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

Abstract

Abstract 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 Co 3 S 4 nanosheet, P doped WS 2 nanosheet, and Co 9 S 8 nanoparticles (Super‐Co 3 S 4 /P‐WS 2 /Co 9 S 8 ) for all‐pH HER is reported. The Super‐Co 3 S 4 /P‐WS 2 /Co 9 S 8 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‐Co 3 S 4 /P‐WS 2 /Co 9 S 8 can not only provide Pt‐like H*‐adsorption Gibbs free energy ( Δ G H* ) but also promote the H 2 O 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.