Design of Highly Active Electrodes for Hydrogen Evolution Reaction Based on Mo-Rich Alloys Electrodeposited from Ammonium Acetate Bath

The given research was driven by prospects to design Mo-rich coatings with iron group metals electrodeposited from a highly saturated ammonium acetate bath. The obtained coatings could be employed as prominent electrodes for the hydrogen evolution reaction (HER). It was found that the Mo content in Ni–Mo alloys can be tuned from 30 to 78 at.% by decreasing the molar ratio [Ni(II)]:[Mo(VI)] in the electrolyte from 1.0 to 0.25 and increasing the cathodic current density from 30 to 100 mA/cm2. However, dense cracks and pits are formed due to hydrogen evolution at high current densities and that diminishes the catalytic activity of the coating for HER. Accordingly, smoother and crack-free Ni–54 at.% Mo, Co–52 at.% Mo and Fe–54 at.% Mo alloys have been prepared at 30 mA/cm2. Their catalytic behavior for HER has been investigated in a 30 wt.% NaOH solution at temperatures ranging from 25 to 65 °C. A significant improvement of electrocatalytic activity with increasing bath temperature was noticed. The results showed that the sequence of electrocatalytic activity in alkaline media decreases in the following order: Co–52 at.% Mo > Ni–54 at.% Mo > Fe–54 at.% Mo. These peculiarities might be linked with different catalytic behavior of formed intermetallics (and active sites) in electrodeposited alloys. The designed electrodeposited Mo-rich alloys have a higher catalytic activity than Mo and Pt cast metals.