Electrodeposited alloy electrodes in the Co–W–Mo system as highly efficient catalysts for hydrogen production from alkaline water electrolysis

In the presented paper the non-precious electrode materials containing Co, Mo, and W demonstrating high catalytic activity towards hydrogen evolution reaction were characterized. The studied alloy electrodes were electrodeposited from electrolytes with a simple composition, containing CoSO4, Na2WO4, Na2MoO4, and Na3C6H5O7. The structure, surface morphology, and composition of the prepared deposits were analyzed using scanning microscopy, X-ray diffraction, and transmission electron microscopy techniques. Cathodic polarization and electrochemical impedance spectroscopy were applied to assess the electrocatalytic activity and elucidate the HER mechanism in 1M KOH solution. The nanocrystalline structure, fine grain size, and presence of microcracks on the surface of the studied alloys contributed to their notably high electrochemically active surface area (ECSA) (65.7e2, 11.7e4, and 99.7e3 cm2 for the Co–W, Co–Mo, and Co–W–Mo, respectively), a crucial factor driving their superior catalytic activity. The intrinsic catalytic activity evaluated at the overpotential of 150 mV was 9.2, 3.3, 0.78 and 1.4 μA cm-2 for the Co, Co–W, Co–Mo and Co–W–Mo electrodes, respectively. This indicates that the superior electrocatalytic characteristics observed for the alloy coatings, compared to Co resulted from the substantial increase in their ECSA. Among the investigated electrodes, the ternary Co–W–Mo alloy was characterized by the highest electrocatalytic performance confirmed by the lowest overpotential (42 mV) required to attain a current density of 10 mA cm−2.