In this work grand canonical Monte Carlo simulations were performed to study gas separation in three pairs of isoreticular metal-organic frameworks (IRMOFs) with and without catenation at room temperature.Mixture comp...In this work grand canonical Monte Carlo simulations were performed to study gas separation in three pairs of isoreticular metal-organic frameworks (IRMOFs) with and without catenation at room temperature.Mixture composed of CO2 and H2 was selected as the model system to separate.The results show that CO2 selectivity in catenated MOFs with multi-porous frameworks is much higher than their non-catenated counterparts.The simulations also show that the electrostatic interactions are very important for the selectivity,and the contributions of different electrostatic interactions are different,depending on pore size,pressure and mixture composition.In fact,changing the electrostatic interactions can even qualitatively change the adsorption behavior.A general conclusion is that the electrostatic interactions between adsorbate molecules and the framework atoms play a dominant role at low pressures,and these interactions in catenated MOFs have much more pronounced effects than those in their non-catenated counterparts,while the electrostatic interactions between adsorbate molecules become evident with increasing pressure,and eventually dominant.展开更多
The design of optimal separation flow sheets for multi-component mixtures is still not a solved problem This is especially the case when non-ideal or azeotropic mixtures or hybrid separation processes are considered. ...The design of optimal separation flow sheets for multi-component mixtures is still not a solved problem This is especially the case when non-ideal or azeotropic mixtures or hybrid separation processes are considered. We review recent developments in this field and present a systematic framework for the design of separation flow sheets. This framework proposes a three-step approach. In the first step different flow sheets are generated. In the second step these alternative flow sheet structures are evaluated with shortcut methods. In the third step a rigorous mixed-integer nonlinear programming (MINLP) optimization of the entire flow sheet is executed to determine the best alternative. Since a number of alternative flow sheets have already been eliminated, only a few optimization runs are necessary in this final step. The whole framework thus allows the systematic generation and evaluation of separation processes and is illustrated with the case study of the separation of ethanol and water.展开更多
Two isomeric metal-organic frameworks(MOFs) with 2-dimensional(2D) and 3-dimensional(3D) topologies both comprised of Cu(Ⅱ) and OTf(OTf = trifluoromethanesulfonate) ions were synthesized and characterized.The CO_2,CH...Two isomeric metal-organic frameworks(MOFs) with 2-dimensional(2D) and 3-dimensional(3D) topologies both comprised of Cu(Ⅱ) and OTf(OTf = trifluoromethanesulfonate) ions were synthesized and characterized.The CO_2,CH_4 and N_2 adsorption properties of the two isomeric MOFs were investigated from 263 K to 298 K at0.1 MPa.The results showed that the 2D MOF exhibited a higher selectivity for CO_2 from CO_2/CH_4 and CH_4from CH_4/N_2 compared to the 3D MOF,even though it possessed a lower surface area and pore volume.The higher adsorption heats of gases on the 2D MOF inferred the strong adsorption potential energy in the layered MOFs.Dynamic separation experiments using CO_2/CH_4 and CH_4/N_2 mixtures on the two MOFs proved that the2 D MOF had a longer elution time than the 3D MOF as well as better separation abilities.展开更多
Reaction of Zn(NO3)2.6H2O with 5-(isonicotinamido) isophthalic acid(H2INAIP) in N,N-dimethylformamide(DMF) affords a new three-dimensional(3D) coordination polymer {[Zn(INAIP)(DMF)].0.5DMF.4H2O}n(1).The X-ray crystall...Reaction of Zn(NO3)2.6H2O with 5-(isonicotinamido) isophthalic acid(H2INAIP) in N,N-dimethylformamide(DMF) affords a new three-dimensional(3D) coordination polymer {[Zn(INAIP)(DMF)].0.5DMF.4H2O}n(1).The X-ray crystallographic structural analysis reveals that complex 1 is a 3D porous framework containing a potential open metal site inside the pores.Topology analysis confirms that complex 1 is a two-fold interpenetrated(10,3)-b net with both metal ion and ligand acting as 3-connecting nodes.The thermal stability,variable temperature X-ray diffraction pattern and N2 adsorption property of the complex are investigated.展开更多
The energy-efficient purification of methane from C2-hydrocarbons is of great significance for the upgrading of natural gas. So does the capture of carbon dioxide for remission of greenhouse effect. It is well establi...The energy-efficient purification of methane from C2-hydrocarbons is of great significance for the upgrading of natural gas. So does the capture of carbon dioxide for remission of greenhouse effect. It is well established that some functional sites, such as open metals sites, Lewis basic nitrogen sites and fluorine groups, have shown significantly enhanced affinity toward more polarizable molecules. Thus, a water-stable Eu3+-based fcu-metal-organic framework(MOF)(compound 1) with amino functional groups has been successfully constructed through a reticular chemistry approach.As a result, the activated compound 1 exhibits moderately high uptakes of C2-hydrocarbons, but a less obvious adsorption of CH4 at the same conditions. Among them, the adsorption capacity of C2 H2 is up to 143.6 cm3 cm-3 and a relatively high selectivity of C2 H2/CH4(107.7) is obtained at near room temperature. Moreover, compound 1 is also validated as an exceptional adsorbent for CO2 capture, with the fairly high capacity of CO2(92.6 cm3 cm-3) and CO2/N2 selectivity(151.7) at ambient conditions. The excellent performance of compound 1 is mainly driven by the exposed amino functional groups within the contracted pores. Such effect thus leads to the achievement of dual-functional platform for methane purification and carbon dioxide capture. Furthermore, compound 1 features a satisfactory water stability,which is confirmed by the powder X-ray diffraction(PXRD)analysis and the retest of porosity after being soaked in water.展开更多
基金Supported by the National Natural Science Foundation of China (20725622, 20706002, and 20876006), Beijing Nova Program (2008B15) and the Dutch STW/CW Separation Technology Program (700.56.655-DPC.6243).
