Electrochemical deposition and characterization of AgPd alloy layers

Abstract

The AgPd alloys were electrodeposited onto Au and glassy carbon disc electrodes from the solution containing 0.001 mol dm-3 PdCl2 + 0.04 mol dm-3 AgCl + 0.1 mol dm-3 HCl + 12 mol dm-3 LiCl under the non-stationary diffusion (quiescent electrolyte) and convective diffusion (? = 1000 rpm) to the different amounts of charge and at different current densities. Electrodeposited alloy layers were characterized by the anodic linear sweep voltammetry (ALSV), scanning electron microscopy, energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The compositions of the AgPd alloys determined by the EDS were almost identical to the theoretically predicted ones, while the compositions obtained by XPS and ALSV analysis were similar to each other, but different from those obtained by EDS. Deviation from the theoretically predicted values (determined by the ratio jL(Pd)/j(Ag)) was more pronounced at lower current densities and lower charges of AgPd alloys electrodeposition, due to the lower current efficiencies for alloys electrodeposition. The ALSV analysis indicated the presence of Ag and Pd, expressed by two ALSV peaks, and in some cases the presence of the additional peak, which was found to correspond to the dissolution of large AgPd crystals, formed at thicker electrodeposits (higher electrodeposition charge), indicating, for the first time, that besides the phase structure, the morphology of alloy electrodeposit could also influence the shape of the ALSV response. In addition to Ag and Pd, the XPS analysis confirmed the presence of AgCl at the surface of samples electrodeposited to low thicknesses (amounts of charge).