Hierarchically Porous Urchin-Like Ni2P Superstructures Supported on Nickel Foam as Efficient Bifunctional Electrocatalysts for Overall Water Splitting

The development of high-performance nonprecious electrocatalysts with both H2 and O2 evolution reaction (HER and OER) activities for overall water splitting is highly desirable but remains a grand challenge. Herein, we report a facile two-step method to synthesize three-dimensional hierarchically porous urchin-like Ni2P microsphere superstructures anchored on nickel foam (Ni2P/Ni/NF) as bifunctional electrocatalysts for overall water splitting. The Ni2P/Ni/NF catalysts were prepared by template-free electrodeposition of porous nickel microspheres on nickel foam followed by phosphidation. The hierarchically macroporous superstructures with 3D configuration can reduce ion transport resistance and facilitate the diffusion of gaseous products (H2 and O2). The optimal Ni2P/Ni/NF exhibited remarkable catalytic performance and outstanding stability for both the HER and OER in alkaline electrolyte (1.0 M KOH). For the HER, Ni2P/Ni/NF afforded a current density of 10 mA cm–2 at a low overpotential of only −98 mV. When it served as an OER electrocatalyst, Ni2P/Ni/NF was partially oxidized to nickel oxides/hydroxides/oxyhydroxides (mainly NiO) on the catalyst surface and exhibited excellent OER activity with small overpotentials of 200 and 268 mV to reach 10 and 100 mA cm–2, respectively. Furthermore, when Ni2P/Ni/NF was employed as the electrocatalyst for both the cathode and anode, a water splitting electrolyzer was able to reach 10 and 100 mA cm–2 in 1.0 M KOH at cell voltages of 1.49 and 1.68 V, respectively, together with robust durability. Various characterization techniques and controlled experiments indicated that the superior activity and strong stability of Ni2P/Ni/NF for overall water splitting originated from its electrochemically active constituents, 3D interconnected porosity, and high conductivity.