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Nitrogen reduction reaction on small iron clusters supported by N-doped graphene: A theoretical study of the atomically precise active-site mechanism

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Abstract

Nonprecious metal catalysts are known of significance for electrochemical N2 reduction reaction (NRR) of which the mechanism has been illustrated by ongoing investigations of single atom catalysis. However, it remains challenging to fully understand the size-dependent synergistic effect of active sites inherited in substantial nanocatalysts. In this work, four types of small iron clusters Fen (n = 1–4) supported on nitrogen-doped graphene sheets are constructed to figure out the size dependence and synergistic effect of active sites for NRR catalytic activities. It is revealed that Fe3 and Fe4 clusters on N4G supports exhibit higher NRR activity than single-iron atom and iron dimer clusters, showing lowered limiting potential and restricted hydrogen evolution reaction (HER) which is a competitive reaction channel. In particular, the Fe4-N4G displays outstanding NRR performance for “side-on” adsorption of N2 with a small limiting potential (−0.45 V). Besides the specific structure and strong interface interaction within the Fe4-N4G itself, the high NRR activity is associated with the unique bonding/antibonding orbital interactions of N-N and N-Fe for the adsorptive N2 and NNH intermediates, as well as relatively large charge transfer between N2 and the cluster Fe4-N4G.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (Nos. 21802146 and 21722308), CAS Key Research Project of Frontier Science (No. QYZDB-SSW-SLH024), and Frontier Cross Project of National Laboratory for Molecular Sciences (No. 051Z011BZ3).

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  1. Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Chaonan Cui, Hongchao Zhang & Zhixun Luo

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Chaonan Cui, Hongchao Zhang & Zhixun Luo

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Nitrogen reduction reaction on small iron clusters supported by N-doped graphene: A theoretical study of the atomically precise active-site mechanism

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Cui, C., Zhang, H. & Luo, Z. Nitrogen reduction reaction on small iron clusters supported by N-doped graphene: A theoretical study of the atomically precise active-site mechanism. Nano Res. 13, 2280–2288 (2020). https://doi.org/10.1007/s12274-020-2847-0

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