The results confirmed that diazepam inhibits the cholinesterase in rat serum,red cell,corpus striatum and diaphragm in vitro,that the higher the diazepam concentration,the stronger the cholinesterase inhibition,and th...The results confirmed that diazepam inhibits the cholinesterase in rat serum,red cell,corpus striatum and diaphragm in vitro,that the higher the diazepam concentration,the stronger the cholinesterase inhibition,and that diazepam is a reversible inhibitor to acetylcholinesterase and diazepam has a stabilizing action on red cell membranes.The role of these effects of diazepam in the treatment of organic phosphate poisoning is discussed展开更多
The dry modification of aluminum hydroxide powders with phosphoric acid and the effects of modification of technological conditions on thermal stability, morphology and oil absorption of aluminum hydroxide powders wer...The dry modification of aluminum hydroxide powders with phosphoric acid and the effects of modification of technological conditions on thermal stability, morphology and oil absorption of aluminum hydroxide powders were investigated. The results show that the increase of mass ratio of phosphoric acid to aluminum hydroxide, the decrease of mass concentration of phosphoric acid and prolongation of mixing time are favorable to the improvement of thermal stability of aluminum hydroxide; when the mass ratio of phosphoric acid to aluminum hydroxide is 5:100, the mass concentration of phosphoric acid is 200 g/L and the mixing time is 10 min, the initial temperature of loss of crystal water in aluminum hydroxide rises from about 192.10 to 208.66 ℃, but the dry modification results in the appearance of agglomeration and macro-aggregate in the modified powders, and the oil absorption of modified powders becomes higher than that of original aluminum hydroxide.展开更多
A column experiment was conducted to investigate the effect of phosphogypsum(PG)on the salinealkalinity,and aggregate stability of bauxite residue.Results showed that:with increasing leaching time,the concentrations o...A column experiment was conducted to investigate the effect of phosphogypsum(PG)on the salinealkalinity,and aggregate stability of bauxite residue.Results showed that:with increasing leaching time,the concentrations of saline−alkali ions decreased while the SO_(4)^(2-)concentration increased in bauxite residue leachate;compared with CK(control group)treatment,pH,electric conductivity(EC),exchangeable sodium percentage(ESP),sodium absorption ratio(SAR),and exchangeable Na+content of bauxite residue were reduced following PG treatment;average particle sizes in aggregates following CK and PG treatments were determined to be 155 and 193 nm,respectively.SR-μCT test results also confirmed that bauxite residue following PG treatment acquired larger aggregates and larger pore diameter.These results indicate that the PG treatment could significantly modulate the saline-alkalinity,and simultaneously enhance aggregate stability of bauxite residue,which provides a facile approach to reclaim bauxite residue disposal areas.展开更多
In this study, phosphorus modification by trimethyl phosphate impregnation was employed to enhance the hydrothermal stability of nano‐sized HZSM‐5 zeolites. A parallel modification was studied by ammonium dihydrogen...In this study, phosphorus modification by trimethyl phosphate impregnation was employed to enhance the hydrothermal stability of nano‐sized HZSM‐5 zeolites. A parallel modification was studied by ammonium dihydrogen phosphate impregnation. The modified zeolites were subjected to steam treatment at 800 °C for 4 h (100% steam) and employed as catalysts for olefin catalyticcracking (OCC) of full‐range fluid catalytic cracking (FCC) gasoline. X‐ray diffraction, N2 physicaladsorption and NH3 temperature‐programmed desorption analysis indicated that, although significantimprovements to the hydrothermal stability of nano‐sized HZSM‐5 zeolites can be observedwhen adopting both phosphorus modification strategies, impregnation with trimethyl phosphatedisplays further enhancement of the hydrothermal stability. This is