Hierarchical Selenium-Doped Nickel–Cobalt Hybrids on Carbon Paper for the Overall Water-Splitting Electrocatalytic System

Designing and constructing hierarchically structured materials with heterogeneous compositions is the key to developing an effective catalyst for overall water-splitting applications. Herein, we report the fabrication of hollow-structured selenium-doped nickel–cobalt hybrids on carbon paper as a self-supported electrode (denoted as Se–Ni|Co/CP, where Ni|Co hybrids consist of nickel–cobalt alloy-incorporated nickel–cobalt oxide). The procedure involves direct growth of zeolitic imidazolate framework-67 (ZIF-67) on bimetal-based nickel–cobalt hydroxide (NiCoOH) electrodeposited on CP, followed by selenous etching and pyrolysis to obtain the final Se–Ni|Co/CP electrocatalytic system. The optimized Se–Ni|Co/CP [Se–Ni1|Co9/CP(0.3)] exhibits remarkable performance in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), displaying a current density of 10 mA cm–2 at small overpotentials of 105 mV for HER and 235 mV for OER. Furthermore, it allows an alkali electrolyzer to achieve a current density of 10 mA cm–2 at a cell voltage of only 1.51 V. The outstanding catalytic activity of Se–Ni|Co/CP is ascribed to the high intrinsic activity of the bimetallic catalyst, efficient interfaces, and charge transport facilitated by the heterogeneous component, the hollow structure inherited from the metal–organic frameworks (MOF)-derived material providing ample porosity and active sites, and structural robustness achieved through self-supported construction.