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Tuning main-group s-block metal Mg as a promising single-atom electrocatalyst for N2 fixation: A DFT study

  • 1.

    Hefei National Laboratory for Physical Sciences at the Microscale, Department of Materials Science and Engineering, University of Science and Technology of China, Hefei 230026, China

  • 2.

    The Anhui High Magnetic Field Laboratory, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China

  • 3.

    Department of Materials Science and Engineering, Center of Super-Diamond and Advanced Films (COSDAF), City University of Hong Kong, Hong Kong 999077, China

  • 4.

    School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, China

Cite this:
https://doi.org/10.52396/JUST-2021-0126
  • Received Date: 07 May 2021
  • Rev Recd Date: 29 June 2021
  • Publish Date: 30 November 2021
    Abstract

  • Abstract

    The electrocatalytic nitrogen reduction reaction (NRR) can transform nitrogen and protons from aqueous electrolytes to ammonia by using renewable electricity under ambient conditions, which is a promising technology to replace the Haber-Bosch process. However, this technology is extremely challenging as it requires highly active electrocatalysts to break the stable triple-bonds of N2.With p bands,main-group s-block metals have been rarely explored in NRR compared with transition metals.Herein, we employ first-principles calculations to propose a Mg single atom catalyst as a promising high-performance electrocatalyst for NRR, where Mg atom is coordinated with four oxygen atoms within graphene (Mg-O4). Our results reveal that N2 can be efficiently activated on Mg-O4 and reduced into NH3 through the alternating mechanism. Moreover, ab initio molecular dynamics simulations demonstrate the Mg-O4 structure has high stability.

