Heterostructure Ni3S4–MoS2 with interfacial electron redistribution used for enhancing hydrogen evolution

Abstract

Developing highly effective and inexpensive electrocatalysts for hydrogen evolution reaction (HER), particularly in a water-alkaline electrolyzer, are crucial to large-scale industrialization. The earth-abundant molybdenum disulfide (MoS₂) is an ideal electrocatalyst in acidic media but suffers from a high overpotential in alkaline solution. Herein, nanospherical heterostructure Ni₃S₄–MoS₂ was obtained via a one-pot synthesis method, in which Ni₃S₄ was uniformly integrated with MoS₂ ultrathin nanosheets. There were abundant heterojunctions in the as-synthesized catalyst, which were verified by X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HRTEM). The structure features with interfacial electron redistribution was proved by XPS and density functional theory (DFT) calculations, which offered several advantages to promote the HER activity of MoS₂, including increased specific surface area, exposed abundant active edge sites and improved electron transfer. Ni₃S₄–MoS₂ exhibited a low overpotential of 116 mV at 10 mA cm⁻² in an alkaline solution with a corresponding Tafel slope of 81 mV dec⁻¹ and long-term stability of over 20 h. DFT simulations indicated that the synergistic effects in the system with the chemisorption of H on the (002) plane of MoS₂ and OH on the (311) plane of Ni₃S₄ accelerated the rate-determining water dissociation steps of HER. This study provides a valuable route for the design and synthesis of inexpensive and efficient HER electrocatalyst, heterostructure Ni₃S₄–MoS₂.