Bottom-up Design of Bimetallic Cobalt-Molybdenum Carbides/Oxides for Overall Water Splitting

Earth-abundant transition-metal-based catalysts for electrochemical water splitting are critical for sustainable energy schemes. In this work, we use a rational design method for the synthesis of ultrasmall and highly dispersed bimetallic CoMo carbide/oxide particles deposited on graphene oxide. Thermal conversion of the molecular precursors [H₃ PMo₁₂ O₄₀ ], Co(OAc)₂ ⋅4 H₂ O and melamine in the presence of graphene oxide gives the mixed carbide/oxide (Co₆ Mo₆ C₂ /Co₂ Mo₃ O₈ ) nanoparticle composite deposited on highly dispersed, N,P-doped carbon. The resulting composite shows outstanding electrocatalytic water-splitting activity for both the oxygen evolution and hydrogen evolution reaction, and superior performance to reference samples including commercial 20 % Pt/C & IrO₂ . Electrochemical and other materials analyses indicate that Co₆ Mo₆ C₂ is the main active phase in the composite, and the N,P-doping of the carbon matrix increases the catalytic activity. The facile design could in principle be extended to multiple bimetallic catalyst classes by tuning of the molecular metal oxide precursor.