Modification of the Electrolyte/Electrode Interface for the Template-free Electrochemical Synthesis of Metal Nanowires from Ionic Liquids.

In electrochemistry, the electrode/electrolyte interface (EEI) governs the charge/mass-transfer processes and controls the nucleation/growth phenomena. The EEI in ionic liquids (ILs) can be controlled by changing the cation/anion of the IL, salt concentration, electrode potential, and temperature. Here, we show that adding a dopant salt leads to the deposition of nanowires. To illustrate, zinc nanowires were electrodeposited from ZnCl2/1-butyl-1-methylpyrrolidinium trifluoromethylsulfonate in the presence of GaCl3 as a dopant salt. The choice of Zn salt and its ratio to GaCl3 were found to be crucial for Zn nanowires formation. AFM studies revealed that the solvation structure of Au(111)/IL changes significantly in the presence of GaCl3 and ZnCl2. Chronoamperometry showed changes in the nucleation/growth process, consequently leading to the formation of nanowires. A similar approach was adopted to synthesize Sn nanowires. Thus, modification of the EEI by adding a dopant to ILs can be a viable method to obtain nanowires.