Key activity descriptors of nickel-iron oxygen evolution electrocatalysts in the presence of alkali metal cations

Mikaela Görlin (), Joakim Halldin Stenlid, Sergey Koroidov, Hsin-Yi Wang, Mia Börner, Mikhail Shipilin, Aleksandr Kalinko, Vadim Murzin, Olga V. Safonova, Maarten Nachtegaal, Abdusalam Uheida, Joydeep Dutta, Matthias Bauer, Anders Nilsson and Oscar Diaz-Morales ()
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Mikaela Görlin: Stockholm University
Joakim Halldin Stenlid: Stockholm University
Sergey Koroidov: Stockholm University
Hsin-Yi Wang: Stockholm University
Mia Börner: Stockholm University
Mikhail Shipilin: Stockholm University
Aleksandr Kalinko: University of Paderborn
Vadim Murzin: Deutsches Elektronen-Synchrotron DESY
Olga V. Safonova: Paul Scherrer Institute
Maarten Nachtegaal: Paul Scherrer Institute
Abdusalam Uheida: Functional Materials, Department of Applied Physics, School of Engineering Sciences, KTH Royal Institute of Technology
Joydeep Dutta: Functional Materials, Department of Applied Physics, School of Engineering Sciences, KTH Royal Institute of Technology
Matthias Bauer: University of Paderborn
Anders Nilsson: Stockholm University
Oscar Diaz-Morales: Stockholm University

Nature Communications, 2020, vol. 11, issue 1, 1-11

Abstract: Abstract Efficient oxygen evolution reaction (OER) electrocatalysts are pivotal for sustainable fuel production, where the Ni-Fe oxyhydroxide (OOH) is among the most active catalysts for alkaline OER. Electrolyte alkali metal cations have been shown to modify the activity and reaction intermediates, however, the exact mechanism is at question due to unexplained deviations from the cation size trend. Our X-ray absorption spectroelectrochemical results show that bigger cations shift the Ni2+/(3+δ)+ redox peak and OER activity to lower potentials (however, with typical discrepancies), following the order CsOH > NaOH ≈ KOH > RbOH > LiOH. Here, we find that the OER activity follows the variations in electrolyte pH rather than a specific cation, which accounts for differences both in basicity of the alkali hydroxides and other contributing anomalies. Our density functional theory-derived reactivity descriptors confirm that cations impose negligible effect on the Lewis acidity of Ni, Fe, and O lattice sites, thus strengthening the conclusions of an indirect pH effect.

Date: 2020
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DOI: 10.1038/s41467-020-19729-2

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