Preparation of CoP/Co@NPC@rGO nanocomposites with an efficient bifunctional electrocatalyst for hydrogen evolution and oxygen evolution reaction

The construction of the highly active transition-metal phosphide/carbon-based electrocatalyst from metal-organic frameworks (MOFs) precursors is considered as an efficient approach. In this work, ZIF-67/GO precursors were firstly obtained by the in situ controllable growth of ZIF-67 nanocrystals on both surfaces of GO sheets. Then, a highly efficient bifunctional electrocatalyst CoP/Co@NPC@rGO nanocomposite was derived by the thermal pyrolysis of ZIF-67/GO precursors under N₂ atmosphere and a subsequent phosphatization process. The structure and elemental composition of the ZIF-67/GO, Co@NPC@rGO, and CoP/Co@NPC@rGO nanocomposites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and N₂ ad-/desorption isotherms analysis. The Co@NPC@rGO‒800 nanocomposite exhibits a high Brunauer-Emmett-Teller (BET) surface area of 186.27 m²·g^‒1, indicating that both micropores and mesopores existed. Subsequently, the electrocatalytic properties of the CoP/Co@NPC@rGO nanocomposites for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) were investigated by electrochemical measurements. The results suggest that the obtained CoP/Co@NPC@rGO‒350 nanocomposite only requires an overpotential of 127 mV to reach a current density of 10 mA·cm^‒2 for HER in 1.0 mol·L^–1 KOH solution. For OER, CoP/Co@NPC@rGO‒350 nanocomposite can reach a current density of 10 mA·cm^‒2 at an overpotential of 276 mV, with a Tafel slope of 42 mV·dec⁻¹, in the same alkaline aqueous solution, which is superior to RuO₂. In addition, for both HER and OER, CoP/Co@NPC@rGO‒350 nanocomposite also shows impressive strong durability in alkaline aqueous solution. The outstanding performance can be attributed to the synergistic effect of coupled highly graphitized N-doped porous carbon and N-doped graphene. The as-prepared CoP/Co@NPC@rGO‒350 electrocatalyst is a promising candidate for overall water splitting in the alkaline solution. This development offers an attractive catalyst material based on MOF/GO composites. It is expected that the presented strategy can be extended to the fabrication of other composites electrode materials for more efficient water splitting.