Searching for non-noble-metal-based electrocatalysts with high efficiency and durability toward the hydrogen evolution reaction (HER) is vitally necessary for the upcoming clean and renewable energy systems. Here we report the synthesis of CoP nanoparticles encapsulated in ultrathin nitrogen-doped porous carbon (CoP@NC) through a metal−organic framework (MOF) route. This hybrid exhibits remarkable electrocatalytic activity toward the HER in both acidic and alkaline media, with good stability. Experiments and theoretical calculations reveal that the carbon atoms adjacent to N dopants on the shells of CoP@NC are active sites for hydrogen evolution and that CoP and N dopants synergistically optimize the binding free energy of H* on the active sites, which results in a higher electrocatalytic activity in comparison to its counterparts without nitrogen doping and/or CoP encapsulation.

        https://doi.org/10.1021/acscatal.7b00587