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Modulating proton diffusion and conductivity in metal–organic frameworks by incorporation of accessible free carboxylic acid groups

Rought, Peter; Marsh, Christopher; Pili, Simona; Silverwood, Ian P.; Sakai, Victoria García; Li, Ming; Brown, Martyn S.; Argent, Stephen P.; Vitorica-Yrezabal, Inigo; Whitehead, George; Warren, Mark R.; Yang, Sihai; Schröder, Martin

Modulating proton diffusion and conductivity in metal–organic frameworks by incorporation of accessible free carboxylic acid groups Thumbnail


Authors

Peter Rought

Christopher Marsh

Simona Pili

Ian P. Silverwood

Victoria García Sakai

MING LI MING.LI@NOTTINGHAM.AC.UK
Associate Professor

Martyn S. Brown

Inigo Vitorica-Yrezabal

George Whitehead

Mark R. Warren

Sihai Yang

Martin Schröder



Abstract

Three multi-carboxylic acid functionalised ligands have been designed, synthesised and utilised to prepare the new barium-based MOFs, MFM-510, -511, and -512, which show excellent stability to water-vapour. MFM-510 and MFM-511 show moderate proton conductivities (2.1 × 10−5 and 5.1 × 10−5 S cm−1, respectively) at 99% RH and 298 K, attributed to the lack of free protons or hindered proton diffusion within the framework structures. In contrast, MFM-512, which incorporates a pendant carboxylic acid group directed into the pore of the framework, shows a two orders of magnitude enhancement in proton conductivity (2.9 × 10−3 S cm−1). Quasi-elastic neutron scattering (QENS) suggests that the proton dynamics of MFM-512 are mediated by “free diffusion inside a sphere” confirming that incorporation of free carboxylic acid groups within the pores of MOFs is an efficient albeit synthetically challenging strategy to improve proton conductivity.

Citation

Rought, P., Marsh, C., Pili, S., Silverwood, I. P., Sakai, V. G., Li, M., …Schröder, M. (2018). Modulating proton diffusion and conductivity in metal–organic frameworks by incorporation of accessible free carboxylic acid groups. Chemical Science, 10(5), 1492-1499. https://doi.org/10.1039/c8sc03022g

Journal Article Type Article
Acceptance Date Nov 2, 2018
Online Publication Date Nov 2, 2018
Publication Date Nov 2, 2018
Deposit Date Dec 23, 2018
Publicly Available Date Mar 29, 2024
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
Volume 10
Issue 5
Pages 1492-1499
DOI https://doi.org/10.1039/c8sc03022g
Keywords General Chemistry
Public URL https://nottingham-repository.worktribe.com/output/1417640
Publisher URL https://pubs.rsc.org/en/Content/ArticleLanding/2019/SC/C8SC03022G#!divAbstract

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