A novel type of metal oxide/activated carbon catalyst was prepared by sol-gel method for the hydrolysis of carbonyl sulfide(COS) .The influences of the calcination temperature,additive content(2.5%-10.0%Fe2O3,mass fra...A novel type of metal oxide/activated carbon catalyst was prepared by sol-gel method for the hydrolysis of carbonyl sulfide(COS) .The influences of the calcination temperature,additive content(2.5%-10.0%Fe2O3,mass fraction) and the basic density of the activation process were thoroughly investigated.The surface of catalysts was characterized by Boehm titration.The products were characterized by scanning electron microscopy(SEM) ,X-ray diffractometry(XRD) and X-ray photoelectron spectroscopy(XPS) .The results show that catalysts with 2.5%-5.0%Fe2O3 after calcining at 500℃have superior activity.The conversion rate of COS increases with increasing the relative density of basic capacity loaded onto activated carbon(AC) ,and the activity follows the order:KOH>Na2CO3>NaHCO3.Boehm titration data clearly show that the total acidity increases(from 0.06 to 0.48 mmol/g) and the basic groups decrease(from 0.78 to 0.56 mmol/g) after COS hydrolysis and H2S adsorption.The XPS results show that the product of H2S may be absorbed by the interaction with metal compounds and O2 to form sulfate(171.28 eV) and element sulfur(164.44 eV) ,which lead to catalysts poisoning.展开更多
Thermal treatment of the pyridyl side chain functionalized tetramethyl cyclopen- tadiene C5Me4CH2（C5H4N） with Fe（CO）5, Ru3（CO）12 and Mo（CO）6 in refluxing xylene respectively gave the corresponding dinuclear me...Thermal treatment of the pyridyl side chain functionalized tetramethyl cyclopen- tadiene C5Me4CH2（C5H4N） with Fe（CO）5, Ru3（CO）12 and Mo（CO）6 in refluxing xylene respectively gave the corresponding dinuclear metal carbonyl complexes 1～3. These complexes have been characterized by elemental analysis, IR and IH NMR spectra. The molecular structures of 1～3 were determined by X-ray diffraction analysis.展开更多
Diethyl malonate was synthesized by transition-metal catalyzed alkoxycarbonylation of ethyl chloroacetate. The results show that the conversion of ethyl chloroacetate is greater than 92%, and the selectivity to diethy...Diethyl malonate was synthesized by transition-metal catalyzed alkoxycarbonylation of ethyl chloroacetate. The results show that the conversion of ethyl chloroacetate is greater than 92%, and the selectivity to diethyl malonate is 67.5%.展开更多
Spectroscopic characterization of CO activation on multiple metal-containing catalysts remains an important and challenging goal for identifying the structure and nature of active site in many industrial processes suc...Spectroscopic characterization of CO activation on multiple metal-containing catalysts remains an important and challenging goal for identifying the structure and nature of active site in many industrial processes such as Fischer-Tropsch chemistry and alcohol synthesis.Here,we use mass-selected photoelectron velocity-map imaging spectroscopy and quantum chemical calculations to study the reactions of CO molecules with several heterobinuclear transition metal-iron clusters M-Fe(M=Ti,V,Cr).The mass spectra reveal the favorable formation of MFe(CO)_(4)^(-)with relatively high thermodynamic stability.The MFe(CO)_(4)^(-)(M=Ti,V,Cr) complexes are established to have a metal-Fe bonded M-Fe(CO)_(4) structure with C_(3 v) geometry.While the positive charge and unpaired electrons are mainly located on the M atom,the natural charge of Fe(CO)_(4) is about-2 e.The MFe(CO)_(4)^(-)(M=Ti,V,Cr) can be seen as being formed via the interactions between the M^(+)fragment and the [Fe(CO)_(4)]^(2-)core,which satisfies the 18-electron rule.The CO molecules are remarkably activated in these MFe(CO)_(4)^(-).These results shed insight into the structure-reactivity relationship of heterobinuclear transition metal carbonyls and would have important implications for understanding of CO activation on alloy surfaces.展开更多
To develop a luminescent material with high color purity, luminous efficiency, and stability, we synthesized diketone by carbonylative Suzuki coupling in the presence of Pd(NHC) complex as the catalyst. Carbonylative ...To develop a luminescent material with high color purity, luminous efficiency, and stability, we synthesized diketone by carbonylative Suzuki coupling in the presence of Pd(NHC) complex as the catalyst. Carbonylative coupling of 4,4’-diiodobiphenyl and phenylboronic acid was investigated to study in detail the catalytic ability of the Pd(NHC) complex. Reactions were carried out using both CO and metal carbonyls. Bis-(1,3-dihydro-1,3-dimethyl-2H-imidazol- 2-ylidene) diiodo palladium was used as the catalytic complex. Reaction products biphenyl-4,4’-diylbis (phenyl- methanone) 3 and (4’-iodobiphenyl-4-yl)(phenyl) methanone 4 were obtained as a result of CO insertion into the palladium(II)-aryl bond. However, when pyridine-4-yl boronic acid was used in place of phenylboronic acid as the starting reagent, synthetic reaction yielding 3 and 4 were found not to occur.展开更多
