Assessment of the roughness factor effect and the intrinsic catalytic activity for hydrogen evolution reaction on Ni-based electrodeposits

The hydrogen evolution reaction (HER) was studied in 30 wt.% KOH solution at temperatures ranging between 30 and 80 °C on three type of electrodes: (i) rough pure Ni electrodeposits, obtained by applying a large current density; (ii) smooth NiCo electrodeposits; (iii) smooth commercial Ni electrodes. By using steady-state polarization curves and electrochemical impedance spectroscopy (EIS) the surface roughness factor and the intrinsic activities of the catalytic layers were determined. These techniques also permitted us to determine the mechanism and kinetics of the HER on the investigated catalysts. Different AC models were tested and the appropriate one was selected. The overall experimental data indicated that the rough/porous Ni electrode yields the highest electrocatalytic activity in the HER. Nevertheless, when the effect of the surface roughness was taken into consideration, it was demonstrated that alloying Ni with Co results in an increased electrocatalytic activity in the HER when comparing to pure Ni. This is due to an improved intrinsic activity of the material, which was explained on the basis of the synergism among the catalytic properties of Ni (low hydrogen overpotential) and of Co (high hydrogen adsorption).

► Electrocatalytic activity of pure Ni porous layers and smooth NiCo alloys.
► The surface roughness factor and the intrinsic catalytic activity were determined.
► The HER is controlled by the Volmer reaction step.
► Surface area determines the electrocatalytic activity of Ni deposited at high current density.
► Allowing Ni with Co results in an increased intrinsic electrocatalytic activity.