Experiments performed on the grwth of mixed crystals of rare earth tartrates (Y1-xSmx)2 (C4H4O6)3.zH2O (0≤x≤1) from silica gels at 35~40℃ and 25~30℃ employing single-diffusion technique. are discussed. The crysta...Experiments performed on the grwth of mixed crystals of rare earth tartrates (Y1-xSmx)2 (C4H4O6)3.zH2O (0≤x≤1) from silica gels at 35~40℃ and 25~30℃ employing single-diffusion technique. are discussed. The crystals maintain spherulitic morphology, irrespective of the value of x, concentration of upper and lower reactants, gel pH, gel age and gel temperature. Formation Of Liesegang rings in this system is a temperature dependent phenomenon. It is shown that with the increase of the value of x the system passes from Liesegangring phenomenon to singlezone phenomenon. Operative mechanism of crystallization in the higher (35~40℃) and lower temperature ranges (25~30℃) is explained. Seeded growth experiments indicate the possibility of increasing the size of the spherulites in the gel medium展开更多
Macroscopic SiO2 spheres with a homogeneous amine distribution were synthesized by a one-step emulsion based synthesis approach in a flow column reactor. The CO2 adsorption capacity of the nanostructured amine-functio...Macroscopic SiO2 spheres with a homogeneous amine distribution were synthesized by a one-step emulsion based synthesis approach in a flow column reactor. The CO2 adsorption capacity of the nanostructured amine-functionalized silica spheres was studied in absence and presence of H2O. The structural properties were adjusted by varying solvents and surfactants during the synthesis and, at constant amine loadings, were found to be the main factor for influencing the CO2 sorption capacities. Under water-free conditions CO2 is bound to the amino groups via the formation of carbamates, which require two neighboring amino groups to adsorb one CO2 molecule. At constant amine concentrations sorbents with lower surface area allow to establish a higher amine density on the surface, which enhances the CO2 uptake capacities under dry conditions. In presence of H2O the CO2 adsorption changes to 1：1 stoichiometry due to stabilization of carbamates by protonation of H2O and formation of further species such as bicarbonates, which should in principle double the adsorption capacities. Low concentrations of physisorbed H2O（0.3 mmol/g） did not impair the adsorption capacity of the adsorbents for CO2, while at higher water uptakes（0.6 and 1.1 mmol/g） the CO2 uptake is reduced, which could be attributed to capillary condensation of H2O or formation of bulky reaction products blocking inner pores and access to active sites.展开更多
The toluene oxidative bromination reaction catalyzed by hollow titanium silicalite(HTS)zeolite in aqueous medium was investigated by employing H2O2 and HBr under mild conditions without the need for organic solvent.A ...The toluene oxidative bromination reaction catalyzed by hollow titanium silicalite(HTS)zeolite in aqueous medium was investigated by employing H2O2 and HBr under mild conditions without the need for organic solvent.A high toluene conversion(90.7%)and high selectivity of mono-bromotoluene(99.0%)was achieved under the optimal reaction conditions.The UV-Raman spectroscopy was applied for the mechanism study and the result reveals that HTS is efficient for catalyzing the oxidation reaction of HBr with H2O2 to produce abundant active bromine species,which can further facilitate the toluene electrophilic bromination reaction.A two-step toluene bromination reaction mechanism involving the HTS catalyzed active bromine species“generation-conversion-utilization”process is proposed based on the UV-Raman spectroscopy analysis.展开更多
Rice husk ash was used as a new, green, and cheap adsorbent for FeCl3. Characterization of the obtained reagent showed that rice husk ash supported FeCl2·2H2O was formed. This reagent is efficient at catalyzing t...Rice husk ash was used as a new, green, and cheap adsorbent for FeCl3. Characterization of the obtained reagent showed that rice husk ash supported FeCl2·2H2O was formed. This reagent is efficient at catalyzing the synthesis of multisubstituted quinolines by the Friedl鋘der heteroannulation of o‐aminoaryl ketones with ketones or β‐diketones under mild reaction conditions. This methodology allows for the synthesis of a broad range of substituted quinolines in high yields and with excellent regioselectivity in the absence of a solvent.展开更多
The synthesis and the structural characterization of the title compound HNa[WO（CCH）-（OCCH）（HO）][HWO]·13.5 HO are described.It is known that the mixed oxo-ethylidyne-capped tritungsten cluster can be obtaine...The synthesis and the structural characterization of the title compound HNa[WO（CCH）-（OCCH）（HO）][HWO]·13.5 HO are described.It is known that the mixed oxo-ethylidyne-capped tritungsten cluster can be obtained by Zn dust reduction of NaWO·2HO in acetic anhydride.The title compound has been characterized by X-ray diffraction,UV/VIS andH NMR spectra.The tungsten atoms in the cluster cation and anion are in the oxidation states of W（IV）and W（VI）respectively.The crystal is rhombohedral with the space group R32,a=17.058（3）,c=49.665（9）,γ=120°,V=12516（9）,Z=6,final R=0.037 for 2071 reflections with I≥3σ（I）.Boththe cluster cation and anion have a Csymmetry.The important interatomic distances in angstroms forthe cluster cation are:W—W,2.730（2）;W—μ-O,2.00;W—O（carboxyl）,2.12;W—O,2.18（2）.展开更多
