A series of Pd catalysts were prepared on different supports（Fe2O3,SiO2,ZnO,MgO,Al2O3,carbon,and Amberlyst-45） and used in the selective hydrogenation of phenol to cyclohexanone in water.The Amberlyst-45 supported P...A series of Pd catalysts were prepared on different supports（Fe2O3,SiO2,ZnO,MgO,Al2O3,carbon,and Amberlyst-45） and used in the selective hydrogenation of phenol to cyclohexanone in water.The Amberlyst-45 supported Pd catalyst（Pd/A-45） was highly active and selective under mild conditions（40-100 ℃,0.2-1 MPa）,giving a selectivity of cyclohexanone higher than 89%even at complete conversion of phenol.Experiments with different Pd loadings（or different particle sizes） confirmed that the formation of cyclohexanone was a structure sensitive reaction,and Pd particles of12-14 nm on Amberlyst-45 gave better selectivity and stability.展开更多
An account of recent work on supported single‐atom catalyst design is given here for reactions as diverse as the low‐temperature water‐gas shift,methanol steam reforming,selective ethanol dehydrogenation,and select...An account of recent work on supported single‐atom catalyst design is given here for reactions as diverse as the low‐temperature water‐gas shift,methanol steam reforming,selective ethanol dehydrogenation,and selective hydrogenation of alkynes and dienes.It is of fundamental interest to investigate the intrinsic activity and selectivity of the active metal atom site and compare them to the properties of the corresponding metal nanoparticles and sub‐nm clusters.It is also important to understand what constitutes a stable active metal atom site in the various reaction environments,and maximize their loadings to allow us to design robust catalysts for industrial applications.Combined activity and stability studies,ideally following the evolution of the active site as a function of catalyst treatment in real time are recommended.Advanced characterization methods with atomic resolution will play a key role here and will be used to guide the design of new catalysts.展开更多
Porous polymer supported palladium catalyst for cross coupling reactions with high activity has been successfully prepared by coordination of Pd 2+ species with Schiff bases functionalized porous polymer. The catalyst...Porous polymer supported palladium catalyst for cross coupling reactions with high activity has been successfully prepared by coordination of Pd 2+ species with Schiff bases functionalized porous polymer. The catalyst has been systemically investi-gated by a series of characterizations such as TEM, N 2 adsorption, NMR, IR, XPS, etc. TEM and N 2 isotherms show that the sample maintains the nanoporous structure after the modification and coordination. XPS results show that chemical state of palladium species in the catalyst is mainly +2. More importantly, the catalyst shows very high activities and excellent recycla-bility in a series of coupling reactions including Suzuki, Sonogashira, and Heck reactions. Hot filtration and poison of catalysts experiments have also been performed and the results indicate that soluble active species (mainly Pd(0) species) in-situ gener-ated from the catalyst under the reaction conditions are the active intermediates, which would redeposit to the supporter after the reactions.展开更多
基金supported by the National Natural Science Foundation of China(21473155,21273198,21073159)the Natural Science Foundation of Zhejiang Province(LZ12B03001)~~
文摘A series of Pd catalysts were prepared on different supports（Fe2O3,SiO2,ZnO,MgO,Al2O3,carbon,and Amberlyst-45） and used in the selective hydrogenation of phenol to cyclohexanone in water.The Amberlyst-45 supported Pd catalyst（Pd/A-45） was highly active and selective under mild conditions（40-100 ℃,0.2-1 MPa）,giving a selectivity of cyclohexanone higher than 89%even at complete conversion of phenol.Experiments with different Pd loadings（or different particle sizes） confirmed that the formation of cyclohexanone was a structure sensitive reaction,and Pd particles of12-14 nm on Amberlyst-45 gave better selectivity and stability.
基金financial support of the work by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Awards Grant Number DE-FG02-05ER15730
文摘An account of recent work on supported single‐atom catalyst design is given here for reactions as diverse as the low‐temperature water‐gas shift,methanol steam reforming,selective ethanol dehydrogenation,and selective hydrogenation of alkynes and dienes.It is of fundamental interest to investigate the intrinsic activity and selectivity of the active metal atom site and compare them to the properties of the corresponding metal nanoparticles and sub‐nm clusters.It is also important to understand what constitutes a stable active metal atom site in the various reaction environments,and maximize their loadings to allow us to design robust catalysts for industrial applications.Combined activity and stability studies,ideally following the evolution of the active site as a function of catalyst treatment in real time are recommended.Advanced characterization methods with atomic resolution will play a key role here and will be used to guide the design of new catalysts.
基金supported by the National Natural Science Foundation of China (20973079 & 21003107)State Basic Research Project of China(2009CB623507)Fundamental Research Funds for the Central Universities (2010QNA3035)
文摘Porous polymer supported palladium catalyst for cross coupling reactions with high activity has been successfully prepared by coordination of Pd 2+ species with Schiff bases functionalized porous polymer. The catalyst has been systemically investi-gated by a series of characterizations such as TEM, N 2 adsorption, NMR, IR, XPS, etc. TEM and N 2 isotherms show that the sample maintains the nanoporous structure after the modification and coordination. XPS results show that chemical state of palladium species in the catalyst is mainly +2. More importantly, the catalyst shows very high activities and excellent recycla-bility in a series of coupling reactions including Suzuki, Sonogashira, and Heck reactions. Hot filtration and poison of catalysts experiments have also been performed and the results indicate that soluble active species (mainly Pd(0) species) in-situ gener-ated from the catalyst under the reaction conditions are the active intermediates, which would redeposit to the supporter after the reactions.
