"Lewis Base-Hungry" Amorphous-Crystalline Nickel Borate-Nickel Sulfide Heterostructures by In Situ Structural Engineering as Effective Bifunctional Electrocatalysts toward Overall Water Splitting.

The development of high-performance, low-cost, and long-lasting electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is urgently needed for effective electrochemical water splitting. In the present study, an engineering process was employed to prepare "Lewis base-hungry" amorphous-crystalline nickel borate-nickel sulfide (Ni3(BO3)2-Ni3S2) heterostructures, which exhibited unprecedentedly high electrocatalytic activity toward both OER and HER in alkaline media. The optimal Ni3(BO3)2-Ni3S2/nickel foam (Ni3(BO3)2-Ni3S2/NF) electrode displayed an ultralow overpotential of only -92 and +217 mV to reach the current density of 10 mA cm-2 for HER and OER, respectively. When the Ni3(BO3)2-Ni3S2/NF electrode was used as both the anode and cathode for overall water splitting, a low cell voltage of 1.49 V was needed to achieve the current density of 10 mA cm-2, which was superior to the performance of most noble metal-free electrocatalysts. Results from density functional theory calculations showed that the Lewis base-hungry sites in the heterostructures effectively enhanced the chemisorption of hydrogen and oxygen intermediates, a critical step in HER and OER electrocatalysis. Results from this study highlight the significance of rational design and engineering of heterostructured materials for the development of high-efficiency electrocatalysts.