Acidic ionic liquid([BsAIm][OTf]) was immobilized on sulfhydryl-group-modified SiO2(MPS-SiO2) via free radical addition reaction. The[BsAIm][OTf] loading on acidic ionic liquid-functionalized silica([BsAIm][OTf]/SiO2)...Acidic ionic liquid([BsAIm][OTf]) was immobilized on sulfhydryl-group-modified SiO2(MPS-SiO2) via free radical addition reaction. The[BsAIm][OTf] loading on acidic ionic liquid-functionalized silica([BsAIm][OTf]/SiO2) was controlled through tuning the sulfydryl(SH)content of MPS-SiO2. All the samples were characterized by FT-IR, elemental analysis, N2adsorption-desorption measurements and TGDTA. The catalytic performance of [BsAIm][OTf]/SiO2in the esterification of oleic acid and the transesterification of glycerol trioleate for biodiesel production was investigated. The results showed that with the increase of [BsAIm][OTf] loading on SiO2the specific surface area and pore volume of [BsAIm][OTf]/SiO2decreased, and the pore diameter of [BsAIm][OTf]/SiO2narrowed. In the esterificaiton of oleic acid, the oleic acid conversion increased with the increasing [BsAIm][OTf] loading. In the transesterification of glycerol trioleate, with the increasing[BsAIm][OTf] loading the glycerol trioleate conversion decreased and the selectivities to glycerol monooleate and methyl oleate increased.展开更多
The carboxylic functionalized ionic liquid was immobilized on the molecular sieve(MCM-22)and then applied in the catalytic synthe-sis of ethyl methyl carbonate(EMC)via transesterification of dimethyl carbonate(DMC)wit...The carboxylic functionalized ionic liquid was immobilized on the molecular sieve(MCM-22)and then applied in the catalytic synthe-sis of ethyl methyl carbonate(EMC)via transesterification of dimethyl carbonate(DMC)with ethanol.Combined characterization results of FT-IR,XRD and TG suggest that the ILs had been immobilized on molecular sieve MCM-22.The influences of reaction temperature,time,and the mass ratio of MCM-22-CPTES-MIL/Ca O have also been investigated in detail.The catalytic tests demonstrated that MCM-22-CPTES-MIL/Ca O could catalyze the transesterification of DMC and ethanol with high efficiency,superior to those results of the heterogeneous catalysts reported previously.展开更多
Supported ionic liquid(IL) catalysts [Cmim]PMoO/Am TiO(amorphous TiO) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characterizations such as FTIR...Supported ionic liquid(IL) catalysts [Cmim]PMoO/Am TiO(amorphous TiO) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characterizations such as FTIR, DRS,wide-angle XRD, Nadsorption–desorption and XPS were applied to analyze the morphology and Keggin structure of the catalysts. In ECODS with hydrogen peroxide as the oxidant, it was found that ILs with longer alkyl chains in the cationic moiety had a better effect on the removal of dibenzothiophene. The desulfurization could reach 100% under optimal conditions, and GC–MS analysis was employed to detect the oxidized product after the reaction. Factors affecting the desulfurization efficiencies were discussed, and a possible mechanism was proposed. In addition, cyclic experiments were also conducted to investigate the recyclability of the supported catalyst. The catalytic activity of [Cmim]PMoO/Am TiOonly dropped from 100% to 92.9% after ten cycles, demonstrating the good recycling performance of the catalyst and its potential industrial application.展开更多
The complicated reaction mechanism and the character of competitive reactions lead to a stringent requirement for the catalyst of C_4 alkylation process. Due to their unique properties, ionic liquids(ILs) are thought ...The complicated reaction mechanism and the character of competitive reactions lead to a stringent requirement for the catalyst of C_4 alkylation process. Due to their unique properties, ionic liquids(ILs) are thought to be new potential acid catalysts for C_4 alkylation. An analysis of the regular and modified chloroaluminate ILs, novel Br?nsted ILs and composite ILs used in isobutane/butene alkylation shows that the use of either ILs or ILs coupled with mineral acid as homogeneous catalysts can help to greatly adjust the acid strength. By modifying the structural parameters of the cations and anions of the ILs, the solubility of the reactants could also be adjusted, which in turn displays a positive effect on improving the activity of ILs. Immobilization of ILs is an effective way to modulate the surface adsorption/desorption properties and acid strength distribution of the solid acid catalysts. Such a process has a tremendous potential to reduce the deactivation of catalyst and enhance the activity of the solid acid catalyst. The development of novel acid catalysts for C_4 alkylation is a comprehensive consideration of acid strength and its distribution, interfacial properties and transport characteristics.展开更多