    Abstract

    The electrocatalytic nitrogen reduction reaction (NRR) can transform nitrogen and protons from aqueous electrolytes to ammonia by using renewable electricity under ambient conditions, which is a promising technology to replace the Haber-Bosch process. However, this technology is extremely challenging as it requires highly active electrocatalysts to break the stable triple-bonds of N2.With p bands,main-group s-block metals have been rarely explored in NRR compared with transition metals.Herein, we employ first-principles calculations to propose a Mg single atom catalyst as a promising high-performance electrocatalyst for NRR, where Mg atom is coordinated with four oxygen atoms within graphene (Mg-O4). Our results reveal that N2 can be efficiently activated on Mg-O4 and reduced into NH3 through the alternating mechanism. Moreover, ab initio molecular dynamics simulations demonstrate the Mg-O4 structure has high stability.
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    • References(42)
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    Chen P Z, Zhang N, Wang S B, et al. Interfacial engineering of cobalt sulfide/graphene hybrids for highly efficient ammonia electrosynthesis. PANS, 2019, 116(14): 6635-6640.
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    Zhang N, Jalil A, Wu D X, et al. Refining defect states in W18O49 by Mo doping: A strategy for tuning N2 activation towards solar-driven nitrogen fixation. J. Am. Chem. Soc., 2018, 140(30): 9434-9443.
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    Deng D H, Novoselov K S, Fu Q, et al. Catalysis with two-dimensional materials and their heterostructures. Nat. Nanotech., 2016, 11: 218-230.
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    Fei H L, Dong J C, Wan C Z, et al. Microwave-assisted rapid synthesis of graphene-supported single atomic metals. Adv. Mater., 2018, 30(35): 1802146.
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    Zhang L Z, Jia Y, Gao G P, et al. Graphene defects trap atomic Ni species for hydrogen and oxygen evolution reactions. Chem, 2018, 4(2): 285-297.
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    Du Z Z, Chen X J, Hu W, et al. Cobalt in nitrogen-doped graphene as single-atom catalyst for high-sulfur content lithium-sulfur batteries. J. Am. Chem. Soc., 2019, 141(9): 3977-3985.
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    Hu B, Hu M W, Seefeldt L, et al. Electrochemical dinitrogen reduction to ammonia by Mo2N: Catalysis or decomposition? ACS Energy Lett., 2019, 4: 1053-1054.
    [25]
    Tang C, Qiao S Z. How to explore ambient electrocatalytic nitrogen reduction reliably and insightfully. Chem. Soc. Rev., 2019, 48: 3166-3180.
    [26]
    Andersen S Z, oli V, Yang S, et al. A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements. Nature, 2019, 570: 504-508.
    [27]
    Kresse G, Hafner J. Ab-initio molecular-dynamics for open-shell transition-metals. Phys. Rev. B, 1993, 48: 13115-13118.
    [28]
    Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys. Rev. Lett., 1996, 77: 3865-3868.
    [29]
    Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B, 1999, 59: 1758-1775.
    [30]
    Maintz S, Deringer V L, Tchougréeff A L, et al. LOBSTER: A tool to extract chemical bonding from plane-wave based DFT. J. Comput. Chemi., 2016, 37: 1030-1035.
    [31]
    Dronskowski R, Bloechl P E. Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations. J. Phys. Chem., 1993, 97: 8617-8624.
    [32]
    Riyaz M, Goel N. Single-atom catalysis using chromium embedded in divacant graphene for conversion of dinitrogen to ammonia. ChemPhysChem, 2019, 20(15): 1954-1959.
    [33]
    Wang J, Huang Z Q, Liu W, et al. Design of N-coordinated dual-metal sites: A stable and active Pt-free catalyst for acidic oxygen reduction reaction. J. Am. Chem. Soc., 2017, 139(48): 17281-17284.
    [34]
    Zheng T T, Jiang K, Ta N, et al. Large-scale and highly selective CO2 electrocatalytic reduction on nickel single-atom catalyst. Joule, 2019, 3(1): 265-278.
    [35]
    Ling C Y, Niu X H, Li Q, et al. Metal-free single atom catalyst for N2 fixation driven by visible light. J. Am. Chem. Soc., 2018, 140(43): 14161-14168.
    [36]
