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

Abstract

Three multi-carboxylic acid functionalised ligands have been designed, synthesised and utilised to synthesise 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 x10-5 and 5.1 x10-5 S cm-1, respectively) at 99RH% 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 x10-3 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 a synthetically challenging strategy to improve proton conductivity.

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Publication details

The article was received on 08 Jul 2018, accepted on 02 Nov 2018 and first published on 02 Nov 2018


Article type: Edge Article
DOI: 10.1039/C8SC03022G
Citation: Chem. Sci., 2019, Accepted Manuscript
  • Open access: Creative Commons BY license
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    Modulating proton diffusion and conductivity in metal-organic frameworks by incorporation of accessible free carboxylic acid groups

    P. Rought, C. Marsh, S. Pili, I. P. Silverwood, V. Garcia Sakai, M. Li, M. Brown, S. Argent, I. Vitorica-Yrzebal, G. F. S. Whitehead, M. R. Warren, S. Yang and M. Schroder, Chem. Sci., 2019, Accepted Manuscript , DOI: 10.1039/C8SC03022G

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