Hierarchical MoP Hollow Nanospheres Anchored on a N,P,S-Doped Porous Carbon Matrix as Efficient Electrocatalysts for the Hydrogen Evolution Reaction.

Developing efficient, nonprecious, and durable electrocatalysts with favorable nanostructures is a persistent challenge yet is significant for the hydrogen evolution reaction (HER). Herein, for the first time, a rationally designed strategy is reported for the synthesis of hierarchical hollow MoP nanospheres anchored on N,P,S co-doped porous carbon (hs-MoP/NPSC). Importantly, the porous shell of the hollow nanosphere is constructed of a number of interwoven MoP subunits, which is beneficial for exposing surface active sites as much as possible and promoting the mass transport during the HER process. In addition, the heteroatom-enriched porous carbon networks can further reduce the electron/ion transfer resistance. As expected, the hs-MoP/NPSC electrocatalyst exhibits an encouraging HER activity with a low overpotential of only 70 mV at a current density of 10 mA cm , a small Tafel slope, and long-term durability in alkaline media, outperforming most of reported Pt-free MoP-based electrocatalysts to date. This present work not only develops a highly efficient electrocatalyst for HER but also opens up opportunities to engineer novel architectures for various applications.