Effective and robust electrocatalysts are mainly based on innovative materials and unique structures. Herein, we designed a flakelike cobalt phosphide-based catalyst supporting on NiCo2O4 nanorods array, which in-situ grew on the nickel foam (NF) current collector, referring as N–Co2P/NiCo2O4/NF electrode. By optimizing the microstructure and electronic structure through 3D hierarchy fabrication and nitrogen doping, the catalyst features with abundant electrochemical surface area, favorable surface wettability, excellent electron transport, as well as tailored d band center. Consequently, the as-prepared N–Co2P/NiCo2O4/NF electrode exhibits an impressive HER activity with a low overpotentials of 58 mV at 10 mA cm−2, a Tafel slop of 75 mV dec−1, as well as superior durability in alkaline medium. This work may provide a new pathway to effectively improve the hydrogen evolution performance of transition metal phosphides and to develop promising electrodes for practical electrocatalysis.