The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid ca...The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation. To regulate the isobutane/1-butene adsorption ratio, four types of ionic liquid (i.e., IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite. The as-synthesized IL-immobilized MCM-22 (i.e., MCM-22-IL) was characterized by FT1R, TGA, BET, XPS and XRD, and their adsorption capacities and adsorption molar ratios of isobutane to l-butene (I/O) were investigated to correlate with surface features of MCM-22-IL Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume. But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene (I/O) was significantly im- proved by the immobilization of ionic liquids. The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs. Although the alkyl chain length oflLs was found to have little effect on the adsorption molar ratio of I/O, the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio. The results illustrated that immobilizing ionic liquids is an effective way to modify the textural, chemical and morphological properties of MCM-22. Accordingly, the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.展开更多
The performance of an electrocatalyst, which is needed e.g. for key energy conversion reactions such as hydrogen evolution, oxygen reduction or CO2 reduction, is determined not only by the inherent structure of active...The performance of an electrocatalyst, which is needed e.g. for key energy conversion reactions such as hydrogen evolution, oxygen reduction or CO2 reduction, is determined not only by the inherent structure of active sites but also by the properties of the interfacial structures at catalytic surfaces. Ionic liquids(ILs), as a unique class of metal salts with melting point below 100 ℃, present themselves as ideal modulators for manipulations of the interfacial structures. Due to their excellent properties such as good chemical stability, high ionic conductivity, wide electrochemical windows and tunable solvent properties the performance of electrocatalysts can be substantially improved through ILs. In the current minireview, we highlight the critical role of the IL phase at the microenvironments created by the IL, the liquid electrolyte, catalytic nanoparticles and/or support materials, by detailing the promotional effect of IL in electrocatalysis as reaction media, binders, and surface modifiers. Updated exemplary applications of IL in electrocatalysis are given and moreover, the latest developments of IL modified electrocatalysts following the "Solid Catalyst with Ionic Liquid Layer(SCILL)" concept are presented.展开更多
The Liaoyang Petrochemical Company has successfullydeveloped a novel ionic liquid catalyst for carbonylationof ethylene oxide with carbon dioxide to form ethylenecarbonate (EC). This catalyst can achieve an 100 % co...The Liaoyang Petrochemical Company has successfullydeveloped a novel ionic liquid catalyst for carbonylationof ethylene oxide with carbon dioxide to form ethylenecarbonate (EC). This catalyst can achieve an 100 % conversionand a 98% selectivity at low temperature andunder low pressure, featuring high catalytic activity, goodstability, good adaptability to feedstocks and low productioncost.展开更多
In this work,a“cyclopentanone-vanillin”strategy was proposed for the preparation of jet fuel range cycloalkanes from lignocellulose-derived ketones and lignin-derived aldehydes via aldol condensation and hydrodeoxyg...In this work,a“cyclopentanone-vanillin”strategy was proposed for the preparation of jet fuel range cycloalkanes from lignocellulose-derived ketones and lignin-derived aldehydes via aldol condensation and hydrodeoxygenation(HDO).Ethanolamine lactate ionic liquid(LAIL)exhibited excellent catalytic activity in the aldol condensation of cyclopentanone and vanillin.Desired mono-condensation and bicondensation products were obtained with yield of 95.2%at 100℃.It is found that the synergy effects between amino group of ethanolamine and hydroxyl group of lactic acid play a key role in the aldol condensation.The condensation products were converted into cycloalkanes by HDO over 5%Pd/Nb_(2)O_(5)catalyst.The density of the obtained HDO products is 0.89 g/cm^(3)and the freezing point is lower than-60℃.These results suggest that the resulted cycloalkanes can be used as additives to improve the density and low-temperature fluidity of the jet fuels.展开更多
基金supported by the National Natural Science Foundation of China(No.20706006 and 20976013)
文摘Acidic ionic liquid([BsAIm][OTf]) was immobilized on sulfhydryl-group-modified SiO2(MPS-SiO2) via free radical addition reaction. The[BsAIm][OTf] loading on acidic ionic liquid-functionalized silica([BsAIm][OTf]/SiO2) was controlled through tuning the sulfydryl(SH)content of MPS-SiO2. All the samples were characterized by FT-IR, elemental analysis, N2adsorption-desorption measurements and TGDTA. The catalytic performance of [BsAIm][OTf]/SiO2in the esterification of oleic acid and the transesterification of glycerol trioleate for biodiesel production was investigated. The results showed that with the increase of [BsAIm][OTf] loading on SiO2the specific surface area and pore volume of [BsAIm][OTf]/SiO2decreased, and the pore diameter of [BsAIm][OTf]/SiO2narrowed. In the esterificaiton of oleic acid, the oleic acid conversion increased with the increasing [BsAIm][OTf] loading. In the transesterification of glycerol trioleate, with the increasing[BsAIm][OTf] loading the glycerol trioleate conversion decreased and the selectivities to glycerol monooleate and methyl oleate increased.
