Manganese‐Doped Bimetallic (Co,Ni)2P Integrated CoP in N,S Co−Doped Carbon: Unveiling a Compatible Hybrid Electrocatalyst for Overall Water Splitting

Abstract Rational design of highly efficient noble‐metal‐unbound electrodes for hydrogen and oxygen production at increased current density is crucial for robust water‐splitting. A facile hydrothermal and room‐temperature aging method is presented, followed by chemical vapor deposition (CVD), to create a self‐sacrificed hybrid heterostructure electrocatalyst. This hybrid material, (Mn−(Co,Ni) 2 P/CoP/(N,S)−C), comprises manganese‐doped cobalt nickel phosphide (Mn−(Co,Ni) 2 P) nanofeathers and cobalt phosphide (CoP) nanocubes embedded in a nitrogen and sulfur co‐doped carbon matrix (N,S)−C on nickel foam. The catalyst exhibits excellent performance in both the hydrogen evolution reaction (HER; η 10 = 61 mV) and oxygen evolution reaction (OER; η 10 = 213 mV) due to abundant active sites, high porosity, and enhanced hetero‐interface interaction between Mn−(Co 2 P−Ni 2 P) CoP, and (N,S)−C supported by significant synergistic effects observed among different phases through density functional theory (DFT) calculations. Impressively, (Mn−(Co,Ni) 2 P/CoP/(N,S)−C (+,−) shows an extra low cell voltage of 1.49 V@10 mA cm −2 . Moreover, the catalyst exhibits remarkable stability at 100 and 300 mA cm −2 when operating as a single stack cell electrolyzer. The superior electrochemical activity is attributed to the enhanced electrode–electrolyte interface among the multiple phases of the hybrid structure.