Epitaxial Heterogeneous Interfaces on N‐NiMoO4/NiS2 Nanowires/Nanosheets to Boost Hydrogen and Oxygen Production for Overall Water Splitting

Abstract Developing bifunctional efficient electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is in high demand for the development of overall water‐splitting devices. In particular, the electrocatalytic performance can be largely improved by designing positive nanoscale‐heterojunction with well‐tuned interfaces. Herein, a novel top‐down strategy is reported to construct the oxide/sulfide heterostructures (N‐NiMoO 4 /NiS 2 nanowires/nanosheets) as a multisite HER/OER catalyst. Starting with the NiMoO 4 nanowires, nitridation in a controlled manner enables activation of Ni sites in NiMoO 4 and then yields oxide/sulfide heterojunction by directly vulcanizing the highly composition‐segregated N‐NiMoO 4 nanowires. The abundant epitaxial heterogeneous interfaces at atomic‐level facilitate the electron transfer from N‐NiMoO 4 to NiS 2 , which further cooperate synergistically toward both the hydrogen and oxygen generation in alkali solution. Furthermore, with N‐NiMoO 4 /NiS 2 grown carbon fiber cloth as the engineering electrode, the assembled N‐NiMoO 4 /NiS 2 –N‐NiMoO 4 /NiS 2 system can deliver a current density of 10 mA cm −2 with the cell voltage of 1.60 V in the water‐splitting reaction. This current density is 3.39 times higher than that of the Pt–Ir set (2.95 mA cm −2 ). The excellent catalytic performance offered of N‐NiMoO 4 /NiS 2 nanowires/nanosheets presents a great example to demonstrate the significance of interface engineering in the field of electrocatalysis.