基金Supported by the Educational Department of Liaoning Province(LZGD2020005)Liaoning Province Innovation and Entrepreneurship Training Project。
文摘The carboxylic functionalized ionic liquid was immobilized on the molecular sieve(MCM-22)and then applied in the catalytic synthe-sis of ethyl methyl carbonate(EMC)via transesterification of dimethyl carbonate(DMC)with ethanol.Combined characterization results of FT-IR,XRD and TG suggest that the ILs had been immobilized on molecular sieve MCM-22.The influences of reaction temperature,time,and the mass ratio of MCM-22-CPTES-MIL/Ca O have also been investigated in detail.The catalytic tests demonstrated that MCM-22-CPTES-MIL/Ca O could catalyze the transesterification of DMC and ethanol with high efficiency,superior to those results of the heterogeneous catalysts reported previously.
基金financially supported by the National Natural Science Foundation of China (Nos. 21576122, 21646001, 21506080)Natural Science Foundation of Jiangsu Province (Nos. BK20150485, BK20170528)+2 种基金China Postdoctoral Science Foundation (2017M611727)Jiangsu Planned Projects for Postdoctoral Research Funds (1701104B)supported by the Student Innovation and Entrepreneurship Training Program (201810299332 W)
文摘Supported ionic liquid(IL) catalysts [Cmim]PMoO/Am TiO(amorphous TiO) were synthesized through a one-step method for extraction coupled catalytic oxidative desulfurization(ECODS) system. Characterizations such as FTIR, DRS,wide-angle XRD, Nadsorption–desorption and XPS were applied to analyze the morphology and Keggin structure of the catalysts. In ECODS with hydrogen peroxide as the oxidant, it was found that ILs with longer alkyl chains in the cationic moiety had a better effect on the removal of dibenzothiophene. The desulfurization could reach 100% under optimal conditions, and GC–MS analysis was employed to detect the oxidized product after the reaction. Factors affecting the desulfurization efficiencies were discussed, and a possible mechanism was proposed. In addition, cyclic experiments were also conducted to investigate the recyclability of the supported catalyst. The catalytic activity of [Cmim]PMoO/Am TiOonly dropped from 100% to 92.9% after ten cycles, demonstrating the good recycling performance of the catalyst and its potential industrial application.
基金Supported by the National Natural Science Foundation of China(21276163,21576168)
文摘The complicated reaction mechanism and the character of competitive reactions lead to a stringent requirement for the catalyst of C_4 alkylation process. Due to their unique properties, ionic liquids(ILs) are thought to be new potential acid catalysts for C_4 alkylation. An analysis of the regular and modified chloroaluminate ILs, novel Br?nsted ILs and composite ILs used in isobutane/butene alkylation shows that the use of either ILs or ILs coupled with mineral acid as homogeneous catalysts can help to greatly adjust the acid strength. By modifying the structural parameters of the cations and anions of the ILs, the solubility of the reactants could also be adjusted, which in turn displays a positive effect on improving the activity of ILs. Immobilization of ILs is an effective way to modulate the surface adsorption/desorption properties and acid strength distribution of the solid acid catalysts. Such a process has a tremendous potential to reduce the deactivation of catalyst and enhance the activity of the solid acid catalyst. The development of novel acid catalysts for C_4 alkylation is a comprehensive consideration of acid strength and its distribution, interfacial properties and transport characteristics.
