Abstract The inefficiency of electrocatalysts for water splitting in neutral media stems from a comprehensive impact of poor intrinsic activity, a limited number of active sites, and inadequate mass transport. Herein, hierarchical ultrathin NiCo 2 Se 4 nanosheets are synthesized by the selenization of NiCo 2 O 4 porous nanoneedles. Theoretical and experimental investigations reveal that the intrinsic hydrogen evolution reaction (HER) activity primarily originate from the NiCo 2 Se 4 , whereas the high oxygen evolution reaction (OER) performance is related to the NiCoOOH due to the structural reconstruction. The abundant Se and O vacancies introduced by atomically thin nanostructure modulate the electronic structure of NiCo 2 Se 4 and NiCoOOH, thereby improving the intrinsic HER and OER activities, respectively. COMSOL simulation demonstrate the edges of extended nanosheets from the main body significantly promote the charge aggregation, boosting the reduction and oxidation current during HER/OER process. This charge aggregation effect notably exceeds the tip effect for the nanoneedle, highlighting the unique advantage of the hierarchical nanosheet structure. Benefiting from abundant vacancies and unique nanostructure, the hierarchical ultrathin nanosheet simultaneously improve the thermodynamics and kinetics of the electrocatalyst. The optimized samples display an overpotential of 92 mV for HER and 214 mV for OER at 100 mA cm −2 , significantly surpassing the performance of currently reported HER/OER catalysts in neutral media.

Hierarchical NiCo<sub>2</sub>Se<sub>4</sub> Arrays Composed of Atomically Thin Nanosheets: Simultaneous Improvements in Thermodynamics and Kinetics for Electrocatalytic Water Splitting in Neutral Media

Hierarchical NiCo2Se4 Arrays Composed of Atomically Thin Nanosheets: Simultaneous Improvements in Thermodynamics and Kinetics for Electrocatalytic Water Splitting in Neutral Media