Walnut-like Transition Metal Carbides with Three-Dimensional Networks by a Versatile Electropolymerization-Assisted Method for Efficient Hydrogen Evolution.

Mo2C@NPC (N,P-doped carbon) electrocatalysts are developed on carbon cloth (CC) as binder-free cathodes for efficient hydrogen evolution through a facile route of electropolymerization followed by pyrolysis. Electropolymerization of pyrrole to form polypyrrole occurs with the homogeneous incorporation of PMo12, driven by Coulombic force between the positively charged polymer backbone and PMo12 anions. This electrochemical synthesis is easily scaled up, requiring neither complex instrumentation nor an intentionally added electrolyte (PMo12 also acts as an electrolyte). After pyrolysis, the resultant Mo2C@NPC/CC electrode exhibits a unique interconnected walnut-like porous structure, which ensures strong adhesion between the active material and the substrate and favors electrolyte penetration into the electrocatalyst. This method is effective with other monomers such as aniline and is readily extended to fabricate other metal carbide electrodes such as WC@NPC/CC. These carbide electrodes exhibit high catalytic performance for hydrogen production, for example, WC@NPC/CC can deliver an unprecedented current density of 600 mA cm-2 at an overpotential of only 200 mV either in an acidic or an alkaline solution. Considering the simplicity, scalability, and versatility of the synthetic method, the unique electrode structure, and the excellent catalysis performance, this study opens up new avenues for the design of various novel binder-free metal carbide cathodes based on electropolymerization.