基金Project(50908110) supported by the National Natural Science Foundation of ChinaProject(2008AA062602) supported by the National High-Tech Research and Development Program of China+1 种基金Project(20090451431) supported by China Postdoctoral Science FoundationProject(2007PY01-10) supported by Young and Middle-aged Academic and Technical Back-up Personnel Program of Yunnan Province,China
文摘A novel type of metal oxide/activated carbon catalyst was prepared by sol-gel method for the hydrolysis of carbonyl sulfide(COS) .The influences of the calcination temperature,additive content(2.5%-10.0%Fe2O3,mass fraction) and the basic density of the activation process were thoroughly investigated.The surface of catalysts was characterized by Boehm titration.The products were characterized by scanning electron microscopy(SEM) ,X-ray diffractometry(XRD) and X-ray photoelectron spectroscopy(XPS) .The results show that catalysts with 2.5%-5.0%Fe2O3 after calcining at 500℃have superior activity.The conversion rate of COS increases with increasing the relative density of basic capacity loaded onto activated carbon(AC) ,and the activity follows the order:KOH>Na2CO3>NaHCO3.Boehm titration data clearly show that the total acidity increases(from 0.06 to 0.48 mmol/g) and the basic groups decrease(from 0.78 to 0.56 mmol/g) after COS hydrolysis and H2S adsorption.The XPS results show that the product of H2S may be absorbed by the interaction with metal compounds and O2 to form sulfate(171.28 eV) and element sulfur(164.44 eV) ,which lead to catalysts poisoning.
基金financially supported by the National Natural Science Foundation of China(No.21372061)Natural Science Foundation of Hebei Province(Nos.B2013205025 and B2014205018)the Key Research Fund of Hebei Normal University(No.L2012Z02)
文摘Thermal treatment of the pyridyl side chain functionalized tetramethyl cyclopen- tadiene C5Me4CH2（C5H4N） with Fe（CO）5, Ru3（CO）12 and Mo（CO）6 in refluxing xylene respectively gave the corresponding dinuclear metal carbonyl complexes 1～3. These complexes have been characterized by elemental analysis, IR and IH NMR spectra. The molecular structures of 1～3 were determined by X-ray diffraction analysis.
文摘Diethyl malonate was synthesized by transition-metal catalyzed alkoxycarbonylation of ethyl chloroacetate. The results show that the conversion of ethyl chloroacetate is greater than 92%, and the selectivity to diethyl malonate is 67.5%.
基金supported by the National Natural Science Foundation of China (21688102, 21873097, and 92061203)the Youth Innovation Promotion Association of the Chinese Academy of Sciences (CAS)(2020187)+3 种基金the Strategic Priority Research Program of CAS (XDB17000000)CAS (GJJSTD20190002)the International Partnership Program of CAS (121421KYSB20170012)the K.C.Wong Education Foundation (GJTD-2018-06)。
文摘Spectroscopic characterization of CO activation on multiple metal-containing catalysts remains an important and challenging goal for identifying the structure and nature of active site in many industrial processes such as Fischer-Tropsch chemistry and alcohol synthesis.Here,we use mass-selected photoelectron velocity-map imaging spectroscopy and quantum chemical calculations to study the reactions of CO molecules with several heterobinuclear transition metal-iron clusters M-Fe(M=Ti,V,Cr).The mass spectra reveal the favorable formation of MFe(CO)_(4)^(-)with relatively high thermodynamic stability.The MFe(CO)_(4)^(-)(M=Ti,V,Cr) complexes are established to have a metal-Fe bonded M-Fe(CO)_(4) structure with C_(3 v) geometry.While the positive charge and unpaired electrons are mainly located on the M atom,the natural charge of Fe(CO)_(4) is about-2 e.The MFe(CO)_(4)^(-)(M=Ti,V,Cr) can be seen as being formed via the interactions between the M^(+)fragment and the [Fe(CO)_(4)]^(2-)core,which satisfies the 18-electron rule.The CO molecules are remarkably activated in these MFe(CO)_(4)^(-).These results shed insight into the structure-reactivity relationship of heterobinuclear transition metal carbonyls and would have important implications for understanding of CO activation on alloy surfaces.
文摘To develop a luminescent material with high color purity, luminous efficiency, and stability, we synthesized diketone by carbonylative Suzuki coupling in the presence of Pd(NHC) complex as the catalyst. Carbonylative coupling of 4,4’-diiodobiphenyl and phenylboronic acid was investigated to study in detail the catalytic ability of the Pd(NHC) complex. Reactions were carried out using both CO and metal carbonyls. Bis-(1,3-dihydro-1,3-dimethyl-2H-imidazol- 2-ylidene) diiodo palladium was used as the catalytic complex. Reaction products biphenyl-4,4’-diylbis (phenyl- methanone) 3 and (4’-iodobiphenyl-4-yl)(phenyl) methanone 4 were obtained as a result of CO insertion into the palladium(II)-aryl bond. However, when pyridine-4-yl boronic acid was used in place of phenylboronic acid as the starting reagent, synthetic reaction yielding 3 and 4 were found not to occur.