    Zheng X N, Yao Y, Wang Y, et al. Tuning the electronic structure of transition metals embedded in nitrogen-doped graphene for electrocatalytic nitrogen reduction: a first-principles study. Nanoscale, 2020, 12: 9696-9707.
    [37]
    Robbins D L, Brock L R, Pilgrim J S, et al. Electronic spectroscopy of the Mg+–N2 complex: evidence for photoinduced activation of N2. J. Chem. Phys., 1995, 102: 1481-1492.
    [38]
    Legare M A, Belanger-Chabot G, Dewhurst R D, et al. Nitrogen fixation and reduction at boron. Science, 2018, 359(6378): 896-899.
    [39]
    Li X F, Li Q K, Cheng J, et al. Conversion of dinitrogen to ammonia by FeN3-embedded graphene. J. Am. Chem. Soc., 2016, 138(28): 8706-8709.
    [40]
    Yin H, Li S L, Gan L Y, et al. Pt-embedded in monolayer g-C3N4 as a promising single-atom electrocatalyst for ammonia synthesis. J. Mater. Chem. A, 2019, 7: 11908-11914.
    [41]
    Liu S S, Wang M F, Qian T, et al. Facilitating nitrogen accessibility to boron-rich covalent organic frameworks via electrochemical excitation for efficient nitrogen fixation. Nat. Commun., 2019, 10: 3898.
    [42]
    Montoya J H, Tsai C, Vojvodic A, et al. The challenge of electrochemical ammonia synthesis: A new perspective on the role of nitrogen scaling relations. ChemSusChem, 2015, 8(13): 2180-2186.
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    [1]
    Chen P Z, Zhang N, Wang S B, et al. Interfacial engineering of cobalt sulfide/graphene hybrids for highly efficient ammonia electrosynthesis. PANS, 2019, 116(14): 6635-6640.
    [2]
    Chen G F, Yuan Y F, Jiang H F, Ren, et al. Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst. Nat. Energy, 2020, 5: 605-613.
    [3]
    Zhang N, Jalil A, Wu D X, et al. Refining defect states in W18O49 by Mo doping: A strategy for tuning N2 activation towards solar-driven nitrogen fixation. J. Am. Chem. Soc., 2018, 140(30): 9434-9443.
    [4]
    Suryanto B H, Du H L, Wang, D B, et al. Challenges and prospects in the catalysis of electroreduction of nitrogen to ammonia. Nat. Catal., 2019, 2: 290-296.
    [5]
    van der Ham C J, Koper M T, Hetterscheid D G. Challenges in reduction of dinitrogen by proton and electron transfer. Chem. Soc. Rev., 2014, 43: 5183-5191.
    [6]
    Chen J G, Crooks R M, Seefeldt L C, et al. Beyond fossil fuel-driven nitrogen transformations. Science, 2018, 360(6391): eaar6611.
    [7]
    Kitano M, Inoue Y, Yamazaki Y, et al. Ammonia synthesis using a stable electride as an electron donor and reversible hydrogen store. Nat. Chem., 2012, 4: 934-940.
    [8]
    Geng Z G, Liu Y, Kong X D, et al. Achieving a record-high yield rate of 120.9 for N2 electrochemical reduction over Ru single-atom catalysts. Adv. Mater., 2018, 30(40): 1803498.
    [9]
    Soloveichik G. Electrochemical synthesis of ammonia as a potential alternative to the Haber–Bosch process. Nat. Catal., 2019, 2: 377-380.
    [10]
    Lee H K, Koh C S, Lee Y H, et al. Favoring the unfavored: selective electrochemical nitrogen fixation using a reticular chemistry approach. Sci. Adv., 2018, 4(3): eaar3208.
    [11]
    Tao H C, Choi C, Ding L X, et al. Nitrogen fixation by Ru single-atom electrocatalytic reduction. Chem, 2019, 5(1): 204-214.
    [12]
    Liu S S, Qian T, Wang M F, et al. Proton-filtering covalent organic frameworks with superior nitrogen penetration flux promote ambient ammonia synthesis. Nat. Catal., 2021, 4: 322-331.
    [13]
    Luo Y R, Chen G F, Ding L, et al. Efficient electrocatalytic N2 fixation with MXene under ambient conditions. Joule, 2019, 3(1): 279-289.
    [14]
    Liu Y, Li Q Y, Guo X, et al. A highly efficient metal-free electrocatalyst of F-doped porous carbon toward N2 electroreduction. Adv. Mater., 2020, 32(24): 1907690.
    [15]
    Tong Y Y, Guo H P, Liu D L, et al. Vacancy engineering of iron-doped W18O49 nanoreactors for low-barrier electrochemical nitrogen reduction. Angew. Chem. Int. Ed., 2020, 59(19): 7356-7361.
    [16]
    Liu Y Y, Han M M, Xiong Q Z, et al. Dramatically enhanced ambient ammonia electrosynthesis performance by in-operando created Li-S interactions on MoS2 electrocatalyst. Adv. Energy Mater., 2019, 9(14): 1803935.
    [17]
    Zhao Y F, Zhou H, Zhu X R, et al. Simultaneous oxidative and reductive reactions in one system by atomic design. Nat. Catal., 2021, 4: 134-143.
