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

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

doi:10.1039/c8sc03022g

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

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

Department of Chemistry

University of Manchester
Rutherford Appleton Laboratory
University of Nottingham
University of Warwick
Diamond Light Source Ltd

Research output: Contribution to journal › Article › peer-review

90 Citations (SciVal)

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.

Original language	English
Pages (from-to)	1492-1499
Number of pages	8
Journal	Chemical Science
Volume	10
Issue number	5
DOIs	https://doi.org/10.1039/c8sc03022g
Publication status	Published - 2019

Funding

We thank EPSRC (EP/I011870, EP/P001386), ERC (AdG 742041), Royal Society and University of Manchester for funding. We are especially grateful to STFC/ISIS Neutron Facility for access to the Beamline IRIS (RB 1620036, DOI: 10.5286/ISIS.E.84764508) and to Diamond Light Source for access to Beamline I19.

ASJC Scopus subject areas

General Chemistry

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Rought, P., Marsh, C., Pili, S., Silverwood, I. P., Sakai, V. G., Li, M., Brown, M. S., Argent, S. P., Vitorica-Yrezabal, I., Whitehead, G., Warren, M. R., Yang, S., & Schröder, M. (2019). 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

Rought, P, Marsh, C, Pili, S, Silverwood, IP, Sakai, VG, Li, M, Brown, MS, Argent, SP, Vitorica-Yrezabal, I, Whitehead, G, Warren, MR, Yang, S & Schröder, M 2019, 'Modulating proton diffusion and conductivity in metal-organic frameworks by incorporation of accessible free carboxylic acid groups', Chemical Science, vol. 10, no. 5, pp. 1492-1499. https://doi.org/10.1039/c8sc03022g

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title = "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 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.",

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year = "2019",

doi = "10.1039/c8sc03022g",

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AU - Rought, Peter

AU - Marsh, Christopher

AU - Pili, Simona

AU - Silverwood, Ian P.

AU - Sakai, Victoria García

AU - Li, Ming

AU - Brown, Martyn S.

AU - Argent, Stephen P.

AU - Vitorica-Yrezabal, Inigo

AU - Whitehead, George

AU - Warren, Mark R.

AU - Yang, Sihai

AU - Schröder, Martin

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N2 - 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.

AB - 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.

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

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