Controlled synthesis of the M doped (M = Fe, Cu, Zn, Mn)-Co4S3/Ni3S2 catalyst with high electrocatalytic performance for hydrogen evolution reaction in seawater and urea

Electrolysis of seawater is a promising method for producing hydrogen, but sluggish reaction kinetics and electrolyte containing corrosive ions limit its development. In this work, a series of M doped (M = Fe, Cu, Zn, Mn)-Co₄S₃/Ni₃S₂ catalyst has been prepared on Ni foam by hydrothermal method with excellent seawater and urea splitting performance. The unique 3D porous structure provides a large number of active sites for the catalyst, which has strong catalytic activity. Fe-Co₄S₃/Ni₃S₂ electrode showed excellent hydrogen evolution reaction (HER) catalytic activity in 1 M KOH + seawater and 1 M KOH + 0.5 M urea, driving a current density of 10 mA cm⁻² at a low overpotential of 81 and 66 mV. In addition, Fe-Co₄S₃/Ni₃S₂ electrode also shows strong stability in 15 h stability test. The results show that although the impurity ions in seawater affect the activity of catalyst, the corrosion resistance of catalyst also improves the catalytic activity and stability. Density functional theory calculations show that this Fe-Co₄S material exhibits the optimal Gibbs free energy of hydrogen, the introduction of this Ni₃S₂ material enhances the electrical conductivity of the material, and the synergistic catalysis of the two materials promotes the optimal hydrogen production performance of the Fe-Co₄S₃/Ni₃S₂ material. This work provides a novel understanding for the research of catalysts used in the electrolysis of seawater and urea.