Atomic‐Scale Core/Shell Structure Engineering Induces Precise Tensile Strain to Boost Hydrogen Evolution Catalysis

Tuning surface strain is a new strategy for boosting catalytic activity to achieve sustainable energy supplies; however, correlating the surface strain with catalytic performance is scarce because such mechanistic studies strongly require the capability of tailoring surface strain on catalysts as precisely as possible. Herein, a conceptual strategy of precisely tuning tensile surface strain on Co₉ S₈ /MoS₂ core/shell nanocrystals for boosting the hydrogen evolution reaction (HER) activity by controlling the MoS₂ shell numbers is demonstrated. It is found that the tensile surface strain of Co₉ S₈ /MoS₂ core/shell nanocrystals can be precisely tuned from 3.5% to 0% by changing the MoS₂ shell layer from 5L to 1L, in which the strained Co₉ S₈ /1L MoS₂ (3.5%) exhibits the best HER performance with an overpotential of only 97 mV (10 mA cm⁻² ) and a Tafel slope of 71 mV dec⁻¹ . The density functional theory calculation reveals that the Co₉ S₈ /1L MoS₂ core/shell nanostructure yields the lowest hydrogen adsorption energy (∆EH ) of -1.03 eV and transition state energy barrier (∆E2H* ) of 0.29 eV (MoS₂ , ∆EH = -0.86 eV and ∆E2H* = 0.49 eV), which are the key in boosting HER activity by stabilizing the HER intermediate, seizing H ions, and releasing H₂ gas.