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Title: Non-Transition-Metal Catalytic System for N2 Reduction to NH3: A Density Functional Theory Study of Al-Doped Graphene

Abstract

The prevalent catalysts for natural and artificial N2 fixation are known to hinge upon transition-metal (TM) elements. In this paper, we demonstrate by density functional theory that Al-doped graphene is a potential non-TM catalyst to convert N2 to NH3 in the presence of relatively mild proton/electron sources. In the integrated structure of the catalyst, the Al atom serves as a binding site and catalytic center while the graphene framework serves as an electron buffer during the successive proton/electron additions to N2 and its various downstream NxHy intermediates. The initial hydrogenation of N2 can readily take place via an internal H-transfer process with the assistance of a Li+ ion as an additive. Finally, in view of the recurrence of H transfer in the first step of N2 reduction observed in biological nitrogenases and other synthetic catalysts, this finding highlights the significance of heteroatom-assisted H transfer in the design of synthetic catalysts for N2 fixation.

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]
+ Show Author Affiliations
  1. Sichuan Univ., Chengdu (China). Research Center of Analytical Instrumentation. College of Life Sciences
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences. Computational Sciences & Engineering Division
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation of China (NSFC)
OSTI Identifier:
1422604
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231; 21443012
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 9; Journal Issue: 3; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Tian, Yong-Hui, Hu, Shuangli, Sheng, Xiaolan, Duan, Yixiang, Jakowski, Jacek, Sumpter, Bobby G., and Huang, Jingsong. Non-Transition-Metal Catalytic System for N2 Reduction to NH3: A Density Functional Theory Study of Al-Doped Graphene. United States: N. p., 2018. Web. doi:10.1021/acs.jpclett.7b03094.
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Tian, Yong-Hui, Hu, Shuangli, Sheng, Xiaolan, Duan, Yixiang, Jakowski, Jacek, Sumpter, Bobby G., & Huang, Jingsong. Non-Transition-Metal Catalytic System for N2 Reduction to NH3: A Density Functional Theory Study of Al-Doped Graphene. United States. https://doi.org/10.1021/acs.jpclett.7b03094
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Tian, Yong-Hui, Hu, Shuangli, Sheng, Xiaolan, Duan, Yixiang, Jakowski, Jacek, Sumpter, Bobby G., and Huang, Jingsong. Tue . "Non-Transition-Metal Catalytic System for N2 Reduction to NH3: A Density Functional Theory Study of Al-Doped Graphene". United States. https://doi.org/10.1021/acs.jpclett.7b03094. https://www.osti.gov/servlets/purl/1422604.
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@article{osti_1422604,
title = {Non-Transition-Metal Catalytic System for N2 Reduction to NH3: A Density Functional Theory Study of Al-Doped Graphene},
author = {Tian, Yong-Hui and Hu, Shuangli and Sheng, Xiaolan and Duan, Yixiang and Jakowski, Jacek and Sumpter, Bobby G. and Huang, Jingsong},
abstractNote = {The prevalent catalysts for natural and artificial N2 fixation are known to hinge upon transition-metal (TM) elements. In this paper, we demonstrate by density functional theory that Al-doped graphene is a potential non-TM catalyst to convert N2 to NH3 in the presence of relatively mild proton/electron sources. In the integrated structure of the catalyst, the Al atom serves as a binding site and catalytic center while the graphene framework serves as an electron buffer during the successive proton/electron additions to N2 and its various downstream NxHy intermediates. The initial hydrogenation of N2 can readily take place via an internal H-transfer process with the assistance of a Li+ ion as an additive. Finally, in view of the recurrence of H transfer in the first step of N2 reduction observed in biological nitrogenases and other synthetic catalysts, this finding highlights the significance of heteroatom-assisted H transfer in the design of synthetic catalysts for N2 fixation.},
doi = {10.1021/acs.jpclett.7b03094},
journal = {Journal of Physical Chemistry Letters},
number = 3,
volume = 9,
place = {United States},
year = {Tue Jan 16 00:00:00 EST 2018},
month = {Tue Jan 16 00:00:00 EST 2018}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acs.jpclett.7b03094
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Cited by: 33 works
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Figures / Tables:

Figure 1 Figure 1: Structure of the Al-doped graphene (G-Al) models with a C atom in the graphene framework substituted by an Al atom: (a) fragment model C120H27Al; (b) periodic model C127Al. A N2 molecule is ligated to the Al center in an end-on fashion. C, gray; N, blue; Al, pink; H,more » white.« less
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    Works referencing / citing this record:

    Photoactive Earth‐Abundant Iron Pyrite Catalysts for Electrocatalytic Nitrogen Reduction Reaction
    journal, October 2019

    Single‐Site Gold Catalysts on Hierarchical N‐Doped Porous Noble Carbon for Enhanced Electrochemical Reduction of Nitrogen
    journal, August 2018

    Transition Metal‐dinitrogen Complex Embedded Graphene for Nitrogen Reduction Reaction
    journal, May 2019

    Nitrogen Fixation Reaction Derived from Nanostructured Catalytic Materials
    journal, August 2018

    • Wang, Shengyao; Ichihara, Fumihiko; Pang, Hong
    • Advanced Functional Materials, Vol. 28, Issue 50
    • DOI: 10.1002/adfm.201803309

    Li 2 S growth on graphene: Impact on the electrochemical performance of Li-S batteries
    journal, January 2020

    • Longo, Roberto C.; Camacho-Forero, Luis E.; Balbuena, Perla B.
    • The Journal of Chemical Physics, Vol. 152, Issue 1
    • DOI: 10.1063/1.5135304

    Electrochemical synthesis of ammonia from N 2 and H 2 O using a typical non-noble metal carbon-based catalyst under ambient conditions
    journal, January 2019

    • Cong, Linchuan; Yu, Zhuochen; Liu, Fangbing
    • Catalysis Science & Technology, Vol. 9, Issue 5
    • DOI: 10.1039/c8cy02316f
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