A facile synthesis of benzo[h]quinolines has been developed via improved Combes reaction. A combination of silica gel, p-toluenesulfonic acid and phosphorus pentoxide was utilized to promote the condensation of 1-naph...A facile synthesis of benzo[h]quinolines has been developed via improved Combes reaction. A combination of silica gel, p-toluenesulfonic acid and phosphorus pentoxide was utilized to promote the condensation of 1-naphthylamines with 1,3-diketones under solvent free conditions. In this case, silica gel was used as reaction media, p-toluenesulfonic acid and phosphorus pentoxide were acted as catalyst and dehydrating agent, respectively.展开更多
Perfluorosulfonic acid/Polysulfone(PFSA/PSf) hollow fiber composite membranes have been prepared by dip-coating method using PSf ultrafiltration(UF) membrane as substrate with recovered PFSA.The composite membranes we...Perfluorosulfonic acid/Polysulfone(PFSA/PSf) hollow fiber composite membranes have been prepared by dip-coating method using PSf ultrafiltration(UF) membrane as substrate with recovered PFSA.The composite membranes were applied to the pervaporation separation of 95% ethanol(EtOH)/H2O mixture.SEM images show that the thickness of the PFSA skin layer of the composite membranes is about 2 μm,much thinner than those of other PFSA composite membranes revealed in the literatures.Effects of annealing temperature,coating solution concentration and counter-ions of PFSA on the pervaporation performances of the composite membranes were investigated.The total flux decreases and separation factor increases with the increase of annealing temperature.The highest permeation flux of 3230 g m-2 h-1 and a separation factor of 5.4 is obtained for the composite membrane annealed at 80°C.The lowest permeation flux of 396 g m-2 h-1 and a separation factor of 27.7 is obtained for the composite membrane annealed at 160°C.The permeation performances of the PFSA/PSf composite membrane are evidently influenced by the counter-ions of PFSA.The flux sequence of the PFSA/PSf composite membranes with different counter-ions is H+>Li+>Ca2+>Mg2+>Na+>K+>Ba2+>Fe3+>Al3+,and the separation factor sequence is H+<Li+<Al3+<Na+<Mg2+<Ca2+<K+ <Ba2+<Fe3+.The apparent activation energy △Eapp values of the composite membranes with different counter-ions were calculated by Arrhenius law.The sequence of △Eapp values for the membranes with monovalent counter-ions is Li+>Na+>K+.There are very little variations of △Eapp values between the composite membranes with three divalent counterions(Mg2+,Ca2+ and Ba2+),and the △Eapp values of the composite membranes with two trivalent counterions(Fe3+ and Al3+) are relatively high.展开更多
文摘Experiments performed on the grwth of mixed crystals of rare earth tartrates (Y1-xSmx)2 (C4H4O6)3.zH2O (0≤x≤1) from silica gels at 35~40℃ and 25~30℃ employing single-diffusion technique. are discussed. The crystals maintain spherulitic morphology, irrespective of the value of x, concentration of upper and lower reactants, gel pH, gel age and gel temperature. Formation Of Liesegang rings in this system is a temperature dependent phenomenon. It is shown that with the increase of the value of x the system passes from Liesegangring phenomenon to singlezone phenomenon. Operative mechanism of crystallization in the higher (35~40℃) and lower temperature ranges (25~30℃) is explained. Seeded growth experiments indicate the possibility of increasing the size of the spherulites in the gel medium
基金supported by the German Research Council(DFG)within the priority program(Schwerpunktprogramm),“Poröse Medien mit definierter Porenstruktur in der Verfahrenstechnik–Modellierung,Anwendngen,Synthese”(SPP 1570)under the projects LE 1187/10 and SP 648/4the framework of the DFG Excellence Initiative the Cluster of Excellence“Engineering of Advanced Materials”(DFG EXC 415)funding via the DFG research training group GRK 1896
文摘Macroscopic SiO2 spheres with a homogeneous amine distribution were synthesized by a one-step emulsion based synthesis approach in a flow column reactor. The CO2 adsorption capacity of the nanostructured amine-functionalized silica spheres was studied in absence and presence of H2O. The structural properties were adjusted by varying solvents and surfactants during the synthesis and, at constant amine loadings, were found to be the main factor for influencing the CO2 sorption capacities. Under water-free conditions CO2 is bound to the amino groups via the formation of carbamates, which require two neighboring amino groups to adsorb one CO2 molecule. At constant amine concentrations sorbents with lower surface area allow to establish a higher amine density on the surface, which enhances the CO2 uptake capacities under dry conditions. In presence of H2O the CO2 adsorption changes to 1：1 stoichiometry due to stabilization of carbamates by protonation of H2O and formation of further species such as bicarbonates, which should in principle double the adsorption capacities. Low concentrations of physisorbed H2O（0.3 mmol/g） did not impair the adsorption capacity of the adsorbents for CO2, while at higher water uptakes（0.6 and 1.1 mmol/g） the CO2 uptake is reduced, which could be attributed to capillary condensation of H2O or formation of bulky reaction products blocking inner pores and access to active sites.
