Crystalline Ni3S2 Nanorods Tuned by Low-Crystalline NiCoSx with Built-In Electric Field for Efficient Overall Water Splitting

Abstract Efficient overall water splitting (OWS) technology has been highly demanded across the world, of which the key is the development of active and stable electrocatalysts for both hydrogen and oxygen evolution reactions (HER/OER). Herein, novel crystalline Ni 3 S 2 nanorods tuned by low-crystalline NiCoS x (NiCoS x @Ni 3 S 2 ) are synthesized via an ion-exchange strategy. The built-in electric field at the heterogeneous interface driven by work function difference, facilitates rapid electron transfer from Ni 3 S 2 to NiCoS x via a robust Ni–S–Co bond bridge. This synergistic combination of the conductive crystalline core and low-crystalline shell optimizes the d-band center, balancing intermediate adsorption/desorption, speeding up water dissociation, enhancing hydrogen adsorption/desorption for HER, and lowering the energy barrier for OER, ultimately boosting OWS efficiency. The defect-rich, low-crystalline NiCoS x shell, bonded to the crystalline core via Ni–S–Co bonds, serves as a protective armor, enabling dynamic reconstruction into NiCoOOH and suppresses sulfide leaching, ensuring catalytic stability. The optimized NiCoS x @Ni 3 S 2 achieves low HER/OER overpotentials of 346/520 mV@1000 mA cm −2 , evidenced by an ultralow cell voltage of 2.10 V@1000 mA cm −2 for OWS and long-term durability up to 400 h. The work paves a novel way to fabricate sulfur-based electrocatalysts with high yet balanced activity and stability for OWS via an interface engineering strategy.