Hierarchical Porous CoS/Nitrogen-Doped Carbon@MoS Polyhedrons as pH Universal Electrocatalysts for Highly Efficient Hydrogen Evolution Reaction.

The development of highly active and stable earth-abundant electrocatalysts to reduce or eliminate the reliance on noble-metal based ones for hydrogen evolution reaction (HER) over a broad pH range remains a great challenge. Herein, hierarchical porous CoS/N-doped carbon@MoS (CoS/NC@MoS) polyhedrons have been synthesized by a facile hydrothermal approach using highly conductive Co/NC polyhedrons composed of cobalt nanoparticles embedded in N-doped carbon matrices as both the structural support and cobalt source. The Co/NC polyhedrons were prepared by direct carbonization of Co-based zeolitic imidazolate framework (ZIF-67) in Ar atmosphere. Benefiting from the prominent synergistic effect of N-doped carbon enhancing the conductivity of the hybrid, MoS and CoS providing abundant catalytically active sites as well as the well-defined polyhedral structure promoting mechanical stability, the as-synthesized CoS/NC@MoS shows excellent HER activity and good stability over a broad pH range, with onset overpotentials of 4, 38, and 45 mV, Tafel slopes of 60.3, 68.8, and 126.1 mV dec, and overpotentials of 67, 117, and 261 mV at 10 mA cm in 1.0 M KOH, 0.5 M HSO, and 1.0 M phosphate buffer solution (PBS), respectively. This work provides a general and promising approach for the design and synthesis of inexpensive and efficient pH-universal HER electrocatalysts.