because higher structural crystallinityis retained, larger specific surface areas/micropore volumes form, and there are greaternumbers of surface acid sites. Reaction experiments conducted using a fixed‐bed micro‐reactor(catalyst/oil ratio = 4, time on stream = 4 s) showed OCC of full‐range FCC gasoline-under a fluidized‐bed reaction mode configuration-to be a viable solution for the olefin problem of FCC gasoline.This reaction significantly decreased the olefin content in the full‐range FCC gasoline feed, andspecifically heavy‐end olefins, by converting the olefins into value‐added C2–C4 olefins and aromatics.At the same time, sulfide content of the gasoline decreased via a non‐hydrodesulfurization process.Nano‐sized HZSM‐5 zeolites modified with trimethyl phosphate exhibited enhanced catalytic performance for OCC of full‐range FCC gasoline.展开更多
Hierarchically porous ZSM‐5 (SiO2/Al2O3 ≈ 120) containing phosphorus was prepared by a one‐step post‐synthesis treatment involving controlled desilication and phosphorous modification. The hierarchically porous ZS...Hierarchically porous ZSM‐5 (SiO2/Al2O3 ≈ 120) containing phosphorus was prepared by a one‐step post‐synthesis treatment involving controlled desilication and phosphorous modification. The hierarchically porous ZSM‐5 featured high thermal and hydrothermal stability. The obtained ZSM‐5zeolites were systematically characterized by X‐ray diffraction, scanning electron microscopy,transmission electron microscopy, N2 adsorption‐desorption, NH3 temperature‐programmed desorption,and 27Al and 31P magic‐angle spinning nuclear magnetic resonance spectroscopy. Theprepared ZSM‐5 displayed enhanced activity and prolonged lifetime toward hydrocarbon cracking.The high activity was attributed to improved coke tolerance owing to the presence of the highlystable mesoporous network of ZSM‐5 and acid sites introduced upon phosphorus modification.Additionally a mechanism of the stabilization of the zeolites by phosphorus was proposed and discussed.展开更多
Na-montruorillonite (Na-MMT) was exchanged with three quaternary atkylphosphonium salts: decyl tributylphosphonium bromide (DTBPBr), dodecyl tributylphosphonium bromide (DDTBPBr) and hexadecyl tributylphosphoni...Na-montruorillonite (Na-MMT) was exchanged with three quaternary atkylphosphonium salts: decyl tributylphosphonium bromide (DTBPBr), dodecyl tributylphosphonium bromide (DDTBPBr) and hexadecyl tributylphosphonium bromide (HDTBPBr), to investigate the effects of phosphonium salts species and relative molecular mass on the characteristics, morphology, thermal stability and long-acting antibacterial property of phosphonium montmorillonites. The resulting modified montmorillonites were characterized by the FTIR, XRD, TEM, and TG/DTG techniques. And minimum inhibitory concentration (MIC) was used to investigate antibacterial activity. The results show that the phosphonium salts are intercalated into Na-MMT, and the basal spacing of P-MMTs is enlarged with the increase of phosphonium salt content or the growth of alkyl chain length. DDTBP-MMT-3 with 19.83% (mass fraction of dodecyl tributylphosphonium salts, displays excellent thermal stability and long-acting antibacterial activity.展开更多
The influences ofphosphite and epoxy soybean oil in combination with liquid calcium/zinc isocaprylates on the thermal stability of flexible poly (vinyl chloride) were studied. The stabilizing effect of poly (vinyl ...The influences ofphosphite and epoxy soybean oil in combination with liquid calcium/zinc isocaprylates on the thermal stability of flexible poly (vinyl chloride) were studied. The stabilizing effect of poly (vinyl chloride) was evaluated by Congo red method, thermoaging test and Thermogravimetric-differential Scanning Calorimetry (TG-DSC). The results showed that the addition of the phosphite or epoxy soybean oil improved the thermal stability of PVC with the calcium/zinc isocaprylates stabilizing system, especially epoxidied soybean oil exhibited a remarkable effect, and the synergism on PVC thermal stability for 3:2 phenyl dioctyl phosphite to epoxidized soybean oil weight ratio was acquired. Accordingly, the rapid mass loss in TG curve occured between 258.9 ℃ and 334.4 ℃, which corresponded to the enthalpy of the pyrogenation of 609.2 J/g. It was also found that the stabilized PVC of the best ratio gave better mechanical and processing properties.展开更多
