Phosphorus-doped NiCo₂S₄ nanocrystals grown on electrospun carbon nanofibers as ultra-efficient electrocatalysts for the hydrogen evolution reaction

Abstract

The development of highly efficient noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) is still a challenge nowadays. In this work, we prepared a highly active electrocatalyst containing phosphorus-doped NiCo₂S₄ nanocrystals grown on carbon nanotube embedded carbon nanofibers (P-NiCo₂S₄@CNT/CNF). The CNTs are involved in enhancing the electrical conductivity of the three-dimensional CNF network through a facile co-electrospinning method, which can facilitate electron transfer to the attached HER active material. Templated by this nanofiber network, the electroactive NiCo₂S₄ is confined to grow perpendicularly onto the CNT/CNF template via a hydrothermal reaction, thus exposing more catalytic active sites. Doping of P into the hybrid via a phosphidation reaction improves the electronic structure of the electroactive NiCo₂S₄, thus decreasing the energy barrier during the HER process. Owing to the synergistic effects from electrical enhancement and the nanostructured morphology, along with P-doping-induced optimization of the electronic structure, the P-NiCo₂S₄@CNT/CNF hybrid exhibits excellent HER performance, with an ultra-low onset overpotential (η) of 27 mV, a remarkable current density of 10 mA cm^-2 at η as low as 74 mV, an impressive exchange current density of 0.79 mA cm^-2 and excellent long-term durability. Furthermore, its electroactivity exceeds that of most reported noble-metal-free electrocatalysts and is comparable to that of Pt, suggesting its great potential as a highly efficient HER catalyst.