Electrochemical fabrication of complex copper oxide nanoarchitectures via copper anodization in aqueous and non-aqueous electrolytes

Abstract

Described is the synthesis of various copper oxide nanostructured thin films by anodization of Cu foil in aqueous and ethylene glycol electrolytes containing hydroxide, chloride and/or fluoride ions at room temperature. The nanostructure topology was found to depend on the pH of the anodization electrolyte, KOH concentration, applied voltage and the presence of chloride and fluoride ions. Our results demonstrate the opportunity to grow complex copper oxide nanostructured films possessing sub-micron thick layers by a simple and straightforward electrochemical route. Although no film was observed on the Cu surface when the anodization was carried out at 10V in KOH solutions with pH≤10, various nanoarchitectures were formed upon increasing the electrolyte pH in the presence of chloride ions. Replacing chloride ions with fluoride ions resulted in the formation of highly porous nanoarchitectures. A simple mechanism for the formation of such porous structures is proposed. Anodizing in ethylene glycol-based electrolytes resulted in the formation of leaf-like nanoarchitectures up to 500nm in thickness. XPS analysis was performed to study the composition of the formed nanoarchitectures. Vacuum annealing of the material at 280°C resulted in the formation of porous Cu2O nanoarchitectures.