Safety is important to lithium ion battery materials. The thermal stability of LiFePOa/C-LiMn204 blended cathode materials is characterized by using TG, XRD, and SEM etc. The results show that LiFePO4/C-LiMn2O4 posses...Safety is important to lithium ion battery materials. The thermal stability of LiFePOa/C-LiMn204 blended cathode materials is characterized by using TG, XRD, and SEM etc. The results show that LiFePO4/C-LiMn2O4 possesses a worse thermal stability than pure spinel LiMn2O4 and pure olivine LiFePO4/C. When LiFePO4/C-LiMn2O4 blended cathode materials are sintered at 500℃ under Ar atmosphere, the sintered cathode materials emit O2, and appear impurity phases (Li3PO4, Fe2O3, Mn3O4). It is deduced that some chemical reactions take place between different materials, which leads to a worse discharge specific capacity. LiFePO4/C-LiMn2O4 blended cathode materials, therefore, need to be managed and controlled strictly for the sake of ther- mal stability and safety.展开更多
We demonstrate that it is possible to form non-phospholipid fluid bilayers in aqueous milieu with a mixture of palmitic acid (PA),cholesterol (Chol),and cholesterol sulfate (Schol) in a molar proportion of 30/28/42.Th...We demonstrate that it is possible to form non-phospholipid fluid bilayers in aqueous milieu with a mixture of palmitic acid (PA),cholesterol (Chol),and cholesterol sulfate (Schol) in a molar proportion of 30/28/42.These self-assemblies are shown to be bilayers in the liquid ordered phase.They are stable between pH 5 and 9.Over this pH range,the protonation/deprotonation of PA carboxylic group is observed but this change does not appear to alter the stability of these bilayers,a behavior contrasting with that observed for binary mixtures of PA/Chol,and PA/Schol.The multilamellar dispersions formed spontaneously from the PA/Chol/Schol mixture could be successfully extruded to form Large Unilamellar Vesicles (LUVs).These LUVs show interesting permeability properties,linked with their high sterol content.These non-phospholipid liposomes can sustain a pH gradient (pH internal 8/pH external 6) 100 times longer than LUVs made of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and cholesterol,with a molar ratio of 60/40.Moreover,the non-phospholipid LUVs are shown to protect ascorbic acid from an oxidizing environment (1 mM iron(III)).Once entrapped in liposomes,ascorbic acid displays a degradation rate similar to that obtained in the absence of iron(III).These results show the possibility to form novel nanocontainers from a mixture of a monoalkylated amphiphile and sterols,with a good pH stability and showing interesting permeability properties.展开更多
The present study reports a highly selective and stable catalytic approach for producing tetralin, an important chemical, solvent, and H2 storage material. Transition metal phosphides (MOP, Ni2P, Co2P, and Fe2P) wer...The present study reports a highly selective and stable catalytic approach for producing tetralin, an important chemical, solvent, and H2 storage material. Transition metal phosphides (MOP, Ni2P, Co2P, and Fe2P) were prepared by wet impregnation and temperature-programmed reduction and characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), EDX mapping, scanning electron microscopy (SEM), transmission electron microscopy (TEM), brunauer-emmett- teller (BET), temperature-programmed desorption of ammonia (NH3-TPD), and fourier transform infrared spectroscopy of pyridine (pyridine-FTIR). Of all the transition metal phosphides MoP was formed at a lower reduction temperature, which resuited in smaller particle size that enhanced the overall surface area of the catalyst. The existence of weak, moderate, and Lewis acidic sites over MoP were responsible for its high tetralin selectivity (90%) and stability during the 100 h reaction on-stream in a fixed-bed reactor.展开更多
