Source: http://www.cjcatal.org/EN/abstract/abstract22343.shtml
Timestamp: 2019-04-24 20:44:48+00:00

Document:
Molybdenum sulfides are promising electrocatalysts for the hydrogen evolution reaction (HER). S-and Mo-related species have been proposed as the active site for forming adsorbed hydrogen to initiate the HER; however, the nature of the interaction between Mo centers and S ligands is unclear. Further, the development of cost-effective water-splitting systems using neutral water as a proton source for H2 evolution is highly desirable, whereas the mechanism of the HER at neutral pH is rarely discussed. Here, the structural change in the Mo-Mo and S-S species in a synthesized molybdenum sulfide was monitored at neutral pH using in situ electrochemical Raman spectroscopy. Analysis of the potential dependent Raman spectra revealed that the band assigned to a terminal S-S species emerged along with synchronized changes in the frequency of the Mo-Mo, Mo3-μ3S, and Mo-S vibrational bands. This indicates that Mo-Mo bonds and terminal S-S ligands play synergistic roles in facilitating hydrogen evolution, likely via the internal reorganization of trinuclear Mo3-thio species. The nature and role of metal-ligand interactions in the HER revealed in this study demonstrated a mechanism that is distinct from those reported previously in which the S or Mo sites function independently.
This work was supported by a JSPS Grant-in-Aid for Scientific Research (26288092).
Yamei Li,Ryuhei Nakamura. Structural change of molybdenum sulfide facilitates the electrocatalytic hydrogen evolution reaction at neutral pH as revealed by in situ Raman spectroscopy[J]. Chinese Journal of Catalysis, 2018, 39(3): 401-406.
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