Insights into Chemical Changes Causing Transient Potential Patterns during Cobalt Electrodeposition: An Operando SHINERS Investigation.

Abstract

Transient potential oscillations in a self-organized system involve a sequence of mass-transfer-limited chemical reactions. Often, these oscillations determine the microstructure of the electrodeposited metallic films. In this study, two distinct potential oscillations have been observed during galvanostatic deposition of cobalt in the presence of butynediol. Understanding the underlying chemical reactions in these potential oscillations is essential for designing efficient electrodeposition systems. Operando shell-isolated nanoparticle-enhanced Raman spectroscopy is deployed to record these chemical changes, and we present direct spectroscopic evidence of adsorbed hydrogen scavenging by butynediol, Co(OH)2 formation, and removal limited by mass transfer of butynediol and protons. The potential oscillatory patterns have four distinguishable segments associated with mass-transfer limitation of either proton or butynediol. These observations improve our understanding of the oscillatory behavior in metal electrodeposition.