, hydrided at 613 K and then ball-milled with 1.5 wt% PdC12 additive for 51 h. The effects of PdCl2 on the hydriding and dehydriding behavior of Mg-25 wt% Mg2Ni...Mg-25 wt% Mg2Ni composite was prepared by sintered method, hydrided at 613 K and then ball-milled with 1.5 wt% PdC12 additive for 51 h. The effects of PdCl2 on the hydriding and dehydriding behavior of Mg-25 wt% Mg2Ni composite were investigated. The absorption and desorption rate of the composite with PdCl2 is fast and the hydrogen storage capacity is more than that of the composite without PdCl2. The maximum hydrogen storage capacity reached 3.48 wt% at 373 K, and 5.05 wt% H at 453 K, respectively. The improvement of sorption and desorption kinetics is attributed to the catalytic effect of PdCl2, and the grain refining and lattice strain introduced by ball milling.展开更多
Direct chemoselective oxidation of δ-lactones via highly stable benzyl radical cyclization is reported. The one-pot conversion of premade substituted 5-aryl pentanoic acid and 8-benzyl-1-naphthoic acid in the presenc...Direct chemoselective oxidation of δ-lactones via highly stable benzyl radical cyclization is reported. The one-pot conversion of premade substituted 5-aryl pentanoic acid and 8-benzyl-1-naphthoic acid in the presence of K2S2Os--CuCl2 results to the δ-lactones in moderate to good yields. The advantages of this methodology is using water as a solvent and utilizing available starting materials.展开更多
The stability of composite palladium membranes is of key importance for their application in hydrogen energy systems. Most of these membranes are prepared by electroless plating, and beforehand the substrate surface i...The stability of composite palladium membranes is of key importance for their application in hydrogen energy systems. Most of these membranes are prepared by electroless plating, and beforehand the substrate surface is activated by a SnCl_2–PdCl_2 process, but this process leads to a residue of Sn, which has been reported to be harmful to the membrane stability. In this work, the Pd/Al_2O_3 membranes were prepared by electroless plating after the SnCl_2–PdCl_2 process. The amount of Sn residue was adjusted by the SnCl_2 concentration, activation times and additional Sn(OH)_2coating. The surface morphology, cross-sectional structure and elemental composition were analyzed by scanning electron microscopy(SEM), metallography and energy dispersive spectroscopy(EDS), respectively. Hydrogen permeation stability of the prepared palladium membranes were tested at450–600 °C for 400 h. It was found that the higher SnCl_2 concentration and activation times enlarged the Sn residue amount and led to a lower initial selectivity but a better membrane stability. Moreover, the additional Sn(OH)_2coating on the Al_2O_3 substrate surface also greatly improved the membrane selectivity and stability.Therefore, it can be concluded that the Sn residue from the SnCl_2–PdCl_2 process cannot be a main factor for the stability of the composite palladium membranes at high temperatures.展开更多
The configuration of[PdCl_2(C_2H_4OH)]^- has been studied by pseudopotential ab initio method.A cis isomer was found to be the reaction intermediate in the Wacker process.
文摘The oxidative carbonylation of phenol to diphenyl carbonate catalyzed by Pd Co, Pd Cu and Pd Mn catalyst systems has been studied with the addition of other components such as benzoquinone, Bu 2NBr and molecular sieve. The results show that Bu 2NBr plays a very important role and Pd Mn catalyst has the highest activity among the three kinds of the catalysts studied. When the reaction is catalyzed by Pd Mn catalyst at n (PdCl 2)∶ n (Mn(OAc) 2)∶ n (Bu 4NBr)∶ n (benzoquinone)=1∶1∶ 10∶ 25, t =100 ℃, P =2 5 MPa( P CO / P O 2 =4∶1), reaction time 8 h, the yield of DPC is 7 23%. The yield of DPC is found to be increased with increase in total pressure of reactor and could be reached to 10 20% at total pressure of 3 5 MPa.
基金Project supported by the Special Funds for Postdoctoral Research Project of China (No. 20060401035)the Hi-Tech Research and Development Program (863) of China (No. 2006AA11A159)
文摘Mg-25 wt% Mg2Ni composite was prepared by sintered method, hydrided at 613 K and then ball-milled with 1.5 wt% PdC12 additive for 51 h. The effects of PdCl2 on the hydriding and dehydriding behavior of Mg-25 wt% Mg2Ni composite were investigated. The absorption and desorption rate of the composite with PdCl2 is fast and the hydrogen storage capacity is more than that of the composite without PdCl2. The maximum hydrogen storage capacity reached 3.48 wt% at 373 K, and 5.05 wt% H at 453 K, respectively. The improvement of sorption and desorption kinetics is attributed to the catalytic effect of PdCl2, and the grain refining and lattice strain introduced by ball milling.
文摘Direct chemoselective oxidation of δ-lactones via highly stable benzyl radical cyclization is reported. The one-pot conversion of premade substituted 5-aryl pentanoic acid and 8-benzyl-1-naphthoic acid in the presence of K2S2Os--CuCl2 results to the δ-lactones in moderate to good yields. The advantages of this methodology is using water as a solvent and utilizing available starting materials.
基金Supported by the National High Technology Research and Development Program of China(863 Program,2009AA05ZI03)the Natural Science Foundation of Jiangsu Province(BK 20130940,BK 20130916)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘The stability of composite palladium membranes is of key importance for their application in hydrogen energy systems. Most of these membranes are prepared by electroless plating, and beforehand the substrate surface is activated by a SnCl_2–PdCl_2 process, but this process leads to a residue of Sn, which has been reported to be harmful to the membrane stability. In this work, the Pd/Al_2O_3 membranes were prepared by electroless plating after the SnCl_2–PdCl_2 process. The amount of Sn residue was adjusted by the SnCl_2 concentration, activation times and additional Sn(OH)_2coating. The surface morphology, cross-sectional structure and elemental composition were analyzed by scanning electron microscopy(SEM), metallography and energy dispersive spectroscopy(EDS), respectively. Hydrogen permeation stability of the prepared palladium membranes were tested at450–600 °C for 400 h. It was found that the higher SnCl_2 concentration and activation times enlarged the Sn residue amount and led to a lower initial selectivity but a better membrane stability. Moreover, the additional Sn(OH)_2coating on the Al_2O_3 substrate surface also greatly improved the membrane selectivity and stability.Therefore, it can be concluded that the Sn residue from the SnCl_2–PdCl_2 process cannot be a main factor for the stability of the composite palladium membranes at high temperatures.
文摘The configuration of[PdCl_2(C_2H_4OH)]^- has been studied by pseudopotential ab initio method.A cis isomer was found to be the reaction intermediate in the Wacker process.
