Influence of the Amide Groups in the CO2/N2 Selectivity of a Series of Isoreticular, Interpenetrated Metal–Organic Frameworks

Here we report the use of a pillaring strategy for the design and synthesis of three novel amide-functionalized metal–organic frameworks (MOFs), TMUs-22/-23/-24, isoreticular to the recently reported imine-functionalized TMU-6 and TMU-21 MOFs. An extensive study of their CO2 sorption properties and selectivity for CO2 over N2, from single gas sorption isotherms to breakthrough measurements, revealed that not only the incorporation of amide groups but also their accessibility is crucial to obtain enhanced CO2 sorption and CO2/N2 selectivity. Therefore, the MOF with more accessible amide groups (TMU-24) shows a CO2/N2 selectivity value of ca. 10 (as revealed by breakthrough experiments), which is ca. 500% and 700% of the selectivity values observed for the other amide-containing (TMU-22 and TMU-23) and imine-containing (TMU-6 and TMU-21) MOFs.This work was supported by the Spanish MINECO (projects PN MAT2015-65354-C2-1-R and MAT2013-45008-P), the Catalan AGAUR (project 2014 SGR 80), and the ERC under the EU FP7 (ERC-Co 615954). I.I. and E.V.R.F. thank the MINECO for their RyC fellowships RYC-2010-06530 and RyC-2012-11427 and V.G. is grateful to the Generalitat de Catalunya for a Beatriu de Pinós Fellowship (2014 BP-B 00155). ICN2 acknowledges the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program, under Grant SEV-2013-0295. E.V.R.F. and J.S.A. acknowledge the Generalitat Valenciana for PROMETEOII/2014/004. Support of this investigation by Tarbiat Modares University is gratefully acknowledged