3D NiMnCo Electrocatalysts with Cauliflower Curd-Shaped Microspherical Morphology for an Efficient and Sustainable HER in Alkaline Freshwater/Seawater Media

Electrocatalytic seawater splitting is an ideal strategy for the large-scale production of green hydrogen. Compared to scarce freshwater, oceanic seawater electrolysis represents a game-changer for the hydrogen economy. Herein, we report a cost-effective one-step synthesis of binder-free, self-supported 3D nickel–manganese–cobalt (NiMnCo) coatings on titanium (Ti) substrates and evaluated their electrocatalytic performance for the hydrogen evolution reactions (HERs) in alkaline media (1.0 M KOH), simulated seawater (SSW, 1.0 M KOH + 0.5 M NaCl) and alkaline natural seawater (ASW, 1.0 M KOH + natural seawater). These ternary coatings were electrodeposited on Ti substrates using an electrochemical deposition method via a dynamic hydrogen bubble template (DHBT) technique. The optimized ternary NiMnCo/Ti-2 electrocatalyst exhibited an enhanced HER activity in both alkaline and seawater media, achieving an ultra-low overpotential of 29, 59 and 66 mV to reach the benchmark current density of 10 mA cm−2 in SSW, ASW and 1.0 M KOH, respectively. This efficient 3D ternary NiMnCo/Ti-2 electrocatalyst demonstrated stable long-term performance at a constant potential of −0.23 V (vs. RHE) and a constant current density of 10 mA cm−2 for 50 h without any significant degradation. Furthermore, it exhibited long-term stability in alkaline electrolyte and simulated seawater during multi-step chronopotentiometric testing at variable current densities from 20 mA cm−2 to 100 mA cm−2 for 18 h. This superior performance can be attributed to its unique intermetallic structure and multi-component composition, which provides good Cl− resistance, electrochemical stability and synergistic effects among its constituents. Therefore, the optimized NiMnCo/Ti-2 electrocatalyst is a promising candidate for practical seawater electrolysis aiming at green hydrogen production.