In Situ-Generated Nanostructured Ni2P in an S,N-Doped Carbon Matrix Using a Metal–Organic Framework and Red Phosphorus as Feedstocks for Boosting Electrocatalysis

Transition-metal phosphides (TMPs) are regarded as ideal HER electrocatalysts owing to their rich reserve, flexible composition, competitive activity, and excellent stability. Yet, TMPs still suffer from poor electrical conductivity and agglomeration under a high synthetic temperature of the solid-state reaction. Benefiting from the monodisperse metal sites with organic matrix surrounded, metal–organic frameworks (MOFs) have great potential as a feedstock to produce MOF-derived TMPs with tailored microenvironments of the active sites. Herein, a series of nanostructured Ni2P@SNC were facilely fabricated by a one-step phosphorization of a well-designed Ni-MOF with red phosphorus as a “P” source. The optimal Ni2P@SNC-800 displayed an overpotential of 80 mV in 1.0 M KOH and 97 mV in 0.5 M H2SO4 at 10 mA cm–2, demonstrating excellent HER performance as well as long durability in both electrolytes. The comprehensive performance of Ni2P@SNC-800 surpasses that of other heteroatom-free MOF-derived Ni2P significantly. This work provides a facile approach for the design and synthesis of MOF-derived TMPs coated with a heteroatom-doped carbon matrix as an electrocatalyst with high activity.