Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 139, Issue 12, Pages 4342-4345Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.7b01350
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Funding
- NSF Chemistry Catalysis Program of the Chemistry Division [CHE-1566106]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [1566106] Funding Source: National Science Foundation
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Redox processes of molybdenum-sulfide (Mo-S) compounds are important in the function of materials for various applications from electrocatalysts for the hydrogen evolution reaction (I-TER) to cathode materials for batteries. Our group has recently described a series of Mo-S molecular HER catalysts based on a MoO(S-2)(2)L-2 structural motif. Herein, reductive pathways of MoO(S-2)(2)bpy (Mo-bpy) (bpy = 2,2'-bipyridine) are presented from both experimental and theoretical studies. We tracked chemical reduction of Mo-bpy with UV vis spectroscopy using sodium napthalenide (NaNpth) as the reducing agent and found that Mo-bpy undergoes anionic persulfide reduction to form the tetragonal Mo(VI) complex [MoOS3](2-). We also identified silver mercury amalgam as an inert working electrode (WE) for spectroectrochemical (SEC) studies. UV-vis spectra in the presence of trifluoroacetic acid with an applied potential confirmed that Mo-bpy maintains its structure during catalytic cycling. Finally, theoretical catalytic reaction pathways were explored, revealing that Mo=O may function as a proton relay. This finding together with the observed anion reduction as the redox center is of broad interest for amorphous Mo-S (a-MoSx) electrocatalytic materials and anion-redox chalcogel battery materials.
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