Separation of trivalent lanthanides (Ln(Ⅲ)) and actinides (An(Ⅲ)) is a key issue in the advanced spent nuclear fuel repro- cessing. In the well-known trivalent actinide lanthanide separation by phosphorus re...Separation of trivalent lanthanides (Ln(Ⅲ)) and actinides (An(Ⅲ)) is a key issue in the advanced spent nuclear fuel repro- cessing. In the well-known trivalent actinide lanthanide separation by phosphorus reagent extraction from aqueous komplexes (TALSPEAK) process, the organophosphorus ligand HDEHP (di-(2-ethylhexyl) phosphoric acid) has been used as an efficient reagent for the partitioning of Ln(Ⅲ) from An(Ⅲ) with the combination of a holdback reagent in aqueous lactate buffer solu- tion. In this work, the structural and electronic properties of Eu3+ and Am3+ complexes with HDEHP in nitric acid solution have been systematically explored by using scalar-relativistic density functional theory (DFT). It was found that HDEHP can coordinate with M(Ⅲ) (M=Eu, Am) cations in the form of hydrogen-bonded dimers HL2 (L=DEHP), and the metal ions pre- fer to coordinate with the phosphoryl oxygen atom of the ligand. For all the extraction complexes, the metal-ligand bonds are mainly ionic in nature. Although Eu(Ⅲ) complexes have higher interaction energies, the HL2- dimer shows comparable affini- ty for Eu(Ⅲ) and Am(Ⅲ) according to thermodynamic analysis, nonahydrate. It is expected that this work could provide insightful HDEHP at the molecular level. which may be attributed to the higher stabilities of Eu(Ⅲ) information on the complexation of An(Ⅲ) and Ln(Ⅲ) with展开更多
N-heterocyclic carbene (NHC) is both a family of strong o-donor ligands for transition metals and a privileged class of organocatalysts with synthetic potential that rivals popu- lar amine and phosphoric acid cataly...N-heterocyclic carbene (NHC) is both a family of strong o-donor ligands for transition metals and a privileged class of organocatalysts with synthetic potential that rivals popu- lar amine and phosphoric acid catalysts. NHC was found as a key catalytic species in thiamine diphosphate catalyzed biochemical reactions [1]. However, due to their inherent chemical instability, free NHCs had not been isolated until 1991 by Ardungo et al. [2]. Since then, the use of chiral NHC as a versatile organocatalyst has enjoyed tremendous advances and has helped to transform modem synthetic chemistry. There are over 2000 research papers dealing with both "N-heterocyclic carbene" and "Catalysis" in the past 15 years [3].展开更多
文摘The results confirmed that diazepam inhibits the cholinesterase in rat serum,red cell,corpus striatum and diaphragm in vitro,that the higher the diazepam concentration,the stronger the cholinesterase inhibition,and that diazepam is a reversible inhibitor to acetylcholinesterase and diazepam has a stabilizing action on red cell membranes.The role of these effects of diazepam in the treatment of organic phosphate poisoning is discussed
基金Project(06SK2011) supported by the Science and Technology Program of Hunan Province, China
文摘The dry modification of aluminum hydroxide powders with phosphoric acid and the effects of modification of technological conditions on thermal stability, morphology and oil absorption of aluminum hydroxide powders were investigated. The results show that the increase of mass ratio of phosphoric acid to aluminum hydroxide, the decrease of mass concentration of phosphoric acid and prolongation of mixing time are favorable to the improvement of thermal stability of aluminum hydroxide; when the mass ratio of phosphoric acid to aluminum hydroxide is 5:100, the mass concentration of phosphoric acid is 200 g/L and the mixing time is 10 min, the initial temperature of loss of crystal water in aluminum hydroxide rises from about 192.10 to 208.66 ℃, but the dry modification results in the appearance of agglomeration and macro-aggregate in the modified powders, and the oil absorption of modified powders becomes higher than that of original aluminum hydroxide.
基金the financial supports from the National Natural Science Foundation of China(Nos.42030711,41877511).
