Super‐Hybrid Transition Metal Sulfide Nanoarrays of Co3S4 Nanosheet/P‐Doped WS2 Nanosheet/Co9S8 Nanoparticle with Pt‐Like Activities for Robust All‐pH Hydrogen Evolution

Highly active and multifunctional non‐precious metal‐based hydrogen evolution reaction (HER) eletcrocatalysts have aroused great interest in the large‐scale conversion of sustainable electrical energy to fuels and feedstocks in different application scenarios. Here, a metal sulfide‐based super hybrid nanoarray composed of a metallic Co3S4 nanosheet, P doped WS2 nanosheet, and Co9S8 nanoparticles (Super‐Co3S4/P‐WS2/Co9S8) for all‐pH HER is reported. The Super‐Co3S4/P‐WS2/Co9S8 only requires 58, 70, and 129 mV in alkaline, acid, and neutral media, respectively, to reach 10 mA cm‐2, which also presents fast reaction kinetics and high long‐term stability. The experimental and density functional theory (DFT) results verify that the abundant active heterostructure in Super‐Co3S4/P‐WS2/Co9S8 can not only provide Pt‐like H*‐adsorption Gibbs free energy (ΔGH*) but also promote the H2O adsorption and dissociation kinetics for all‐pH HER. Moreover, the collaboration of favorable metallic components and special nanoarray morphology can also strengthen the electric conductivity for electron transfer and promote the maximum exposure of active heterointerfaces for mass transport in electrocatalysis. The interesting strategy herein is expected to inspire the future design of advanced metal sulfide‐based heterostructures for energy storage and conversion.