基金Supported by the National Natural Science Foundation of China(21576168,21276163)
文摘The adsorption ratio of isobutane/1-butene on the catalyst surface is one of the most important factors for the C4 alkylation process. Regulation of isobutane/1-butene adsorption ratio on the zeolite-supported acid catalyst is a big challenge for catalyst preparation. To regulate the isobutane/1-butene adsorption ratio, four types of ionic liquid (i.e., IL) with different alkyl chain lengths and different acid group numbers were synthesized and were subsequently immobilized onto the MCM-22 zeolite. The as-synthesized IL-immobilized MCM-22 (i.e., MCM-22-IL) was characterized by FT1R, TGA, BET, XPS and XRD, and their adsorption capacities and adsorption molar ratios of isobutane to l-butene (I/O) were investigated to correlate with surface features of MCM-22-IL Results showed that the immobilization of ILs led to a decrease of specific surface area and pore volume. But the surface density of acid groups was increased and the adsorption molar ratio of isobutane/1-butene (I/O) was significantly im- proved by the immobilization of ionic liquids. The adsorption molar ratio of I/O is substantially improved from 0.75 to above 0.9 at 300 kPa upon immobilizing ILs. Although the alkyl chain length oflLs was found to have little effect on the adsorption molar ratio of I/O, the increase of acid group numbers led to a dramatic decrease in the adsorption I/O ratio. The results illustrated that immobilizing ionic liquids is an effective way to modify the textural, chemical and morphological properties of MCM-22. Accordingly, the immobilization of ionic liquids provides a novel and a feasible way to regulate the adsorption I/O ratio on an adsorbent or a solid catalyst.
基金supported by the funding of the German Research Council (DFG), which, within the framework of its Excellence Initiative, supports the Cluster of Excellence “Engineering of Advanced Materials” (www.eam.uni-erlangen.de) at the University of Erlangen-Nürnberg
文摘The performance of an electrocatalyst, which is needed e.g. for key energy conversion reactions such as hydrogen evolution, oxygen reduction or CO2 reduction, is determined not only by the inherent structure of active sites but also by the properties of the interfacial structures at catalytic surfaces. Ionic liquids(ILs), as a unique class of metal salts with melting point below 100 ℃, present themselves as ideal modulators for manipulations of the interfacial structures. Due to their excellent properties such as good chemical stability, high ionic conductivity, wide electrochemical windows and tunable solvent properties the performance of electrocatalysts can be substantially improved through ILs. In the current minireview, we highlight the critical role of the IL phase at the microenvironments created by the IL, the liquid electrolyte, catalytic nanoparticles and/or support materials, by detailing the promotional effect of IL in electrocatalysis as reaction media, binders, and surface modifiers. Updated exemplary applications of IL in electrocatalysis are given and moreover, the latest developments of IL modified electrocatalysts following the "Solid Catalyst with Ionic Liquid Layer(SCILL)" concept are presented.
文摘The Liaoyang Petrochemical Company has successfullydeveloped a novel ionic liquid catalyst for carbonylationof ethylene oxide with carbon dioxide to form ethylenecarbonate (EC). This catalyst can achieve an 100 % conversionand a 98% selectivity at low temperature andunder low pressure, featuring high catalytic activity, goodstability, good adaptability to feedstocks and low productioncost.
基金funded by grants from the National Natural Science Foundation of China(No.52236010,51876210)the Fundamental Research Funds for the Central Universities(No.2242022R10058)。
文摘In this work,a“cyclopentanone-vanillin”strategy was proposed for the preparation of jet fuel range cycloalkanes from lignocellulose-derived ketones and lignin-derived aldehydes via aldol condensation and hydrodeoxygenation(HDO).Ethanolamine lactate ionic liquid(LAIL)exhibited excellent catalytic activity in the aldol condensation of cyclopentanone and vanillin.Desired mono-condensation and bicondensation products were obtained with yield of 95.2%at 100℃.It is found that the synergy effects between amino group of ethanolamine and hydroxyl group of lactic acid play a key role in the aldol condensation.The condensation products were converted into cycloalkanes by HDO over 5%Pd/Nb_(2)O_(5)catalyst.The density of the obtained HDO products is 0.89 g/cm^(3)and the freezing point is lower than-60℃.These results suggest that the resulted cycloalkanes can be used as additives to improve the density and low-temperature fluidity of the jet fuels.