文摘A column experiment was conducted to investigate the effect of phosphogypsum(PG)on the salinealkalinity,and aggregate stability of bauxite residue.Results showed that:with increasing leaching time,the concentrations of saline−alkali ions decreased while the SO_(4)^(2-)concentration increased in bauxite residue leachate;compared with CK(control group)treatment,pH,electric conductivity(EC),exchangeable sodium percentage(ESP),sodium absorption ratio(SAR),and exchangeable Na+content of bauxite residue were reduced following PG treatment;average particle sizes in aggregates following CK and PG treatments were determined to be 155 and 193 nm,respectively.SR-μCT test results also confirmed that bauxite residue following PG treatment acquired larger aggregates and larger pore diameter.These results indicate that the PG treatment could significantly modulate the saline-alkalinity,and simultaneously enhance aggregate stability of bauxite residue,which provides a facile approach to reclaim bauxite residue disposal areas.
基金supported by the National Natural Science Foundation of China (21603023)the Petro China Innovation Foundation, China (2014D-5006-0501)~~
文摘In this study, phosphorus modification by trimethyl phosphate impregnation was employed to enhance the hydrothermal stability of nano‐sized HZSM‐5 zeolites. A parallel modification was studied by ammonium dihydrogen phosphate impregnation. The modified zeolites were subjected to steam treatment at 800 °C for 4 h (100% steam) and employed as catalysts for olefin catalyticcracking (OCC) of full‐range fluid catalytic cracking (FCC) gasoline. X‐ray diffraction, N2 physicaladsorption and NH3 temperature‐programmed desorption analysis indicated that, although significantimprovements to the hydrothermal stability of nano‐sized HZSM‐5 zeolites can be observedwhen adopting both phosphorus modification strategies, impregnation with trimethyl phosphatedisplays further enhancement of the hydrothermal stability. This is because higher structural crystallinityis retained, larger specific surface areas/micropore volumes form, and there are greaternumbers of surface acid sites. Reaction experiments conducted using a fixed‐bed micro‐reactor(catalyst/oil ratio = 4, time on stream = 4 s) showed OCC of full‐range FCC gasoline-under a fluidized‐bed reaction mode configuration-to be a viable solution for the olefin problem of FCC gasoline.This reaction significantly decreased the olefin content in the full‐range FCC gasoline feed, andspecifically heavy‐end olefins, by converting the olefins into value‐added C2–C4 olefins and aromatics.At the same time, sulfide content of the gasoline decreased via a non‐hydrodesulfurization process.Nano‐sized HZSM‐5 zeolites modified with trimethyl phosphate exhibited enhanced catalytic performance for OCC of full‐range FCC gasoline.
基金supported by the National Natural Science Foundation of China (21403070, 21573073)National Key Technology Research and De-velopment Program (2012BAE05B02)Shanghai Leading Academic Discipline Project (B409)~~
文摘Hierarchically porous ZSM‐5 (SiO2/Al2O3 ≈ 120) containing phosphorus was prepared by a one‐step post‐synthesis treatment involving controlled desilication and phosphorous modification. The hierarchically porous ZSM‐5 featured high thermal and hydrothermal stability. The obtained ZSM‐5zeolites were systematically characterized by X‐ray diffraction, scanning electron microscopy,transmission electron microscopy, N2 adsorption‐desorption, NH3 temperature‐programmed desorption,and 27Al and 31P magic‐angle spinning nuclear magnetic resonance spectroscopy. Theprepared ZSM‐5 displayed enhanced activity and prolonged lifetime toward hydrocarbon cracking.The high activity was attributed to improved coke tolerance owing to the presence of the highlystable mesoporous network of ZSM‐5 and acid sites introduced upon phosphorus modification.Additionally a mechanism of the stabilization of the zeolites by phosphorus was proposed and discussed.
