Electronic Structure Reconfiguration Toward Pyrite NiS Via Engineered Heteroatom Defect Boosting Overall Water Splitting

Developing highly active and low-cost heterogeneous catalysts toward overall electrochemical water splitting is extremely desirable but still a challenge. Herein, we report pyrite NiS nanosheets doped with vanadium heteroatoms as bifunctional electrode materials for both hydrogen- and oxygen-evolution reaction (HER and OER). Notably, the electronic structure reconfiguration of pyrite NiS is observed from typical semiconductive characteristics to metallic characteristics by engineering vanadium (V) displacement defect, which is confirmed by both experimental temperature-dependent resistivity and theoretical density functional theory calculations. Furthermore, elaborate X-ray absorption spectroscopy measurements reveal that electronic structure reconfiguration of NiS is rooted in electron transfer from doped V to Ni sites, consequently enabling Ni sites to gain more electrons. The metallic V-doped NiS nanosheets exhibit extraordinary electrocatalytic performance with overpotentials of about 290 mV for OER and about 110 mV for HER at 10 mA cm with long-term stability in 1 M KOH solutions, representing one of the best non-noble-metal bifunctional electrocatalysts to date. This work provides insights into electronic structure engineering from well-designed atomic defect metal sulfide.