Issue 6, 2023

On the mechanistic complexity of oxygen evolution: potential-dependent switching of the mechanism at the volcano apex

Abstract

The anodic four-electron oxygen evolution reaction (OER) corresponds to the limiting process in acidic or alkaline electrolyzers to produce gaseous hydrogen at the cathode of the device. In the last decade, tremendous efforts have been dedicated to the identification of active OER materials by electronic structure calculations in the density functional theory approximation. Most of these works rely on the assumption that the mononuclear mechanism, comprising the *OH, *O, and *OOH intermediates, is operative under OER conditions, and that a single elementary reaction step (most likely *OOH formation) governs the kinetics. In the present manuscript, six different OER mechanisms are analyzed, and potential-dependent volcano curves are constructed to comprehend the electrocatalytic activity of these pathways in the approximation of the descriptor Gmax(U), a potential-dependent activity measure based on the notion of the free-energy span model. While the mononuclear description mainly describes the legs of the volcano plot, corresponding to electrocatalysts with low intrinsic activity, it is demonstrated that the preferred pathway at the volcano apex is a strong function of the applied electrode potential. The observed mechanistic complexity including a switch of the favored pathway with increasing overpotential sets previous investigations aiming at the identification of reaction mechanisms and limiting steps into question since the entire breadth of OER pathways was not accounted for. A prerequisite for future atomic-scale studies on highly active OER catalysts refers to the evaluation of several mechanistic pathways so that neither important mechanistic features are overlooked nor limiting steps are incorrectly determined.

Graphical abstract: On the mechanistic complexity of oxygen evolution: potential-dependent switching of the mechanism at the volcano apex

Supplementary files

Article information

Article type
Communication
Submitted
11 1 2023
Accepted
20 2 2023
First published
17 3 2023
This article is Open Access
Creative Commons BY-NC license

Mater. Horiz., 2023,10, 2086-2095

On the mechanistic complexity of oxygen evolution: potential-dependent switching of the mechanism at the volcano apex

K. S. Exner, Mater. Horiz., 2023, 10, 2086 DOI: 10.1039/D3MH00047H

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party commercial publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements