A series of metal-organic frameworks MOF-808-X(6-connected)were synthesized by regulating the ZrOCl2·8H2O/1,3,5-benzenetricarboxylic acid(BTC)molar ratio(X)and tested for the direct synthesis of dimethyl carbonat...A series of metal-organic frameworks MOF-808-X(6-connected)were synthesized by regulating the ZrOCl2·8H2O/1,3,5-benzenetricarboxylic acid(BTC)molar ratio(X)and tested for the direct synthesis of dimethyl carbonate(DMC)from CO2 and CH3OH with 1,1,1-trimethoxymethane(TMM)as a dehydrating agent.The effect of the ZrOCl2·8H2O/BTC molar ratio on the physicochemical properties and catalytic performance of MOF-808-X was investigated.Results showed that a proper ZrOCl2·8H2O/BTC molar ratio during MOF-808-X synthesis was fairly important to reduce the redundant BTC or zirconium clusters trapped in the micropores of MOF-808-X.MOF-808-4,with almost no redundant BTC or zirconium clusters trapped in the micropores,exhibited the largest surface area,micropore size,and the number of acidic-basic sites,and consequently showed the best activity among all MOF-808-X,with the highest DMC yield of 21.5% under the optimal reaction conditions.Moreover,benefiting from the larger micropore size,MOF-808-4 outperformed our previously reported UiO-66-24(12-connected),which had even more acidic-basic sites and larger surface area than MOF-808-4,mainly because the larger micropore size of MOF-808-4 provided higher accessibility for the reactant to the active sites located in the micropores.Furthermore,a possible reaction mechanism over MOF-808-4 was proposed based on the in situ FT-IR results.The effects of different reaction parameters on DMC formation and the reusability of MOF-808-X were also studied.展开更多
The vapor-liquid equilibrium (VLE) data for the dimethyl carbonate-n-butyl acetate binary system were measured by an Ellis equilibrated distillator. The experimental data were checked for their thermodynamic consisten...The vapor-liquid equilibrium (VLE) data for the dimethyl carbonate-n-butyl acetate binary system were measured by an Ellis equilibrated distillator. The experimental data were checked for their thermodynamic consistency through statistical methods. The VLE data was correlated with Wilson and NRTL activity coefficient models and also with the calculation of the vapor phase fugacity coefficient by the modified Peng-Robinson equation of state.展开更多
Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is ...Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carded out under the following conditions： the reaction temperature 250℃, molar ratio of EC to DMT 3 ： 1, reaction time 3h, and catalyst amount 0.004 （molar ratio to DMT）, the yield of DMC was 68.9%.展开更多
A facile route for the synthesis of dimethyl adipate （DAP） from cyclopentanone and dimethyl carbonate （DMC） in the pres- ence of solid base catalysts has been developed. It was found that the intermediate carbomet...A facile route for the synthesis of dimethyl adipate （DAP） from cyclopentanone and dimethyl carbonate （DMC） in the pres- ence of solid base catalysts has been developed. It was found that the intermediate carbomethoxycyclopentanone （CMCP） was produced from cyclopentanone with DMC in the first step, and then CMCP was further converted to DAP by reacting with a methoxide group. The role of the basic catalysts can be mainly ascribed to the activation of cyclopentanone via the abstraction of a proton in the a-position by base sites, and solid bases with moderate strength, such as MgO, favor the formation of DAP.展开更多
Single-walled carbon nanotubes （SWNTs） possess high conductivity, mechanical strength, transparency, and flexibility, and are thus suitable for use in flexible electronics, transparent electrodes, and energy-storage...Single-walled carbon nanotubes （SWNTs） possess high conductivity, mechanical strength, transparency, and flexibility, and are thus suitable for use in flexible electronics, transparent electrodes, and energy-storage and energy-harvesting applications. However, to exploit these properties, SWNTs must be de-bundled in a surfactant solution to permit processing and use. We report a new method to prepare a SWNT-based transparent conducting film （TCF） using the diazo dye 3,3＇-（[1,1＇-biphenyl]-4,4＇-diyl）bis（4-amino naphthalene-1-sulfonic acid）, commonly known as Congo red （CR）, as a dispersant. Uniform 20-nm-thick TCFs were prepared on rigid glass and flexible polyethylene terephthalate （PET） substrates. The CR-SWNT dispersion and the CR-SWNT TCFs were characterized via UV-Vis-NIR, Raman spectroscopy, FT-IR spectroscopy, transmission electron microscopy （TEM）, field-emission scanning electron microscopy （FE-SEM） and dynamic light scattering （DLS） measurements. The sheet resistivity of the CRSWNT TCF was -34 ±6.6 Ω/□ with a transmittance of 81% at 550 nm, comparable to that of indium tin oxide-based films. Unlike SWNT dispersions prepared in common surfactants, such as sodium dodecyl sulfate （SDS）, sodium cholate （SC）, and Triton X-100, the CR-SWNT dispersion was amenable to forming TCF by drop coating. The CR-SWNT TCF was also very stable, maintaining a very low sheet resistivity even after 1,000 consecutive bending cycles of 8 mm bending radius. Further, manganese dioxide （MnO2） was electrochemically deposited on the CR-SWNT-PET film （MnO2-CR-SWNT-PET）. The as-prepared MnO2- CR-SWNT-PET electrode exhibited high specific capacitance and bendability, demonstrating promise as a candidate electrode material for flexible supercapacitors.展开更多
