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Characterisation of redox states of metal-organic frameworks by growth on modified thin-film electrodes

Mitra, Tamoghna; Moreau, Florian; Nevin, Adam; Perotto, Carlo U.; Summerfield, Alex; Davies, E. Stephen; Schröder, Martin; Gibson, Elizabeth; Easun, Timothy L.

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Authors

Tamoghna Mitra

Florian Moreau

Adam Nevin

Carlo U. Perotto

Alex Summerfield

Martin Schröder

Elizabeth Gibson

Timothy L. Easun



Abstract

The application of metal-organic framework (MOF) materials in electrochemical and electrochromic devices remain rare. One of the main reasons for this is the inability to readily access their detailed electrochemistry. The inherent insolubility of these materials does not allow interrogation by traditional solution-based electrochemical or spectroscopic methods. In this study, we report a straightforward alternative approach to the spectroelectrochemical study of MOFs. We have used two systems as exemplars in this study, MFM-186 and MFM-180. The method involves chemical modification of a working electrode to attach MOF materials without using corrosive reagents such as inorganic acids or bases which otherwise could limit their application in device development. MFM-186 demonstrates the formation of a stable radical species [MFM-186]●+ on electrochemical oxidation, and this has been characterised by electrochemical, spectroelectrochemical and EPR spectroscopic techniques coupled to DFT analysis.

Journal Article Type Article
Acceptance Date May 28, 2018
Online Publication Date Jun 4, 2018
Deposit Date Jul 16, 2018
Publicly Available Date Jul 16, 2018
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
DOI https://doi.org/10.1039/C8SC00803E
Public URL https://nottingham-repository.worktribe.com/output/936528
Publisher URL http://pubs.rsc.org/en/content/articlelanding/2018/sc/c8sc00803e#!divAbstract

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