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The major bottlenecks for ammonia (NH3) synthesis under mild conditions are the activation of the extremely inert N N bond (941 kJ mol(-1)) and/or the desorption of NH3 from the catalyst surface. Electron donation from the appropriate promoters is essential to enhance N-2 activation over Fe or Ru catalysts. Nevertheless, despite typical element promoters enhancing the N-2 activation efficiency, they induce strong NH3 binding on the catalyst surface, leading to the need for high temperatures and pressures for the reaction to complete. Herein, we propose the use of a molecular promoter (C-60) to tackle the difficulties. The positioning role of C-60 at a 1 nm scale on small Ru nanoclusters drives the exposure of more terrace sites (geometric effect) and induces d-pi interactions at the Ru-C-60 junctions. The latter electronically modifies the Ru sites (electronic effect), thereby synergistically contributing to N-2 and H-2 activation as well as to the release of NH3 on the Ru sites. The significant electron buffer attribute of C-60 and the strong electronic interaction between Ru and C-60 facilitate a shift of d-band center toward the Fermi level and a decrease of work function, simultaneously satisfying the electronic requirements for N-2 activation enhancement and NH3 binding weakening. Consequently, the C-60-promoted Ru/LaN catalyst exhibits a high NH3 synthesis rate. It is envisioned that our findings have significant implications for the rational search of molecular promoters for high-efficiency NH3 synthesis.
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ACS CATALYSIS
ISSN: 2155-5435
Year: 2025
Issue: 4
Volume: 15
Page: 2827-2838
1 1 . 7 0 0
JCR@2023
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ESI Highly Cited Papers on the List: 0 Unfold All
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30 Days PV: 2