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

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dc.contributor.author Chen, Shoushun
dc.contributor.author Mukherjee, Soumya
dc.contributor.author Lucier, Bryan E.G.
dc.contributor.author Guo, Ying
dc.contributor.author Tung, Ying
dc.contributor.author Wong, Angel
dc.contributor.author Terskikh, Victor V.
dc.contributor.author Zaworotko, Michael J.
dc.contributor.author Huang, Yining
dc.date.accessioned 2019-09-26T11:23:28Z
dc.date.issued 2019
dc.identifier.uri http://hdl.handle.net/10344/8078
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.relation.uri https://doi.org/10.1021/jacs.9b06194
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 https://doi.org/10.1021/jacs.9b06194 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
dc.date.embargoEndDate 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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