Nanopatterning Palladium Surface Layers Through Electrochemical Deposition and Dissolution of Zinc in Ionic Liquid

Cracklike nanopatterned palladium surface layers have been produced by a green chemistry method based on in situ electrochemical deposition-dissolution of zinc (Zn-ECDD) in an ionic liquid bath. During the cathodic process, reactive Zn was electrochemically deposited onto a polycrystalline Pd substrate. During the subsequent anodic process, Zn was removed from the substrate through electrochemical dissolution. Scanning electron microscope (SEM) measurements showed that repetitive Zn-ECDD mediated by potential cycles results in the nanopatterning of Pd surface layers, characterized by uniform crack appearance with well-distributed concave spacings separated by nanowidth cracks. Energy-dispersive X-ray microscopy (EDX) studies revealed that the nanopatterned surface layers chemically contain a small amount of Zn. A mechanism based on the development of stress induced by the Zn-ECDD on Pd surfaces was proposed to be responsible for the nanopatterning of Pd surface layers. Electrochemical oxidation of formic acid and reduction of nitrite were studied as model reactions to demonstrate potential applications of the nanopatterned Pd electrode to electrocatalysis and electrochemical determination of environmental contaminants. Highly improved electrochemical responses were obtained on the nanopatterned Pd for the two reactions, compared to the untreated Pd.