Metal–Organic Framework‐Derived Hollow CoSx Nanoarray Coupled with NiFe Layered Double Hydroxides as Efficient Bifunctional Electrocatalyst for Overall Water Splitting

Abstract For effective hydrogen production by water splitting, it is essential to develop earth‐abundant, highly efficient, and durable electrocatalysts. Herein, the authors report a bifunctional electrocatalyst composed of hollow CoS x and Ni–Fe based layered double hydroxide (NiFe LDH) nanosheets for efficient overall water splitting (OWS). The optimized heterostructure is obtained by the electrodeposition of NiFe LDH nanosheets on metal–organic framework‐derived hollow CoS x nanoarrays, which are supported on nickel foam (H‐CoS x @NiFe LDH/NF). The unique structure of the hybrid material not only provides ample active sites, but also facilitates electrolyte penetration and gas release during the reactions. Additionally, the strong coupling and synergy between the hydrogen evolution reaction (HER) active CoS x and the oxygen evolution reaction (OER) active NiFe LDH gives rise to the excellent bifunctional properties. Consequently, H‐CoS x @NiFe LDH/NF exhibits remarkable HER and OER activities with overpotentials of 95 and 250 mV, respectively at 10 mA cm −2 in 1.0 M KOH. Even at 1.0 A cm −2 , the electrode requires small overpotentials of 375 mV (for HER) and 418 mV (for OER), respectively. An electrolyzer based on H‐CoS x @NiFe LDH/NF demonstrates a low cell voltage of 1.98 V at a current density of 300 mA cm −2 and good durability for 100 h in OWS application.