基金Projects(20676049, 20871058) supported by the National Natural Science Foundation of China Project(05200555) supported by the Natural Science Foundation of Guangdong Province, China Projects(2007B090400105, 2008A010500005) supported by the Foundation of Enterprise-University-Research Institute Cooperation from Guangdong Province and Ministry of Education of China
文摘Na-montruorillonite (Na-MMT) was exchanged with three quaternary atkylphosphonium salts: decyl tributylphosphonium bromide (DTBPBr), dodecyl tributylphosphonium bromide (DDTBPBr) and hexadecyl tributylphosphonium bromide (HDTBPBr), to investigate the effects of phosphonium salts species and relative molecular mass on the characteristics, morphology, thermal stability and long-acting antibacterial property of phosphonium montmorillonites. The resulting modified montmorillonites were characterized by the FTIR, XRD, TEM, and TG/DTG techniques. And minimum inhibitory concentration (MIC) was used to investigate antibacterial activity. The results show that the phosphonium salts are intercalated into Na-MMT, and the basal spacing of P-MMTs is enlarged with the increase of phosphonium salt content or the growth of alkyl chain length. DDTBP-MMT-3 with 19.83% (mass fraction of dodecyl tributylphosphonium salts, displays excellent thermal stability and long-acting antibacterial activity.
文摘The influences ofphosphite and epoxy soybean oil in combination with liquid calcium/zinc isocaprylates on the thermal stability of flexible poly (vinyl chloride) were studied. The stabilizing effect of poly (vinyl chloride) was evaluated by Congo red method, thermoaging test and Thermogravimetric-differential Scanning Calorimetry (TG-DSC). The results showed that the addition of the phosphite or epoxy soybean oil improved the thermal stability of PVC with the calcium/zinc isocaprylates stabilizing system, especially epoxidied soybean oil exhibited a remarkable effect, and the synergism on PVC thermal stability for 3:2 phenyl dioctyl phosphite to epoxidized soybean oil weight ratio was acquired. Accordingly, the rapid mass loss in TG curve occured between 258.9 ℃ and 334.4 ℃, which corresponded to the enthalpy of the pyrogenation of 609.2 J/g. It was also found that the stabilized PVC of the best ratio gave better mechanical and processing properties.
基金supported by National Natural Science Foundation of China(Grant No.51364021)Natural Science Foundation of Yunnan Province(Grant No.2014FA025)+1 种基金Innovative Research Team in University of Ministry of Education of China(Grant No.IRT1250)Academician free exploration project of Yunnan Province(Grant No.14051600)
文摘Safety is important to lithium ion battery materials. The thermal stability of LiFePOa/C-LiMn204 blended cathode materials is characterized by using TG, XRD, and SEM etc. The results show that LiFePO4/C-LiMn2O4 possesses a worse thermal stability than pure spinel LiMn2O4 and pure olivine LiFePO4/C. When LiFePO4/C-LiMn2O4 blended cathode materials are sintered at 500℃ under Ar atmosphere, the sintered cathode materials emit O2, and appear impurity phases (Li3PO4, Fe2O3, Mn3O4). It is deduced that some chemical reactions take place between different materials, which leads to a worse discharge specific capacity. LiFePO4/C-LiMn2O4 blended cathode materials, therefore, need to be managed and controlled strictly for the sake of ther- mal stability and safety.
基金financially supported by the Natural Sciences and Engineering Research Council of Canadaby the Fonds Québécois de la Recherche sur la Nature et les Technologies through its Strategic Clusterprogram
文摘We demonstrate that it is possible to form non-phospholipid fluid bilayers in aqueous milieu with a mixture of palmitic acid (PA),cholesterol (Chol),and cholesterol sulfate (Schol) in a molar proportion of 30/28/42.These self-assemblies are shown to be bilayers in the liquid ordered phase.They are stable between pH 5 and 9.Over this pH range,the protonation/deprotonation of PA carboxylic group is observed but this change does not appear to alter the stability of these bilayers,a behavior contrasting with that observed for binary mixtures of PA/Chol,and PA/Schol.The multilamellar dispersions formed spontaneously from the PA/Chol/Schol mixture could be successfully extruded to form Large Unilamellar Vesicles (LUVs).These LUVs show interesting permeability properties,linked with their high sterol content.These non-phospholipid liposomes can sustain a pH gradient (pH internal 8/pH external 6) 100 times longer than LUVs made of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and cholesterol,with a molar ratio of 60/40.Moreover,the non-phospholipid LUVs are shown to protect ascorbic acid from an oxidizing environment (1 mM iron(III)).Once entrapped in liposomes,ascorbic acid displays a degradation rate similar to that obtained in the absence of iron(III).These results show the possibility to form novel nanocontainers from a mixture of a monoalkylated amphiphile and sterols,with a good pH stability and showing interesting permeability properties.
