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Exploring trimetallic clusters containing alkali and alkaline earth metal atoms with high activity for nitrogen activation

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Abstract

Activation of dinitrogen (N2) is the critical step in nitrogen reduction reaction (NRR) in ammonia synthesis. In this paper, reaction mechanisms of N2 activation on trimetallic clusters Mo2M (M = Li, Na, K, Mg, and Ca) and Mo3−xCax (x = 2–3) were systematically studied by density functional theory calculations. Unlike Mo2 which is inert to N2, clusters with alkali or alkaline earth metal atoms have much higher reactivity toward N2 in terms of both thermodynamics and kinetics. Particularly, in one reaction path of N2 with MoCa2, all the intermediates and transition states are well below the energy sum of the reactants, indicating that the dissociation of N2 on MoCa2 can take place spontaneously in gas-phase reactions. N2 transfers on clusters with different coordination modes, and the N−N bond is gradually activated. When N2 is bonded with three metal atoms with end-on: side-on: side-on coordination mode, it is fully activated and easily dissociated into two adsorbed N atoms. These results may serve as a prototype to design single-cluster catalysts with a trimetallic center for nitrogen activation and conversion.

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Funding

This work was financially supported by the National Natural Science Foundation of China (92161115, 61704054), the Fundamental Research Fund for the Central Universities (JB2015RCY03, JB2019MS052, JB2017MS056), and the Beijing Natural Science Foundation (2214064).

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Authors and Affiliations

  1. School of Mathematics and Physics, North China Electric Power University, Beinong Road 2, Huilongguan, Beijing, 102206, People’s Republic of China

    Xue-Qian Huang, Xun-Lei Ding, Jian Wang, Ya-Ya Wang, Joseph Israel Gurti, Yan Chen, Meng-Meng Wang, Wei Li & Xin Wang

  2. Institute of Clusters and Low Dimensional Nanomaterials, North China Electric Power University, Beinong Road 2, Huilongguan, Beijing, 102206, People’s Republic of China

    Xue-Qian Huang, Xun-Lei Ding, Jian Wang, Ya-Ya Wang, Joseph Israel Gurti, Yan Chen, Meng-Meng Wang, Wei Li & Xin Wang

  3. School of New Energy, North China Electric Power University, Beinong Road 2, Huilongguan, Beijing, 102206, People’s Republic of China

    Ya-Ya Wang, Yan Chen & Meng-Meng Wang

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  1. Xue-Qian Huang
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  7. Meng-Meng Wang
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  9. Xin Wang
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Contributions

Xue-Qian Huang: writing – original draft, investigation. Xun-Lei Ding: supervision, project administration, writing – review and editing. Jian Wang: data curation, visualization. Ya-Ya Wang: conceptualization, review. Joseph Israel Gurti: data curation, review. Yan Chen: data curation, validation. Meng-Meng Wang: validation, review. Wei Li: conceptualization, project administration. Xin Wang: methodology, validation.

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Correspondence to Xun-Lei Ding or Wei Li.

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Huang, XQ., Ding, XL., Wang, J. et al. Exploring trimetallic clusters containing alkali and alkaline earth metal atoms with high activity for nitrogen activation. Struct Chem 34, 87–96 (2023). https://doi.org/10.1007/s11224-022-01919-x

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  • DOI: https://doi.org/10.1007/s11224-022-01919-x

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