Cobalt-Modulated Molybdenum–Dinitrogen Interaction in MoS2 for Catalyzing Ammonia Synthesis
Dinitrogen conversion to ammonia via electrochemical reduction with over 10% Faradaic efficiency is demonstrated in this work. Co-doped MoS2-x polycrystalline nanosheets with S vacancies as the catalysts are loaded onto carbon cloth by hydrothermal growth from Mo, Co, and S precursors. A sulfur vacancy on the MoS2-x basal plane mimicking the natural Mo-nitrogenase active site is modified by Co doping and exhibits superior dinitrogen-to-ammonia conversion activity. Density-functional simulation reveals that the free energy barrier, which can be compensated by applied overpotential, is reduced from 1.62 to 0.59 eV after Co doping. Meanwhile, dinitrogen tends to be chemically adsorbed to defective MoS2-x, which effectively activates the dinitrogen molecule for the dissociation of the N≡N triple bond. Here, this process is further accelerated by Co doping, resulting from the modulation of Mo–N bonding configuration.
- Research Organization:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- SC0012704
- OSTI ID:
- 1574916
- Report Number(s):
- BNL-212342-2019-JAAM
- Journal Information:
- Journal of the American Chemical Society, Vol. 141, Issue 49; ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
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