    [18]
    Borah K D, Bhuyan J. Magnesium porphyrins with relevance to chlorophylls. Dalton Trans., 2017, 46: 6497–6509.
    [19]
    Deshpande C N, Ruwe T A, Shawki A, et al. Calcium is an essential cofactor for metal efflux by the ferroportin transporter family. Nat. Commun., 2018, 9: 3075.
    [20]
    Deng D H, Novoselov K S, Fu Q, et al. Catalysis with two-dimensional materials and their heterostructures. Nat. Nanotech., 2016, 11: 218-230.
    [21]
    Fei H L, Dong J C, Wan C Z, et al. Microwave-assisted rapid synthesis of graphene-supported single atomic metals. Adv. Mater., 2018, 30(35): 1802146.
    [22]
    Zhang L Z, Jia Y, Gao G P, et al. Graphene defects trap atomic Ni species for hydrogen and oxygen evolution reactions. Chem, 2018, 4(2): 285-297.
    [23]
    Du Z Z, Chen X J, Hu W, et al. Cobalt in nitrogen-doped graphene as single-atom catalyst for high-sulfur content lithium-sulfur batteries. J. Am. Chem. Soc., 2019, 141(9): 3977-3985.
    [24]
    Hu B, Hu M W, Seefeldt L, et al. Electrochemical dinitrogen reduction to ammonia by Mo2N: Catalysis or decomposition? ACS Energy Lett., 2019, 4: 1053-1054.
    [25]
    Tang C, Qiao S Z. How to explore ambient electrocatalytic nitrogen reduction reliably and insightfully. Chem. Soc. Rev., 2019, 48: 3166-3180.
    [26]
    Andersen S Z, oli V, Yang S, et al. A rigorous electrochemical ammonia synthesis protocol with quantitative isotope measurements. Nature, 2019, 570: 504-508.
    [27]
    Kresse G, Hafner J. Ab-initio molecular-dynamics for open-shell transition-metals. Phys. Rev. B, 1993, 48: 13115-13118.
    [28]
    Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys. Rev. Lett., 1996, 77: 3865-3868.
    [29]
    Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B, 1999, 59: 1758-1775.
    [30]
    Maintz S, Deringer V L, Tchougréeff A L, et al. LOBSTER: A tool to extract chemical bonding from plane-wave based DFT. J. Comput. Chemi., 2016, 37: 1030-1035.
    [31]
    Dronskowski R, Bloechl P E. Crystal orbital Hamilton populations (COHP): energy-resolved visualization of chemical bonding in solids based on density-functional calculations. J. Phys. Chem., 1993, 97: 8617-8624.
    [32]
    Riyaz M, Goel N. Single-atom catalysis using chromium embedded in divacant graphene for conversion of dinitrogen to ammonia. ChemPhysChem, 2019, 20(15): 1954-1959.
    [33]
    Wang J, Huang Z Q, Liu W, et al. Design of N-coordinated dual-metal sites: A stable and active Pt-free catalyst for acidic oxygen reduction reaction. J. Am. Chem. Soc., 2017, 139(48): 17281-17284.
    [34]
    Zheng T T, Jiang K, Ta N, et al. Large-scale and highly selective CO2 electrocatalytic reduction on nickel single-atom catalyst. Joule, 2019, 3(1): 265-278.
    [35]
    Ling C Y, Niu X H, Li Q, et al. Metal-free single atom catalyst for N2 fixation driven by visible light. J. Am. Chem. Soc., 2018, 140(43): 14161-14168.
    [36]
    Zheng X N, Yao Y, Wang Y, et al. Tuning the electronic structure of transition metals embedded in nitrogen-doped graphene for electrocatalytic nitrogen reduction: a first-principles study. Nanoscale, 2020, 12: 9696-9707.
    [37]
    Robbins D L, Brock L R, Pilgrim J S, et al. Electronic spectroscopy of the Mg+–N2 complex: evidence for photoinduced activation of N2. J. Chem. Phys., 1995, 102: 1481-1492.
    [38]
    Legare M A, Belanger-Chabot G, Dewhurst R D, et al. Nitrogen fixation and reduction at boron. Science, 2018, 359(6378): 896-899.
    [39]
    Li X F, Li Q K, Cheng J, et al. Conversion of dinitrogen to ammonia by FeN3-embedded graphene. J. Am. Chem. Soc., 2016, 138(28): 8706-8709.
    [40]
    Yin H, Li S L, Gan L Y, et al. Pt-embedded in monolayer g-C3N4 as a promising single-atom electrocatalyst for ammonia synthesis. J. Mater. Chem. A, 2019, 7: 11908-11914.
    [41]
    Liu S S, Wang M F, Qian T, et al. Facilitating nitrogen accessibility to boron-rich covalent organic frameworks via electrochemical excitation for efficient nitrogen fixation. Nat. Commun., 2019, 10: 3898.
    [42]
    Montoya J H, Tsai C, Vojvodic A, et al. The challenge of electrochemical ammonia synthesis: A new perspective on the role of nitrogen scaling relations. ChemSusChem, 2015, 8(13): 2180-2186.
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