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

Zhang, Jing; Tian, Xiaoyin; Liu, Mingjie; Guo, Hua; Zhou, Jiadong; Fang, Qiyi; Liu, Zheng; Wu, Qin; Lou, Jun

doi:10.1021/jacs.9b02501

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

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Abstract

Dinitrogen conversion to ammonia via electrochemical reduction with over 10% Faradaic efficiency is demonstrated in this work. Co-doped MoS_2-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 MoS_2-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 MoS_2-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:

^[1]; Tian, Xiaoyin ^[1];

^[2]; Guo, Hua ^[1]; Zhou, Jiadong ^[3]; Fang, Qiyi ^[1];

^[3];

^[2];

^[1]

Rice Univ., Houston, TX (United States). Dept. of Materials Science & Nanoengineering
Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Nanyang Technological Univ. (Singapore). School of Materials Science and Engineering

Publication Date:: Fri Nov 08 00:00:00 EST 2019

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.  doi:10.1021/jacs.9b02501.

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                    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

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                    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.

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@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         = {Fri Nov 08 00:00:00 EST 2019},

  month        = {Fri Nov 08 00:00:00 EST 2019}

}

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

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