A Comparison between Porous to Fully Dense Electrodeposited CuNi Films: Insights on Electrochemical Performance.

Nanostructuring of metals is nowadays considered as a promising strategy towards the development of materials with enhanced electrochemical performance. Porous and fully dense CuNi films were electrodeposited on a Cu plate by electrodeposition in view of their application as electrocatalytic materials for the hydrogen evolution reaction (HER). Porous CuNi film were synthesized using the hydrogen bubble template electrodeposition method in an acidic electrolyte, while fully dense CuNi were electrodeposited from a citrate-sulphate bath with the addition of saccharine as a grain refiner. The prepared films were characterized chemically and morphologically by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD). The Rietveld analysis of the XRD data illustrates that both CuNi films have a nanosized crystallite size. Contact angle measurements reveal that the porous CuNi film exhibits remarkable superhydrophobic behavior, and fully dense CuNi film shows hydrophilicity. This is predominately ascribed to the surface roughness of the two films. The HER activity of the two prepared CuNi films were investigated in 1 M KOH solution at room temperature by polarization measurements and electrochemical impedance spectroscopy (EIS) technique. Porous CuNi exhibits an enhanced catalysis for HER with respect to fully dense CuNi. The HER kinetics for porous film is processed by the Volmer-Heyrovsky reaction, whereas the fully dense counterpart is Volmer-limited. This study presents a clear comparison of HER behavior between porous and fully dense CuNi films.