A1 Journal article (refereed)
Adiabatic versus non-adiabatic electron transfer at 2D electrode materials (2021)

Liu, D.-Q., Kang, M., Perry, D., Chen, C.-H., West, G., Xia, X., Chaudhuri, S., Laker, Z. P. L., Wilson, N. R., Meloni, G. N., Melander, M. M., Maurer, R. J., & Unwin, P. R. (2021). Adiabatic versus non-adiabatic electron transfer at 2D electrode materials. Nature Communications, 12, Article 7110. https://doi.org/10.1038/s41467-021-27339-9

JYU authors or editors

Melander, Marko

Publication details

All authors or editors: Liu, Dan-Qing; Kang, Minkyung; Perry, David; Chen, Chang-Hui; West, Geoff; Xia, Xue; Chaudhuri, Shayantan; Laker, Zachary P. L.; Wilson, Neil R.; Meloni, Gabriel N.; et al.

Journal or series: Nature Communications

eISSN: 2041-1723

Publication year: 2021

Volume: 12

Article number: 7110

Publisher: Nature Publishing Group

Publication country: United Kingdom

Publication language: English

DOI: https://doi.org/10.1038/s41467-021-27339-9

Publication open access: Openly available

Publication channel open access: Open Access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/79286

Publication is parallel published: https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8651748/

Abstract

2D electrode materials are often deployed on conductive supports for electrochemistry and there is a great need to understand fundamental electrochemical processes in this electrode configuration. Here, an integrated experimental-theoretical approach is used to resolve the key electronic interactions in outer-sphere electron transfer (OS-ET), a cornerstone elementary electrochemical reaction, at graphene as-grown on a copper electrode. Using scanning electrochemical cell microscopy, and co-located structural microscopy, the classical hexaamineruthenium (III/II) couple shows the ET kinetics trend: monolayer > bilayer > multilayer graphene. This trend is rationalized quantitatively through the development of rate theory, using the Schmickler-Newns-Anderson model Hamiltonian for ET, with the explicit incorporation of electrostatic interactions in the double layer, and parameterized using constant potential density functional theory calculations. The ET mechanism is predominantly adiabatic; the addition of subsequent graphene layers increases the contact potential, producing an increase in the effective barrier to ET at the electrode/electrolyte interface.

Keywords: electrochemistry; electrodes; graphene; density functional theory

Fields of science: