000070693 001__ 70693 000070693 005__ 20190709135531.0 000070693 0247_ $$2doi$$a10.1039/c7ce00086c 000070693 0248_ $$2sideral$$a98452 000070693 037__ $$aART-2017-98452 000070693 041__ $$aeng 000070693 100__ $$0(orcid)0000-0002-0238-3127$$aCacho-Bailo, Fernando$$uUniversidad de Zaragoza 000070693 245__ $$aSequential amine functionalization inducing structural transition in an aldehyde-containing zeolitic imidazolate framework: Application to gas separation membranes 000070693 260__ $$c2017 000070693 5060_ $$aAccess copy available to the general public$$fUnrestricted 000070693 5203_ $$aA modification in the gas separation performance of zeolitic imidazolate framework (ZIF)-supported hollow fiber (HF) membranes by means of an imine-condensation functionalization reaction carried out by microfluidics is reported. The accommodation of voluminous amine molecules in the SIM-1, Zn(4-methyl-5-imidazolecarboxaldehyde)2, also known as ZIF-94, sod structure during the functionalization reaction caused the ZIF atoms to be rearranged in a less dense rho structure, with a wider pore diameter and a diminished CO2 affinity. These changes had effects on the membrane performance, resulting in an enhanced CO2 permeance while maintaining a good permeance-selectivity balance. ZIF aldehyde-containing SIM-1 membranes were earlier prepared on the inner side of polymeric P84® HF using a microfluidic approach. The SIM-1 membranes displayed very interesting results in the separation of gas mixtures of great relevance to the natural gas field. High selectivities in the separation of He/CH4 (160), H2/CH4 (136) and CO2/CH4 (38) mixtures were achieved, and these are the first SIM-1 membranes with such a high separation performance to the best of our knowledge. These SIM-1 membranes were in situ stepwise functionalized with long-chain amine solutions, namely, hexyl- and nonylamine. Microfluidics allowed the easy sequential implementation of this post-reaction step in the membrane fabrication procedure. An imine-condensation reaction took place between the aldehyde groups in the 4-methyl-5-imidazolecarboxaldehyde ligand forming SIM-1 and the corresponding amines. The extent of the reaction was analyzed by FTIR, TGA and XRD, together with the changes in the textural properties and the adsorption capacities. 000070693 536__ $$9info:eu-repo/grantAgreement/ES/DGA/T05$$9info:eu-repo/grantAgreement/ES/MINECO/MAT2013-40566-R$$9info:eu-repo/grantAgreement/ES/MINECO/MAT2016-77290-R 000070693 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/ 000070693 590__ $$a3.304$$b2017 000070693 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b62 / 171 = 0.363$$c2017$$dQ2$$eT2 000070693 591__ $$aCRYSTALLOGRAPHY$$b8 / 26 = 0.308$$c2017$$dQ2$$eT1 000070693 592__ $$a0.998$$b2017 000070693 593__ $$aChemistry (miscellaneous)$$c2017$$dQ1 000070693 593__ $$aMaterials Science (miscellaneous)$$c2017$$dQ1 000070693 593__ $$aCondensed Matter Physics$$c2017$$dQ1 000070693 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion 000070693 700__ $$aEtxeberría-Benavides, Miren 000070693 700__ $$aKarvan, Oguz 000070693 700__ $$0(orcid)0000-0002-4954-1188$$aTéllez, Carlos$$uUniversidad de Zaragoza 000070693 700__ $$0(orcid)0000-0003-1512-4500$$aCoronas, Joaquín$$uUniversidad de Zaragoza 000070693 7102_ $$15005$$2555$$aUniversidad de Zaragoza$$bDpto. Ing.Quím.Tecnol.Med.Amb.$$cÁrea Ingeniería Química 000070693 773__ $$g19 (2017), [20 pp.]$$pCrystEngComm$$tCRYSTENGCOMM$$x1466-8033 000070693 8564_ $$s1041491$$uhttps://zaguan.unizar.es/record/70693/files/texto_completo.pdf$$yPostprint 000070693 8564_ $$s74233$$uhttps://zaguan.unizar.es/record/70693/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint 000070693 909CO $$ooai:zaguan.unizar.es:70693$$particulos$$pdriver 000070693 951__ $$a2019-07-09-12:02:36 000070693 980__ $$aARTICLE