基金financially supported by the Natural Science Foundation of Shanxi Province,China(201601D102006)the Science Foundation for Young Scientists of Shanxi Province,China(201701D221052)+2 种基金the National Natural Science Foundation of China(21776294)the Key Science and Technology Program of Shanxi Province,China(MD2014-09,MD2014-10)the Independent Research Project of the State Key Laboratory of Coal Conversion(2018BWZ002)~~
文摘A series of metal-organic frameworks MOF-808-X(6-connected)were synthesized by regulating the ZrOCl2·8H2O/1,3,5-benzenetricarboxylic acid(BTC)molar ratio(X)and tested for the direct synthesis of dimethyl carbonate(DMC)from CO2 and CH3OH with 1,1,1-trimethoxymethane(TMM)as a dehydrating agent.The effect of the ZrOCl2·8H2O/BTC molar ratio on the physicochemical properties and catalytic performance of MOF-808-X was investigated.Results showed that a proper ZrOCl2·8H2O/BTC molar ratio during MOF-808-X synthesis was fairly important to reduce the redundant BTC or zirconium clusters trapped in the micropores of MOF-808-X.MOF-808-4,with almost no redundant BTC or zirconium clusters trapped in the micropores,exhibited the largest surface area,micropore size,and the number of acidic-basic sites,and consequently showed the best activity among all MOF-808-X,with the highest DMC yield of 21.5% under the optimal reaction conditions.Moreover,benefiting from the larger micropore size,MOF-808-4 outperformed our previously reported UiO-66-24(12-connected),which had even more acidic-basic sites and larger surface area than MOF-808-4,mainly because the larger micropore size of MOF-808-4 provided higher accessibility for the reactant to the active sites located in the micropores.Furthermore,a possible reaction mechanism over MOF-808-4 was proposed based on the in situ FT-IR results.The effects of different reaction parameters on DMC formation and the reusability of MOF-808-X were also studied.
基金Supported by the China Petrochemical Corporation.
文摘The vapor-liquid equilibrium (VLE) data for the dimethyl carbonate-n-butyl acetate binary system were measured by an Ellis equilibrated distillator. The experimental data were checked for their thermodynamic consistency through statistical methods. The VLE data was correlated with Wilson and NRTL activity coefficient models and also with the calculation of the vapor phase fugacity coefficient by the modified Peng-Robinson equation of state.
基金the National High Technology Research and Development Program of China(No.2003AA321010).
文摘Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carded out under the following conditions： the reaction temperature 250℃, molar ratio of EC to DMT 3 ： 1, reaction time 3h, and catalyst amount 0.004 （molar ratio to DMT）, the yield of DMC was 68.9%.
基金supported by the Zhangjiang Science and Technology Development Foundation of Guangdong,China (2009C3101015)Doctoral Starting Foundation of Guangdong Medical College (XB0811)
文摘A facile route for the synthesis of dimethyl adipate （DAP） from cyclopentanone and dimethyl carbonate （DMC） in the pres- ence of solid base catalysts has been developed. It was found that the intermediate carbomethoxycyclopentanone （CMCP） was produced from cyclopentanone with DMC in the first step, and then CMCP was further converted to DAP by reacting with a methoxide group. The role of the basic catalysts can be mainly ascribed to the activation of cyclopentanone via the abstraction of a proton in the a-position by base sites, and solid bases with moderate strength, such as MgO, favor the formation of DAP.
文摘Single-walled carbon nanotubes （SWNTs） possess high conductivity, mechanical strength, transparency, and flexibility, and are thus suitable for use in flexible electronics, transparent electrodes, and energy-storage and energy-harvesting applications. However, to exploit these properties, SWNTs must be de-bundled in a surfactant solution to permit processing and use. We report a new method to prepare a SWNT-based transparent conducting film （TCF） using the diazo dye 3,3＇-（[1,1＇-biphenyl]-4,4＇-diyl）bis（4-amino naphthalene-1-sulfonic acid）, commonly known as Congo red （CR）, as a dispersant. Uniform 20-nm-thick TCFs were prepared on rigid glass and flexible polyethylene terephthalate （PET） substrates. The CR-SWNT dispersion and the CR-SWNT TCFs were characterized via UV-Vis-NIR, Raman spectroscopy, FT-IR spectroscopy, transmission electron microscopy （TEM）, field-emission scanning electron microscopy （FE-SEM） and dynamic light scattering （DLS） measurements. The sheet resistivity of the CRSWNT TCF was -34 ±6.6 Ω/□ with a transmittance of 81% at 550 nm, comparable to that of indium tin oxide-based films. Unlike SWNT dispersions prepared in common surfactants, such as sodium dodecyl sulfate （SDS）, sodium cholate （SC）, and Triton X-100, the CR-SWNT dispersion was amenable to forming TCF by drop coating. The CR-SWNT TCF was also very stable, maintaining a very low sheet resistivity even after 1,000 consecutive bending cycles of 8 mm bending radius. Further, manganese dioxide （MnO2） was electrochemically deposited on the CR-SWNT-PET film （MnO2-CR-SWNT-PET）. The as-prepared MnO2- CR-SWNT-PET electrode exhibited high specific capacitance and bendability, demonstrating promise as a candidate electrode material for flexible supercapacitors.
