Synchrotron-based in situ soft X-ray microscopy of Ag corrosion in aqueous chloride solution

In this paper we report an in situ X-ray microscopy study of a model metal electrochemistry system, incorporating faradaic reactivity: the anodic corrosion and cathodic electrodeposition of Ag in aqueous systems. The information at sub-rim scale about morpho-chemical evolution of the electrified interface, provided by this novel electroanalytical approach fosters fundamental understanding of important issues concerning material fabrication and stability, which are crucial in developing the next generation electrochemical technologies, such as fuel cells and biosensors. The key methodology challenge faced in this pilot electrochemical experiments is combining a three-electrode configuration and wet environment, which required metal electrodes suitable for transmitting soft X-rays and a sealed cell allowing working in high vacuum. This has been solved via lithographic fabrication route fabricating 75 nm thick Ag electrodes and using Si3N4 membranes as X-ray windows and electrode support. Imaging in the STXM mode with phase contrast allowed us to monitor the corrosion morphologies and metal outgrowth features. Localised thickness variation and the build-up of reaction products of electron density different from that of the starting material have been detected with high sensitivity.