文摘In this work grand canonical Monte Carlo simulations were performed to study gas separation in three pairs of isoreticular metal-organic frameworks (IRMOFs) with and without catenation at room temperature.Mixture composed of CO2 and H2 was selected as the model system to separate.The results show that CO2 selectivity in catenated MOFs with multi-porous frameworks is much higher than their non-catenated counterparts.The simulations also show that the electrostatic interactions are very important for the selectivity,and the contributions of different electrostatic interactions are different,depending on pore size,pressure and mixture composition.In fact,changing the electrostatic interactions can even qualitatively change the adsorption behavior.A general conclusion is that the electrostatic interactions between adsorbate molecules and the framework atoms play a dominant role at low pressures,and these interactions in catenated MOFs have much more pronounced effects than those in their non-catenated counterparts,while the electrostatic interactions between adsorbate molecules become evident with increasing pressure,and eventually dominant.
基金the Deutsche Forschungsgemeinschaft (German Research Foundation),DAAD (German Academic Exchange Service) and FUNDAYACUCHO, and Bayer Technology Services
文摘The design of optimal separation flow sheets for multi-component mixtures is still not a solved problem This is especially the case when non-ideal or azeotropic mixtures or hybrid separation processes are considered. We review recent developments in this field and present a systematic framework for the design of separation flow sheets. This framework proposes a three-step approach. In the first step different flow sheets are generated. In the second step these alternative flow sheet structures are evaluated with shortcut methods. In the third step a rigorous mixed-integer nonlinear programming (MINLP) optimization of the entire flow sheet is executed to determine the best alternative. Since a number of alternative flow sheets have already been eliminated, only a few optimization runs are necessary in this final step. The whole framework thus allows the systematic generation and evaluation of separation processes and is illustrated with the case study of the separation of ethanol and water.
基金Supported by National Natural Science Foundation of China(No.21136007,No.51302184)the National Research Fund for Fundamental Key Projects(No.2014CB260402)
文摘Two isomeric metal-organic frameworks(MOFs) with 2-dimensional(2D) and 3-dimensional(3D) topologies both comprised of Cu(Ⅱ) and OTf(OTf = trifluoromethanesulfonate) ions were synthesized and characterized.The CO_2,CH_4 and N_2 adsorption properties of the two isomeric MOFs were investigated from 263 K to 298 K at0.1 MPa.The results showed that the 2D MOF exhibited a higher selectivity for CO_2 from CO_2/CH_4 and CH_4from CH_4/N_2 compared to the 3D MOF,even though it possessed a lower surface area and pore volume.The higher adsorption heats of gases on the 2D MOF inferred the strong adsorption potential energy in the layered MOFs.Dynamic separation experiments using CO_2/CH_4 and CH_4/N_2 mixtures on the two MOFs proved that the2 D MOF had a longer elution time than the 3D MOF as well as better separation abilities.
基金supported by the National Natural Science Foundation of China(U0934003,20903120,20821001&20731005)the Research Fund for the Doctoral Program of Higher Education of Chinathe Fundamental Research Funds for the Central Universities
文摘Reaction of Zn(NO3)2.6H2O with 5-(isonicotinamido) isophthalic acid(H2INAIP) in N,N-dimethylformamide(DMF) affords a new three-dimensional(3D) coordination polymer {[Zn(INAIP)(DMF)].0.5DMF.4H2O}n(1).The X-ray crystallographic structural analysis reveals that complex 1 is a 3D porous framework containing a potential open metal site inside the pores.Topology analysis confirms that complex 1 is a two-fold interpenetrated(10,3)-b net with both metal ion and ligand acting as 3-connecting nodes.The thermal stability,variable temperature X-ray diffraction pattern and N2 adsorption property of the complex are investigated.
基金supported by the National Natural Science Foundation of China(U1609219,51632008,61721005,51432001and 51772268)Zhejiang Provincial Natural Science Foundation(LD18E020001)
文摘The energy-efficient purification of methane from C2-hydrocarbons is of great significance for the upgrading of natural gas. So does the capture of carbon dioxide for remission of greenhouse effect. It is well established that some functional sites, such as open metals sites, Lewis basic nitrogen sites and fluorine groups, have shown significantly enhanced affinity toward more polarizable molecules. Thus, a water-stable Eu3+-based fcu-metal-organic framework(MOF)(compound 1) with amino functional groups has been successfully constructed through a reticular chemistry approach.As a result, the activated compound 1 exhibits moderately high uptakes of C2-hydrocarbons, but a less obvious adsorption of CH4 at the same conditions. Among them, the adsorption capacity of C2 H2 is up to 143.6 cm3 cm-3 and a relatively high selectivity of C2 H2/CH4(107.7) is obtained at near room temperature. Moreover, compound 1 is also validated as an exceptional adsorbent for CO2 capture, with the fairly high capacity of CO2(92.6 cm3 cm-3) and CO2/N2 selectivity(151.7) at ambient conditions. The excellent performance of compound 1 is mainly driven by the exposed amino functional groups within the contracted pores. Such effect thus leads to the achievement of dual-functional platform for methane purification and carbon dioxide capture. Furthermore, compound 1 features a satisfactory water stability,which is confirmed by the powder X-ray diffraction(PXRD)analysis and the retest of porosity after being soaked in water.