Jinzhen Huang^1*, Adam H. Clark^2*, Natasha Hales^1*, Kenneth Crossley^1*, Julie Guehl^1*, Radim Skoupy^3*, Thomas J. Schmidt^1,4*, Emiliana Fabbri^1*

1 PSI Center for Energy and Environmental Sciences , Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland

2 PSI Center for Photon Sciences, Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland

3 PSI Center for Life Sciences, Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland

4 Institute for Physical Molecular Sciences, ETH Zürich, CH-8093 Zürich, Switzerland

* Corresponding authors emails: jinzhen.huang@psi.ch, adam.clark@psi.ch, natasha.hales@psi.ch, kenneth.crossley@psi.ch, julie.guehl@etu.unistra.fr, radim.skoupy@psi.ch, thomasjustus.schmidt@psi.ch, emiliana.fabbri@psi.ch

DOI10.24435/materialscloud:33-ch [version v1]

Publication date: Mar 17, 2025

How to cite this record

Jinzhen Huang, Adam H. Clark, Natasha Hales, Kenneth Crossley, Julie Guehl, Radim Skoupy, Thomas J. Schmidt, Emiliana Fabbri, Oxidation of interfacial cobalt controls the pH-dependence of the oxygen evolution reaction, Materials Cloud Archive 2025.40 (2025), https://doi.org/10.24435/materialscloud:33-ch

Description

Transition metal oxides (e.g., cobalt oxides) often undergo a dynamic surface reconstruction under oxygen evolution reaction (OER) conditions to form the active state, which differs in response to the electrolyte pH. The resulting pH-dependency of OER activity is commonly observed but poorly understood. Herein, we demonstrate that operando X-ray absorption spectroscopy (XAS) characterization enables tracking of the Co oxidation transformation at different pH-directed (hydr)oxide/electrolyte interfaces. Combined with in situ electrochemical analyses, correlations between Co redox dynamics, flat band potential and Co oxidation transformations are established to explain the pH-dependency of OER activity. In alkaline environments, the low flat band potential allows a low-potential Co redox transformation, which in turns favors surface reconstruction. In neutral and acidic environments, an anodic shift of the Co redox transformation increases the OER overpotential, particularly in an acidic environment. The largest OER overpotential, in a neutral environment, is further attributable to the poor polarizability of Co atoms and the slowest Co oxidation transformation with respect to the change in applied potential (or OER current). These findings reveal that the Co oxidation transformation at the interface is the factor directly determining the pH-dependency of OER activity, therefore providing insight into designing efficient OER catalysts in different pH environments.

Materials Cloud sections using this data

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Keywords

Oxygen evolution reaction Operando X-ray adsorption spectroscopy Cobalt Oxides Electrocatalytic interface