Sun, C. orcid.org/0000-0001-7307-5685, Pask, C.M. orcid.org/0000-0002-2241-5069, Pham, S.T. et al. (8 more authors) (2024) Modulating proton conductivity through crystal structure tuning in arenedisulfonate coordination polymers. Journal of Materials Chemistry A: materials for energy and sustainability. ISSN 2050-7488
Abstract
The functional group-directed structures of coordination polymers (CPs) and metal–organic frameworks (MOFs) have made them key candidates for proton exchange membranes in fuel cell technologies. Sulfonate group chemistry is well established in proton conducting polymers but has seen less exploration in CPs. Here, we report solvent-directed crystal structures of Cu²⁺ and Ca²⁺ CPs constructed with naphthalenedisulfonate (NDS) and anthraquinone-1,5-disulfonate (ADS) ligands, and we correlate single crystal structures across this set with proton conductivities determined by electrochemical impedance spectroscopy. Starting from the Cu²⁺-based NDS and aminotriazolate MOF designated Cu-SAT and the aqueous synthesis of the known Ca²⁺-NDS structure incorporating water ligands, we now report a further five sulfonate CP structures. These syntheses include a direct synthesis of the primary degradation product of Cu-SAT in water, solvent-substituted Ca-NDS structures prepared using dimethylformamide and dimethylsulfoxide solvents, and ADS variants of Cu-SAT and Ca-NDS. We demonstrate a consistent 2D layer motif in the NDS CPs, while structural modifications introduced by the ADS ligand result in a 2D hydrogen bonding network with Cu²⁺ and aminotriazolate ligands and a 1D CP with Ca²⁺ in water. Proton conductivities across the set span 10ˉ⁴ to >10ˉ³ S cmˉ¹ at 80 °C and 95% RH. These findings reveal an experimental structure–function relationship between proton conductivity and the tortuosity of the hydrogen bonding network and establish a general, cross-structure descriptor for tuning the sulfonate CP unit cell to systematically modulate proton conductivity.
Metadata
Item Type: | Article |
---|---|
Authors/Creators: |
|
Copyright, Publisher and Additional Information: | © The Royal Society of Chemistry 2024. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. |
Keywords: | Inorganic Chemistry; Macromolecular and Materials Chemistry; Chemical Sciences |
Dates: |
|
Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemical & Process Engineering (Leeds) The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > EPS Faculty Services (Leeds) |
Funding Information: | Funder Grant number EU - European Union EP/Y024583/1 EPSRC (Engineering and Physical Sciences Research Council) EP/V028855/1 |
Depositing User: | Symplectic Publications |
Date Deposited: | 09 Jul 2024 09:41 |
Last Modified: | 24 Jan 2025 11:04 |
Published Version: | https://pubs.rsc.org/en/content/articlelanding/202... |
Status: | Published online |
Publisher: | Royal Society of Chemistry |
Identification Number: | 10.1039/d4ta01716a |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:214050 |
Download
Filename: Modulating proton conductivity through crystal.pdf
Licence: CC-BY 3.0