Silver UPD ultra-thin film modified nanoporous gold electrode with applications in the electrochemical detection of chloride

Nanoporous noble metals are usually expected to exhibit much higher surface areas than smooth ones, making them of particular importance in many electrochemical applications. This paper describes a simple electrochemical method to modify a nanoporous Au (NPG) surface by using an under potentially deposited (UPD) Ag adlayer. The NPG electrode was obtained by the dealloying of Zn from AuxZn1−x in a 40–60 mol% zinc chloride–1-ethyl-3-methylimidazolium chloride (ZnCl2–EMIC) ionic liquid. The Ag UPD modified nanoporous gold (NPG/Ag(UPD)) electrode possessed dual properties, including an intrinsic high surface area from the nanoporous structure and the characteristics of the Ag UPD adlayer. The potential utility of using NPG/Ag(UPD) for sensors was demonstrated by its excellent sensitivity and selectivity in the electrochemical determination of chloride ions. An atomic scale metal monolayer obtained in the UPD process was selected as a sensing agent. The long-term storability and operational stability of the electrode were strongly demonstrated. Specifically, two couples of redox waves at ∼552 mV and ∼272 mV, respectively, were observed in the cyclic voltammograms (CVs) of the NPG/Ag(UPD) after the adsorption of chloride ions. The first couple of redox waves was related to the UPD and silver stripping and the second couple of redox waves was induced by the adsorption of Cl−. The Cl− adsorption process on the NPG/Ag(UPD) electrode followed the transient Langmuir adsorption kinetic model. The ratio of the integrated charges for these two anodic stripping peaks was selectively used to determine dilute chloride ion levels. The calibration curve was linear in the Cl− concentration range of 0.5–30.0 μM.