S−S Bond Strategy at Sulfide Heterointerface: Reversing Charge Transfer and Constructing Hydrogen Spillover for Boosted Hydrogen Evolution

• Published in: Angewandte Chemie International Edition 2024-11, Vol.63 (48), p.e202409465-n/a
• Main Authors: Yue, Haoyu, Guo, Zhongnan, Zhou, Ziwen, Zhang, Xuemeng, Guo, Wenjing, Zhen, Shuang, Wang, Pu, Wang, Kang, Yuan, Wenxia
• Format: Article
• Language: English
• Subjects: Adsorption; Basal plane; Bonding strength; Catalysis; Charge reversal; Charge transfer; Electrocatalysts; Heterostructures; Hydrogen; Hydrogen evolution; Hydrogen evolution reactions; Hydrogen spillover; Nanoparticles; Reversed charge transfer; Ruthenium; Sulfide heterointerface; Sulfides; S−S bond
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202409465

Developing efficient electrocatalyst in sulfides for hydrogen evolution reaction (HER) still poses challenges due to the lack of understanding the role of sulfide heterointerface. Here, we report a sulfide heterostructure RuSx/NbS2, which is composed of 3R‐type NbS2 loaded by amorphous RuSx nanoparticles with S−S bonds formed at the interface. As HER electrocatalyst, the RuSx/NbS2 shows remarkable low overpotential of 38 mV to drive a current density of 10 mA cm−2 in acid, and also low Tafel slope of 51.05 mV dec−1. The intrinsic activity of RuSx/NbS2 is much higher than that of Ru/NbS2 reference as well as the commercial Pt/C. Both experiments and theoretical calculations unveil a reversed charge transfer at the interface from NbS2 to RuSx that driven by the formation of S−S bonds, resulting in electron‐rich Ru configuration for strong hydrogen adsorption. Meanwhile, electronic redistribution induced by the sulfide heterostructure facilitates hydrogen spillover (HSo) effect in this system, leading to accelerated hydrogen desorption at the basal plane of NbS2. This study provides an effective S−S bond strategy in sulfide heterostructure to synergistically modulate the charge transfer and adsorption thermodynamics, which is very valuable for the development of efficient electrocatalysts in practical applications. RuSx/NbS2 heterostructure was synthesized by the introducing of amorphous RuSx onto crystalline NbS2 surface. It shows a Pt‐like HER activity with a low overpotential as 38 mV at 10 mA ⋅ cm−2, which is mainly benefit from hydrogen spillover caused by reversing charge transfer that induced by S−S bonds at RuSx/NbS2 heterointerface.