Hierarchical nitrogen-doped porous graphene/carbon (NPGC) composites were fabricated by a simple and nontemplate method. The morphology characterizations demonstrate that reduced graphene oxide was successfully coated by the carbon derived from glucose, and a well-organized and interpenetrated hierarchical porous structure of NPGC was formed after pyrolysis at 950 °C. Notably, the prepared material, denoted as NPGC-950, has superlarge specific surface area (1510.83 m(2) g(-1)) and relatively high content percentage of pyridinic and graphitic nitrogen. As an efficient metal-free electrocatalyst, NPGC-950 exhibits a high onset potential (0.91 V vs RHE) and a nearly four-electron pathway for oxygen reduction reaction in alkaline solution as well as stronger methanol tolerance and better long-term durability than commercial Pt/C. In view of these excellent features, the obtained hierarchical N-doped metal-free porous carbon material is a promising catalyst for oxygen reduction reaction and could be widely applied in industry.

In order to decrease the electricity consumption of hydrogen generation, hydrazine‐assisted water electrolysis is intensively investigated recently. Herein, hierarchical nanostructure of ultrathin NiCo(OH)x nanosheets (NSs) that in‐situ grown on the NiCoP nanowires (NWs) was deposited on nickel foam (NF) to construct NiCo(OH)x@NiCoP/NF electrode. NiCoP NWs extend the surface area, spatial utilization of NF and enhance the electron conduction to the outmost NiCo(OH)x NSs. NiCo(OH)x NSs interlace to form regular mesoporous channels, which improve the structural stability and mass transfer rate. Moreover, NiCoP NWs enhance the adsorption of protons and the transfer of electrons, while NiCo(OH)x NSs facilitate the adsorption of OHad during reaction. As a result, NiCo(OH)x@NiCoP/NF exhibits excellent activity for both hydrazine oxidation reaction (HzOR) and hydrogen evolution reaction (HER). Based on the NiCo(OH)x@NiCoP/NF||NiCo(OH)x@NiCoP/NF couples, electrolysis of hydrazine for hydrogen generation only requires an extremely low cell voltage of 0.03 V.