Deciphering the Interplay Between Local and Global Dynamics of Anodic Metal Dissolution

The stark difference between global and local metal dissolution dynamics underscores the need for methodologies capable of performing precise sub-µm-scale and wide-field measurements. In this study, we present Reflective Microscopy (RM) as a tool developed to address this challenge, illustrated by the example of chronoamperometric Fe oxidation in NaCl solution. Analysis at a local scale of 10s of µm has revealed three distinct periods of Fe oxidation: the initial covering of the metal interface with a surface film, followed by the electrochemical conversion of the formed surface film, and finally, the in-depth oxidation of Fe. In addition, thermodynamic calculations and the quantitative analysis of changes in optical signal (light intensity), correlated with variations in refractive indexes, suggests the initial formation of hematite, followed by its subsequent conversion to magnetite. The reactivity maps for all three periods are heterogeneous, which can be attributed to the preferential oxidation of certain crystallographic grains. Notably, at the global scale of 100s of µm, reactivity initiates at the electrode border and progresses towards its center, demonstrating a unique pattern that is independent of local metal structure. This finding underscores the significance of simultaneously employing sub-µm-precise and wide-field measurements for a comprehensive description of metal dissolution processes.