基金financial support from the Special Funds of the National Natural Science Foundation of China(21127011)National High Technology Research and Development Program of China(2011AA050606)National Natural Science Foundation of China(Petrochemical Joint Fund,U1162106)
文摘The present study reports a highly selective and stable catalytic approach for producing tetralin, an important chemical, solvent, and H2 storage material. Transition metal phosphides (MOP, Ni2P, Co2P, and Fe2P) were prepared by wet impregnation and temperature-programmed reduction and characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), EDX mapping, scanning electron microscopy (SEM), transmission electron microscopy (TEM), brunauer-emmett- teller (BET), temperature-programmed desorption of ammonia (NH3-TPD), and fourier transform infrared spectroscopy of pyridine (pyridine-FTIR). Of all the transition metal phosphides MoP was formed at a lower reduction temperature, which resuited in smaller particle size that enhanced the overall surface area of the catalyst. The existence of weak, moderate, and Lewis acidic sites over MoP were responsible for its high tetralin selectivity (90%) and stability during the 100 h reaction on-stream in a fixed-bed reactor.
基金the National Natural Science Foundation of China (21201166, 11275090)the Major Research Plan of Natural Science Foundation of China (91426302, 91326202)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences (XDA030104)the Natural Science Foundation of Hunan Province (12JJ9006)the Scientific Research Fund of Hunan Provincial Education Department (12A116)
文摘Separation of trivalent lanthanides (Ln(Ⅲ)) and actinides (An(Ⅲ)) is a key issue in the advanced spent nuclear fuel repro- cessing. In the well-known trivalent actinide lanthanide separation by phosphorus reagent extraction from aqueous komplexes (TALSPEAK) process, the organophosphorus ligand HDEHP (di-(2-ethylhexyl) phosphoric acid) has been used as an efficient reagent for the partitioning of Ln(Ⅲ) from An(Ⅲ) with the combination of a holdback reagent in aqueous lactate buffer solu- tion. In this work, the structural and electronic properties of Eu3+ and Am3+ complexes with HDEHP in nitric acid solution have been systematically explored by using scalar-relativistic density functional theory (DFT). It was found that HDEHP can coordinate with M(Ⅲ) (M=Eu, Am) cations in the form of hydrogen-bonded dimers HL2 (L=DEHP), and the metal ions pre- fer to coordinate with the phosphoryl oxygen atom of the ligand. For all the extraction complexes, the metal-ligand bonds are mainly ionic in nature. Although Eu(Ⅲ) complexes have higher interaction energies, the HL2- dimer shows comparable affini- ty for Eu(Ⅲ) and Am(Ⅲ) according to thermodynamic analysis, nonahydrate. It is expected that this work could provide insightful HDEHP at the molecular level. which may be attributed to the higher stabilities of Eu(Ⅲ) information on the complexation of An(Ⅲ) and Ln(Ⅲ) with
基金the National Natural Science Foundation of China (21372013, 21572004)the Shenzhen Peacock Program (KQTD201103)
文摘N-heterocyclic carbene (NHC) is both a family of strong o-donor ligands for transition metals and a privileged class of organocatalysts with synthetic potential that rivals popu- lar amine and phosphoric acid catalysts. NHC was found as a key catalytic species in thiamine diphosphate catalyzed biochemical reactions [1]. However, due to their inherent chemical instability, free NHCs had not been isolated until 1991 by Ardungo et al. [2]. Since then, the use of chiral NHC as a versatile organocatalyst has enjoyed tremendous advances and has helped to transform modem synthetic chemistry. There are over 2000 research papers dealing with both "N-heterocyclic carbene" and "Catalysis" in the past 15 years [3].