Manipulating Intermetallic Charge Transfer for Switchable External Stimulus-Enhanced Water Oxidation Electrocatalysis

Electrocatalytic processes involving the oxygen evolution reaction (OER) present a kinetic bottleneck due to the existence of linear-scaling relationships, which bind the energies of the different intermediates in the mechanism limiting optimization. Here, we offer a way to break these scaling relat...

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Veröffentlicht in:Angewandte Chemie International Edition 2023-10, Vol.62 (44), p.e202308647-e202308647
Hauptverfasser: Chalil Oglou, Ramadan, Ulusoy Ghobadi, T Gamze, Hegner, Franziska Simone, Galán-Mascarós, José Ramón, López, Núria, Ozbay, Ekmel, Karadas, Ferdi
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Sprache:eng
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Zusammenfassung:Electrocatalytic processes involving the oxygen evolution reaction (OER) present a kinetic bottleneck due to the existence of linear-scaling relationships, which bind the energies of the different intermediates in the mechanism limiting optimization. Here, we offer a way to break these scaling relationships and enhance the electrocatalytic activity of a Co-Fe Prussian blue modified electrode in OER by applying external stimuli. Improvements of ~11% and ~57% were achieved under magnetic field (0.2 T) and light irradiation (100 mW.cm-2), respectively, when working at fixed overpotential, ƞ = 0.6 V at pH 7. The observed enhancements strongly tie in with the intermetallic charge transfer (IMCT) intensity between Fe and Co sites. Density Functional Theory simulations suggest that tuning the IMCT can lead to a change of the OER mechanism to an external stimuli-sensitive spin crossover-based pathway, which opens the way for switchable electrocatalytic devices.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202308647