Construction of self-supporting, hierarchically structured caterpillar-like NiCo<sub>2</sub>S<sub>4</sub> arrays as an efficient trifunctional electrocatalyst for water and urea electrolysis
Wenjiao Song, Mingze Xu, Xue Teng, Yanli Niu, Shuaiqi Gong, Xuan Liu, Xiaoming He, Zuofeng Chen
Abstract
In this study, we have developed intriguing self-supporting caterpillar-like spinel NiCo2S4 arrays with a hierarchical structure of nanowires on a nanosheet skeleton, which can be used as a self-supporting trifunctional electrocatalyst for the oxygen evolution reaction (OER), hydrogen evolution reaction (HER) and urea oxidation reaction (UOR). The caterpillar-like NiCo precursor arrays are first in situ grown on carbon cloth (NiCo2O4/CC) by a facile hydrothermal reaction, which is followed by an anion exchange process (or sulfuration treatment) with Na2S to form self-supporting spinel NiCo2S4 arrays (NiCo2S4/CC) with a roughened nanostructure. Taking advantage of the bimetallic synergistic effect, the unique hierarchical nanostructure, and the self-supporting nature, the resultant NiCo2S4/CC electrode exhibits high activities toward the OER, HER and UOR, which are highly superior to the monometallic counterparts of NiS nanosheets and Co9S8 nanowires on a carbon cloth substrate. The comparison of the three electrodes also indicates that the hierarchically structured bimetallic electrode combines the morphological and structural characteristics of monometallic Ni-based nanosheets and Co-based nanowires. When assembling a two-electrode electrolytic cell with NiCo2S4/CC as both the anode and cathode, an applied cell voltage of only 1.66 V is required to deliver a current density of 10 mA cm-2 in water electrolysis. By using the same two-electrode setup, the applied voltage for urea electrolysis is further reduced to 1.45 V that produces hydrogen at the cathode with the same current density. This study paves the way for exploring the feasibility of future less energy-intensive and large-scale hydrogen production.