Issue 12, 2025

Beyond diffusion: ion and electron migration contribute to charge transport in redox-conducting metal–organic frameworks

Abstract

Electrical conductivity through redox conducting MOFs (RCMOFs) proceeds by electron hopping between linkers of differing oxidation states. While this process is treated as a purely diffusional process in the literature, we show herein that this prevalent description is an oversimplification, and that emerging electric fields under applied potential result in electron and ion migration which are sizable contributors to charge transport through RCMOFs. This insight is obtained by electrochemical experiments that are conducted under steady-state conditions, which are created by the addition of an electron acceptor to the electrolyte solution, effectively creating a source-drain architecture of the electrode|RCMOF|electrolyte system. In contrast to transient potential-step experiments, such as chronoamperometry that are ubiquitous in the literature, the steady-state conditions in our experiments avoid net ingress or exit of charge balancing counter ions, allowing the assessment of electron diffusion with negligible counter ion flux. The strategy effectively isolates the diffusional response from ion diffusion–migration and electric field effects. Most importantly, it is shown that for transient experiments, the additional flux from migration, resulting from emerging electric fields after the potential step, leads to an overestimation of the experimentally determined apparent diffusion coefficients. The work described herein also demonstrates that the separate determination of electron and ion diffusion through RCMOFs is challenging with simplified models, as the two processes are connected through migration.

Graphical abstract: Beyond diffusion: ion and electron migration contribute to charge transport in redox-conducting metal–organic frameworks

Supplementary files

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Article information

Article type
Edge Article
Submitted
05 Dec 2024
Accepted
13 Feb 2025
First published
14 Feb 2025
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2025,16, 5214-5222

Beyond diffusion: ion and electron migration contribute to charge transport in redox-conducting metal–organic frameworks

B. A. Johnson, A. T. Castner, H. Agarwala and S. Ott, Chem. Sci., 2025, 16, 5214 DOI: 10.1039/D4SC08246J

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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