C3 hydrocarbons(HCs),especially propylene and propane,are high‐volume products of the chemical industry as they are utilized for the production of fuels,polymers,and chemical commodities.Demand for C3 HCs as chemical...C3 hydrocarbons(HCs),especially propylene and propane,are high‐volume products of the chemical industry as they are utilized for the production of fuels,polymers,and chemical commodities.Demand for C3 HCs as chemical building blocks is increasing but obtaining them in sufficient purity(>99.95%)for polymer and chemical processes requires economically and energetically costly methods such as cryogenic distillation.Adsorptive separations using porous coordination networks(PCNs)could offer an energy‐efficient alternative to current technolo-gies for C3 HC purification because of the lower energy footprint of sorbent separations for recycling versus alternatives such as distillation,solvent extraction,and chemical transformation.In this review,we address how the structural modularity of porous PCNs makes them amenable to crystal engineering that in turn enables control over pore size,shape,and chemistry.We detail how control over pore structure has enabled PCN sorbents to offer benchmark performance for C3 separations thanks to several distinct mechanisms,each of which is highlighted.We also discuss the major challenges and opportunities that remain to be addressed before the commercial development of PCNs as advanced sorbents for C3 separation becomes viable.展开更多
C_(2)H_(2)/CO_(2)separation is an industrially important process that remains challenging because of the similar physicochemical properties of C_(2)H_(2)and CO_(2).We herein report that the new square lattice(sql)coor...C_(2)H_(2)/CO_(2)separation is an industrially important process that remains challenging because of the similar physicochemical properties of C_(2)H_(2)and CO_(2).We herein report that the new square lattice(sql)coordination network[Cu(bipy‐xylene)2(NO3)2]n,sql‐16‐Cu‐NO3,16=bipy‐xylene=4,4′‐(2,5‐dimethyl‐1,4‐phenylene)dipyridine,exists in at least three forms,as‐synthesised(α),activated(α′)and hydrated(β).The activated phase,sql‐16‐Cu‐NO3‐α′,is an ultramicroporous material that exhibits high selectivity towards C_(2)H_(2)over CO_(2)as revealed by dynamic gas breakthrough experiments(1:1,C_(2)H_(2)/CO_(2))that afforded 99.87%pure CO_(2)in the effluent stream.The separation selectivity at 298 K and 1 bar,78,is the third best value yet reported for C_(2)H_(2)selective physisorbents whereas the mid‐loading performance sets a new benchmark.The performance of sql‐16‐Cu‐NO3‐α′is attributed to a new type of C_(2)H_(2)binding site in which CH···ONO2 interactions enable moderately strong sorbent‐sorbate binding(Qst(C_(2)H_(2))=38.6 kJ/mol)at low loading.Conversely,weak CO_(2)binding(Qst(CO_(2))=25.6 kJ/mol)at low loading means that(ΔQst)AC[Qst(C_(2)H_(2))–Qst(CO_(2))]is 13 kJ/mol at low coverage and 11.4 kJ/mol at mid‐loading.Analysis of in situ powder X‐ray diffraction and modelling experiments provide insight into the sorption properties and high C_(2)H_(2)/CO_(2)separation performance of sql‐16‐Cu‐NO3‐α′.展开更多
基金Science Foundation Ireland,Grant/Award Numbers:13/RP/B2549,16/IA/4624H2020 European Research Council,Grant/Award Number:ADG 885695Irish Research Council,Grant/Award Number:IRCLA/2019/167。
文摘C3 hydrocarbons(HCs),especially propylene and propane,are high‐volume products of the chemical industry as they are utilized for the production of fuels,polymers,and chemical commodities.Demand for C3 HCs as chemical building blocks is increasing but obtaining them in sufficient purity(>99.95%)for polymer and chemical processes requires economically and energetically costly methods such as cryogenic distillation.Adsorptive separations using porous coordination networks(PCNs)could offer an energy‐efficient alternative to current technolo-gies for C3 HC purification because of the lower energy footprint of sorbent separations for recycling versus alternatives such as distillation,solvent extraction,and chemical transformation.In this review,we address how the structural modularity of porous PCNs makes them amenable to crystal engineering that in turn enables control over pore size,shape,and chemistry.We detail how control over pore structure has enabled PCN sorbents to offer benchmark performance for C3 separations thanks to several distinct mechanisms,each of which is highlighted.We also discuss the major challenges and opportunities that remain to be addressed before the commercial development of PCNs as advanced sorbents for C3 separation becomes viable.
基金Science Foundation Ireland,Grant/Award Numbers:13/RP/B2549,16/IA/4624Japan Society for the Promotion of Science,Grant/Award Numbers:JP18H05262,JP19K15584Irish Research Council,Grant/Award Number:IRCLA/2019/167。
文摘C_(2)H_(2)/CO_(2)separation is an industrially important process that remains challenging because of the similar physicochemical properties of C_(2)H_(2)and CO_(2).We herein report that the new square lattice(sql)coordination network[Cu(bipy‐xylene)2(NO3)2]n,sql‐16‐Cu‐NO3,16=bipy‐xylene=4,4′‐(2,5‐dimethyl‐1,4‐phenylene)dipyridine,exists in at least three forms,as‐synthesised(α),activated(α′)and hydrated(β).The activated phase,sql‐16‐Cu‐NO3‐α′,is an ultramicroporous material that exhibits high selectivity towards C_(2)H_(2)over CO_(2)as revealed by dynamic gas breakthrough experiments(1:1,C_(2)H_(2)/CO_(2))that afforded 99.87%pure CO_(2)in the effluent stream.The separation selectivity at 298 K and 1 bar,78,is the third best value yet reported for C_(2)H_(2)selective physisorbents whereas the mid‐loading performance sets a new benchmark.The performance of sql‐16‐Cu‐NO3‐α′is attributed to a new type of C_(2)H_(2)binding site in which CH···ONO2 interactions enable moderately strong sorbent‐sorbate binding(Qst(C_(2)H_(2))=38.6 kJ/mol)at low loading.Conversely,weak CO_(2)binding(Qst(CO_(2))=25.6 kJ/mol)at low loading means that(ΔQst)AC[Qst(C_(2)H_(2))–Qst(CO_(2))]is 13 kJ/mol at low coverage and 11.4 kJ/mol at mid‐loading.Analysis of in situ powder X‐ray diffraction and modelling experiments provide insight into the sorption properties and high C_(2)H_(2)/CO_(2)separation performance of sql‐16‐Cu‐NO3‐α′.