Abstract
Cyclic voltammetry and linear sweep voltammetry with an ultramicroelectrode (UME) were employed to study Zn and Mg electrodeposition and the corresponding mechanistic pathways. CVs obtained at a Pt UME for Zn electroreduction from a trifluoromethylsulfonyl imide (TFSI–) and chloride-containing electrolyte in acetonitrile exhibit current densities that are scan rate independent, as expected for a simple electron transfer at a UME. However, CVs obtained from three different Mg-containing electrolytes in THF exhibit an inverse dependence between scan rate and current density. COMSOL-based simulation suggests that Zn electrodeposition proceeds via a simple one-step, two-electron transfer (E) mechanism. Alternatively, the Mg results are best described by invoking a chemical step prior to electron transfer: a chemical–electrochemical (CE) mechanism. The chemical step exhibits an activation energy of 51 kJ/mol. This chemical step is likely the disproportionation of the chloro-bridged dimer [Mg2(μ–Cl)3·6THF]+ pre...
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