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Cleaving carboxyls: understanding thermally triggered hierarchical pores in the metal-organic framework MIL-121

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Show simple item record Chen, Shoushun Mukherjee, Soumya Lucier, Bryan E.G. Guo, Ying Tung, Ying Wong, Angel Terskikh, Victor V. Zaworotko, Michael J. Huang, Yining 2019-09-26T11:23:28Z 2019
dc.description peer-reviewed en_US
dc.description The full text of this article will not be available in ULIR until the embargo expires on the 19/08/2020
dc.description.abstract Carboxylic acid linker ligands are known to form strong metalcarboxylate bonds to afford many different variations of permanently microporous metal-organic frameworks (MOFs). A controlled approach to decarboxylation of the ligands in carboxylate-based MOFs could result in structural modifications, offering scope to improve existing properties or to unlock entirely new properties. In this work, we demonstrate that the microporous MOF MIL-121 is transformed to a hierarchically porous MOF via thermally triggered decarboxylation of its linker. Decarboxylation and the introduction of hierarchical porosity increases the surface area of this material from 13 m2/g to 908 m2/g, and enhances gas adsorption uptake for industrially relevant gases (i.e., CO2, C2H2, C2H4 and CH4). For example, CO2 uptake in hierarchically porous MIL-121 is improved 8.5 times over MIL-121, reaching 215.7 cm3/g at 195 K and 1 bar; CH4 uptake is 132.3 cm3/g at 298 K and 80 bar in hierarchically porous MIL-121 versus zero in unmodified MIL-121. The approach taken was validated using a related aluminum based MOF, ISOMIL-53. However, many specifics of the decarboxylation procedure in MOFs have yet to be unraveled and demand prompt examination. Decarboxylation, the formation of heterogeneous hierarchical pores, gas uptakes, and host-guest interactions are comprehensively investigated using variable temperature multinuclear solid-state NMR spectroscopy, Xray diffraction, electron microscopy, and gas adsorption; we propose a mechanism for decarboxylation proceeds and which local structural features are involved. Understanding the complex relationship between molecular-level MOF structure, thermal stability, and the decarboxylation process is essential to fine-tune MOF porosity, thus offering a systematic approach to the design of hierarchically porous, custom-built MOFs suited for targeted applications. en_US
dc.language.iso eng en_US
dc.publisher American Chemical Society en_US
dc.relation 13RPB2549 en_US
dc.relation.ispartofseries Journal of the American Chemical Society;141 (36), pp. 14257-14271
dc.rights © 2019 ACS This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal Title, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see en_US
dc.subject ligands en_US
dc.title Cleaving carboxyls: understanding thermally triggered hierarchical pores in the metal-organic framework MIL-121 en_US
dc.type info:eu-repo/semantics/article en_US
dc.type.supercollection all_ul_research en_US
dc.type.supercollection ul_published_reviewed en_US
dc.identifier.doi 10.1021/jacs.9b06194
dc.contributor.sponsor SFI en_US
dc.contributor.sponsor Natural Science and Engineering Research Council (NSERC) of Canada en_US
dc.contributor.sponsor National Research Council Canada (NRC) en_US
dc.contributor.sponsor Natural Science Foundation of China en_US
dc.relation.projectid 13/RP/B2549 en_US
dc.relation.projectid 16/IA/4624 en_US
dc.relation.projectid NSFC51472021 en_US
dc.relation.projectid 12060093063 en_US 2020-08-19
dc.embargo.terms 2020-08-19 en_US
dc.rights.accessrights info:eu-repo/semantics/embargoedAccess en_US

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