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Crystal engineering of porous coordination networks for C3 hydrocarbon separation

SmartMat 2021年第1期2卷 38-55页

作者： Mei‐Yan Gao Bai‐Qiao Song debobroto sensharma Michael J.Zaworotko Department of Chemical Sciences Bernal InstituteUniversity of LimerickLimerickRepublic of Ireland

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 *** 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 *** 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 *** 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 *** 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 *** 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.

关键词： binding sites C3 hydrocarbon PCNs separation

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A square lattice topology coordination network that exhibits highly selectiveC_(2)H_(2)/CO_(2)separation performance

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SmartMat 2020年第1期1卷 48-55页

作者： Naveen Kumar Soumya Mukherjee Andrey A.Bezrukov Matthias Vandichel Mohana Shivanna debobroto sensharma Alankriti Bajpai Victoria Gascón Ken‐ichi Otake Susumu Kitagawa Michael J.Zaworotko Department of Chemical Sciences Bernal InstituteUniversity of LimerickLimerickRepublic of Ireland Institute for Integrated Cell‐Material Sciences(iCeMS) Kyoto University(KUIAS)Yoshida UshinomiyachoKyotoJapan

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 *** 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 *** 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 ***,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‐*** 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′.

关键词： acetylene adsorption coordination networks crystal engineering ultramicroporosity

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