Coupling Mo₂C with Nitrogen‐Rich Nanocarbon Leads to Efficient Hydrogen‐Evolution Electrocatalytic Sites

Abstract In our efforts to obtain electrocatalysts with improved activity for water splitting, meticulous design and synthesis of the active sites of the electrocatalysts and deciphering how exactly they catalyze the reaction are vitally necessary. Herein, we report a one‐step facile synthesis of a novel precious‐metal‐free hydrogen‐evolution nanoelectrocatalyst, dubbed Mo 2 C@NC that is composed of ultrasmall molybdenum carbide (Mo 2 C) nanoparticles embedded within nitrogen‐rich carbon (NC) nanolayers. The Mo 2 C@NC hybrid nanoelectrocatalyst shows remarkable catalytic activity, has great durability, and gives about 100 % Faradaic yield toward the hydrogen‐evolution reaction (HER) over a wide pH range (pH 0–14). Theoretical calculations show that the Mo 2 C and N dopants in the material synergistically co‐activate adjacent C atoms on the carbon nanolayers, creating superactive nonmetallic catalytic sites for HER that are more active than those in the constituents.