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Title: Cobalt-Modulated Molybdenum–Dinitrogen Interaction in MoS2 for Catalyzing Ammonia Synthesis

Abstract

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.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2];  [1];  [3];  [1]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Rice Univ., Houston, TX (United States). Dept. of Materials Science & Nanoengineering
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  3. Nanyang Technological Univ. (Singapore). School of Materials Science and Engineering
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1574916
Report Number(s):
BNL-212342-2019-JAAM
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 49; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; Co-doped MoS2-x; Sulfur vacancy; Nitrogen reduction reaction; Faradic efficiency

Citation Formats

Zhang, Jing, Tian, Xiaoyin, Liu, Mingjie, Guo, Hua, Zhou, Jiadong, Fang, Qiyi, Liu, Zheng, Wu, Qin, and Lou, Jun. Cobalt-Modulated Molybdenum–Dinitrogen Interaction in MoS2 for Catalyzing Ammonia Synthesis. United States: N. p., 2019. Web. https://doi.org/10.1021/jacs.9b02501.
Zhang, Jing, Tian, Xiaoyin, Liu, Mingjie, Guo, Hua, Zhou, Jiadong, Fang, Qiyi, Liu, Zheng, Wu, Qin, & Lou, Jun. Cobalt-Modulated Molybdenum–Dinitrogen Interaction in MoS2 for Catalyzing Ammonia Synthesis. United States. https://doi.org/10.1021/jacs.9b02501
Zhang, Jing, Tian, Xiaoyin, Liu, Mingjie, Guo, Hua, Zhou, Jiadong, Fang, Qiyi, Liu, Zheng, Wu, Qin, and Lou, Jun. Fri . "Cobalt-Modulated Molybdenum–Dinitrogen Interaction in MoS2 for Catalyzing Ammonia Synthesis". United States. https://doi.org/10.1021/jacs.9b02501. https://www.osti.gov/servlets/purl/1574916.
@article{osti_1574916,
title = {Cobalt-Modulated Molybdenum–Dinitrogen Interaction in MoS2 for Catalyzing Ammonia Synthesis},
author = {Zhang, Jing and Tian, Xiaoyin and Liu, Mingjie and Guo, Hua and Zhou, Jiadong and Fang, Qiyi and Liu, Zheng and Wu, Qin and Lou, Jun},
abstractNote = {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.},
doi = {10.1021/jacs.9b02501},
journal = {Journal of the American Chemical Society},
number = 49,
volume = 141,
place = {United States},
year = {2019},
month = {11}
}

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