Heterogeneous Structure of Ni–Mo Nanoalloys Decorated on MoOx for an Efficient Hydrogen Evolution Reaction Using Hydrogen Spillover

• Published in: Advanced science 2024-10, Vol.11 (39), p.e2403752-n/a
• Main Authors: Song, DongHoon, Roh, Jeonghan, Choi, Jungwoo, Lee, Hyein, Koh, Gyungmo, Kwon, YongKeun, Kim, HyoWon, Lee, Hyuck Mo, Kim, MinJoong, Cho, EunAe
• Format: Article
• Language: English
• Subjects: electrodeposition; Electrodes; Green hydrogen; heterogeneous Ni–Mo electrocatalyst; hydrogen evolution reaction; hydrogen molybdenum bronze; hydrogen spillover; Metals; Molybdenum; Spectrum analysis
• ISSN: 2198-3844; 2198-3844
• DOI: 10.1002/advs.202403752

Herein, a heterogeneous structure of Ni–Mo catalyst comprising Ni4Mo nanoalloys decorated on a MoOx matrix via electrodeposition is introduced. This catalyst exhibits remarkable hydrogen evolution reaction (HER) activity across a range of pH conditions. The heterogeneous Ni–Mo catalyst showed low overpotentials only of 24 and 86, 21 and 60, and 37 and 168 mV to produce a current density of 10 and 100 mA cm−2 (η10 and η100) in alkaline, acidic, and neutral media, respectively, which represents one of the most active catalysts for the HER. The enhanced activity is attributed to the hydrogen spillover effect, where hydrogen atoms migrate between the Ni4Mo alloys and the MoOx matrix, forming hydrogen molybdenum bronze as additional active sites. Additionally, the Ni4Mo facilitated the water dissociation process, which helps the Volmer step in the alkaline/neutral HER. Through electrochemical analysis, in situ Raman spectroscopy, and density functional theory calculations, the fast HER mechanism is elucidated. Ni–Mo electrocatalyst with a tailored nanostructure is synthesized by simple electrodeposition. The heterogeneous structure composed of Ni4Mo nanoalloys decorated on a MoOx matrix displays efficient HER across a wide range of pH conditions: alkaline (1 m KOH), acidic (0.5 m H2SO4), and neutral (1 m PBS) electrolytes.