Adiabatic versus non-adiabatic electron transfer at 2D electrode materials

Dan-Qing Liu, Minkyung Kang, David Perry, Chang-Hui Chen, Geoff West, Xue Xia, Shayantan Chaudhuri, Zachary P. L. Laker, Neil R. Wilson, Gabriel N. Meloni, Marko M. Melander (), Reinhard J. Maurer () and Patrick R. Unwin ()
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Dan-Qing Liu: University of Warwick
Minkyung Kang: University of Warwick
David Perry: University of Warwick
Chang-Hui Chen: University of Warwick
Geoff West: Warwick Manufacturing Group, University of Warwick
Xue Xia: University of Warwick
Shayantan Chaudhuri: University of Warwick
Zachary P. L. Laker: University of Warwick
Neil R. Wilson: University of Warwick
Gabriel N. Meloni: University of Warwick
Marko M. Melander: University of Jyväskylä
Reinhard J. Maurer: University of Warwick
Patrick R. Unwin: University of Warwick

Nature Communications, 2021, vol. 12, issue 1, 1-11

Abstract: 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.

Date: 2021
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DOI: 10.1038/s41467-021-27339-9

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