Unveiling the Optimal Interfacial Synergy of Plasma Modulated Trimetallic Mn-Ni-Co Phosphides: Tailoring Deposition Ratio for Complementary Water Splitting

Designing highly active, durable, and nonprecious metal-based bifunctional electrocatalysts for overall water electrolysis is of urgent scientific importance to realize sustainable hydrogen production, which remains a grand challenge. Herein, an innovative approach is demonstrated to synthesize flower-like 3D homogenous trimetallic Mn, Ni, Co phosphide catalysts directly on nickel foam via electrodeposition followed by plasma phosphidation. The electrochemical activity of the catalysts with varying Mn: Ni: Co ratios is assessed to identify the optimal composition, demonstrating that the equimolar trimetallic phosphide yields an outstanding HER catalytic performance with a current density of 10 mA/cm² at an ultra-low overpotential of ~14 mV, outperforming the best-reported electrocatalysts. This is asserted by the DFT calculations, revealing a strong interaction of the metals and the P atom, resulting in enhanced water activation and optimized G_H* values for the HER process. Moreover, this optimal composition appreciably catalyzes the OER by exposing more intrinsic active species in-situ formed on the catalyst surface during the OER. Therefore, the Mn₁-Ni₁-Co₁-P-(O)/NF catalyst exhibits a decreased overpotential of ~289 mV at 10 mA/cm². More importantly, the electrocatalyst sustains perfect durability up to 48 h at a current density of 10 mA/cm² and continued 5000 cycling stability for both HER and OER. Meanwhile, the assembled MNC-P/NF||MNC-P/NF full water electrolyzer system attains an extremely low cell voltage of 1.48 V at 10 mA/cm². Significantly, the robust stability of the overall system results in remarkable current retention of ~96% after a continuous 50 h run. Therefore, this study provides a facile design and a scalable construction of superb bifunctional ternary MNC-phosphide electrocatalysts for efficient electrochemical energy production systems.