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

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.