The Oxygen Evolution Reaction Drives Passivity Breakdown for Ni-Cr-Mo Alloys.

Corrosion is the main factor limiting the lifetime of metallic materials, and a fundamental understanding of the governing mechanism and surface processes is difficult to achieve since the thin oxide films at the metal-liquid interface governing passivity are notoriously challenging to study. Here, a combination of synchrotron-based techniques and electrochemical methods are used to investigate the passive film breakdown of a Ni-Cr-Mo alloy used in many industrial applications. This alloy is found to be active toward oxygen evolution reaction (OER), and the OER onset coincides with the loss of passivity and severe metal dissolution. The OER mechanism involves the oxidation of Mo sites in the oxide film to Mo that can be dissolved, which results in passivity breakdown. This is fundamentally different from typical transpassive breakdown of Cr-containing alloys where Cr is postulated to be dissolved at high anodic potentials, which was not observed here. At high current densities, OER also leads to acidification of the solution near the surface, further triggering metal dissolution. OER plays an important role in the mechanism of passivity breakdown of Ni-Cr-Mo alloys due to their catalytic activity, and this effect needs to be considered when studying the corrosion of catalytically active alloys. This article is protected by copyright. All rights reserved.