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

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

74 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.",

author = "Peter Rought and Christopher Marsh and Simona Pili and Silverwood, {Ian P.} and Sakai, {Victoria Garc{\'i}a} and Ming Li and Brown, {Martyn S.} and Argent, {Stephen P.} and Inigo Vitorica-Yrezabal and George Whitehead and Warren, {Mark R.} and Sihai Yang and Martin Schr{\"o}der",

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doi = "10.1039/c8sc03022g",

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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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