Vesicle-Shaped Co-Ni-S designed by first principles screening and d-Band center control for active hydrogen evolution

• Achieve 185 mV overpotential at 100 mA·cm −2 and close to 0 mV at 10 mA·cm −2 for hydrogen evolution . • A brand-new morphology resembles chipped or cracked vesicle with cross-linked nanospheres inside. • Modified the d-band center to regulate the interaction between the surface and adsorbates. Hydrogen evolution reaction (HER) is considered as an effective pathway for hydrogen production. Herein, to obtain efficient HER catalyst, density functional theory is employed to figure out the optimal candidate for nickel sulfide. Guided by the mechanistic screening, the highly active HER electrocatalyst, Co-substituted Ni 3 S 4 , is synthesized by one-step hydrothermal method, resembling a vesicle composed of a broken spherical membrane and encapsulated clusters of nanospheres . Cracks on membrane provide a rational entry for reactant molecules to be enclosed in the vesicle. Additionally, the enhanced intrinsic activity also attributes to the upward shift of the d-band center. From the reaction energy diagrams, the decomposition of H 2 O* is confirmed as the rate-determining step (RDS) and the energy required for the RDS is efficiently lowered by the elevated d-band center, which made the catalyst achieves 185 mV overpotential at 100 mA·cm −2 and 38 mV at 20 mA·cm −2 lower than utmost Co-Ni-S relative electrocatalyst.