Nanoporous gold microelectrode prepared from potential modulated electrochemical alloying–dealloying in ionic liquid

• A green chemistry method for producing nanoporous gold microelectrode was studied.
• An ionic liquid plating bath was utilized for electrochemical alloying–dealloying.
• Nanostructures of gold surface layers can be tuned by modulating potential.
• Nanoporous gold microelectrode has high surface area and merit of a microelectrode.
• Nitrite oxidation and reduction on nanoporous gold microelectrode were studied.

Nanoporous gold (NPG) microelectrodes with high surface area and open pore network were successfully prepared by applying modulated potential to a polycrystalline Au-disk microelectrode in ionic liquid electrolyte containing ZnCl2 at elevated temperature. During cathodic process, Zn is electrodeposited and interacted with Au microdisk substrate to form a AuZn alloy phase. During subsequent anodic process, Zn is selectively dissolved from the alloy phase, leading to the formation of a NPG layer which can grow with repetitive potential modulation. Scanning-electron microscope and energy dispersive X-ray microscope measurements show that the NPG microelectrodes possessing nanoporous structures can be tuned via potential modulation, and chemically contain a small amount of Zn whose presence has no obvious influence on electrochemical responses of the electrodes. Steady-state and cyclic voltammetric studies suggest that the NPG microelectrodes have high surface area and keep diffusional properties of a microelectrode. Electrochemical nitrite reduction and oxidation are studied as model reactions to demonstrate potential applications of the NPG microelectrodes in electrocatalysis and electroanalysis. These facts suggest that the potential-modulated electrochemical alloying/dealloying in ionic liquid electrolyte offers a convenient green-chemistry method for the preparation of nanoporous microelectrodes.