基金The author thanks for the financial support of SINOPEC Corporation(S413108).
文摘The toluene oxidative bromination reaction catalyzed by hollow titanium silicalite(HTS)zeolite in aqueous medium was investigated by employing H2O2 and HBr under mild conditions without the need for organic solvent.A high toluene conversion(90.7%)and high selectivity of mono-bromotoluene(99.0%)was achieved under the optimal reaction conditions.The UV-Raman spectroscopy was applied for the mechanism study and the result reveals that HTS is efficient for catalyzing the oxidation reaction of HBr with H2O2 to produce abundant active bromine species,which can further facilitate the toluene electrophilic bromination reaction.A two-step toluene bromination reaction mechanism involving the HTS catalyzed active bromine species“generation-conversion-utilization”process is proposed based on the UV-Raman spectroscopy analysis.
文摘Rice husk ash was used as a new, green, and cheap adsorbent for FeCl3. Characterization of the obtained reagent showed that rice husk ash supported FeCl2·2H2O was formed. This reagent is efficient at catalyzing the synthesis of multisubstituted quinolines by the Friedl鋘der heteroannulation of o‐aminoaryl ketones with ketones or β‐diketones under mild reaction conditions. This methodology allows for the synthesis of a broad range of substituted quinolines in high yields and with excellent regioselectivity in the absence of a solvent.
基金the National Natural Science Foundation of China.
文摘The synthesis and the structural characterization of the title compound HNa[WO（CCH）-（OCCH）（HO）][HWO]·13.5 HO are described.It is known that the mixed oxo-ethylidyne-capped tritungsten cluster can be obtained by Zn dust reduction of NaWO·2HO in acetic anhydride.The title compound has been characterized by X-ray diffraction,UV/VIS andH NMR spectra.The tungsten atoms in the cluster cation and anion are in the oxidation states of W（IV）and W（VI）respectively.The crystal is rhombohedral with the space group R32,a=17.058（3）,c=49.665（9）,γ=120°,V=12516（9）,Z=6,final R=0.037 for 2071 reflections with I≥3σ（I）.Boththe cluster cation and anion have a Csymmetry.The important interatomic distances in angstroms forthe cluster cation are:W—W,2.730（2）;W—μ-O,2.00;W—O（carboxyl）,2.12;W—O,2.18（2）.
文摘A facile synthesis of benzo[h]quinolines has been developed via improved Combes reaction. A combination of silica gel, p-toluenesulfonic acid and phosphorus pentoxide was utilized to promote the condensation of 1-naphthylamines with 1,3-diketones under solvent free conditions. In this case, silica gel was used as reaction media, p-toluenesulfonic acid and phosphorus pentoxide were acted as catalyst and dehydrating agent, respectively.
基金supported by the Leading Academic Discipline Project of SHNU (No.DZL807)Innovation Program of Shanghai Municipal Education Commission (No.09YZ163)Shanghai Municipal Natural Science Foundation (No.09ZR1423300)
文摘Perfluorosulfonic acid/Polysulfone(PFSA/PSf) hollow fiber composite membranes have been prepared by dip-coating method using PSf ultrafiltration(UF) membrane as substrate with recovered PFSA.The composite membranes were applied to the pervaporation separation of 95% ethanol(EtOH)/H2O mixture.SEM images show that the thickness of the PFSA skin layer of the composite membranes is about 2 μm,much thinner than those of other PFSA composite membranes revealed in the literatures.Effects of annealing temperature,coating solution concentration and counter-ions of PFSA on the pervaporation performances of the composite membranes were investigated.The total flux decreases and separation factor increases with the increase of annealing temperature.The highest permeation flux of 3230 g m-2 h-1 and a separation factor of 5.4 is obtained for the composite membrane annealed at 80°C.The lowest permeation flux of 396 g m-2 h-1 and a separation factor of 27.7 is obtained for the composite membrane annealed at 160°C.The permeation performances of the PFSA/PSf composite membrane are evidently influenced by the counter-ions of PFSA.The flux sequence of the PFSA/PSf composite membranes with different counter-ions is H+>Li+>Ca2+>Mg2+>Na+>K+>Ba2+>Fe3+>Al3+,and the separation factor sequence is H+<Li+<Al3+<Na+<Mg2+<Ca2+<K+ <Ba2+<Fe3+.The apparent activation energy △Eapp values of the composite membranes with different counter-ions were calculated by Arrhenius law.The sequence of △Eapp values for the membranes with monovalent counter-ions is Li+>Na+>K+.There are very little variations of △Eapp values between the composite membranes with three divalent counterions(Mg2+,Ca2+ and Ba2+),and the △Eapp values of the composite membranes with two trivalent counterions(Fe3+ and Al3+) are relatively high.
