Electrochemical Behavior of Nanostructured Fe-Pd Alloy During Electrodeposition on Different Substrates

In this work, Fe-Pd alloy films have been electrodeposited on different substrates using an electrolyte containing $[Pd(NH_3)_4]^{2+}$ (0.02 M) and $[Fe-Citrate]^{2+}$ (0.2 M). The influences of substrate and overpotential on chemical composition, nucleation and growth kinetics as well as the electrodeposited films morphology have been investigated using energy dispersive X-ray spectroscopy (EDS), current-time transients, scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD) patterns. In all substrates - brass, copper and sputtered fluorine doped tin oxide on glass (FTO/glass) - Fe content of the electrodeposited alloys increases by increasing the overpotential. Also the cathodic current efficiency is low due to high rate of $H_2$ co-reduction. Regarding the chronoamperometry current-time transients, it has been demonstrated that the nucleation mechanism is instantaneous with a typical three dimensional (3D) diffusion-controlled growth in the case of brass and copper substrates; while for FTO, the growth mode changes to 3D progressive. At a constant overpotential, the calculated number of active nucleation sites for metallic substrates is much higher than that of FTO/glass; however by increasing the overpotential, the number of active nucleation sites increases. The SEM micrographs as well as the XRD patterns reveal the formation of Fe-Pd alloy thin films with nanostructure arrangement and ultra-fine grains.