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Plasmon-mediated photodecomposition of NH3 via intramolecular charge transfer

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Abstract

As an excellent clean medium for hydrogen storage and fuel cell applications, the photolysis of ammonia via localized surface plasmon could be invoked as a promising route towards significantly reducing the temperature for conventional thermolysis. Here, we explore the underlying microscopic mechanism of ultrafast carrier dynamics in plasmon-mediated NH3 photodecomposition at the single-molecular level using real-time time-dependent density functional theory. The NH3 molecule adsorbed on the tip of archetypal magic metal clusters represented by tetrahedral Ag20 and icosahedral Ag147, splits within a hundred femtoseconds upon laser pulse illumination. We found that the splitting of the first N-H bond is dominated by the intramolecular charge transfer driven by localized surface plasmon. Surprisingly, the phase of laser pulse could modulate the dynamics of charge transfer and thus affect the plasmon-induced bond breaking. These findings offer a new avenue for NH3 decomposition and provide in-depth insights in designing highly efficient plasmon-mediated photocatalysts.

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Acknowledgements

We acknowledge financial support from MOST, the National Key Research and Development Project (No. 2021YFA1400200), the National Natural Science Foundation of China (NSFC) (Nos. 12025407, 11774396, 91850120, 11934003, and 11674289), and CAS (XDB330301).

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Authors and Affiliations

  1. Beijing National Laboratory for Condensed Matter Physics and Institute of Physics, Chinese Academy of Sciences, Beijing, 100190, China

    Yimin Zhang, Daqiang Chen & Sheng Meng

  2. Key Laboratory of Material Physics, Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou, 450001, China

    Yimin Zhang, Weite Meng, Lili Zhang & Shunfang Li

  3. School of Chemical Engineering, Anhui University of Science and Technology, Huainan, 232000, China

    Weite Meng

  4. School of Physical Sciences, University of Chinese Academy of Sciences, Beijing, 100190, China

    Yimin Zhang, Daqiang Chen & Sheng Meng

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  1. Yimin Zhang
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Correspondence to Shunfang Li or Sheng Meng.

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Zhang, Y., Meng, W., Chen, D. et al. Plasmon-mediated photodecomposition of NH3 via intramolecular charge transfer. Nano Res. 15, 3894–3900 (2022). https://doi.org/10.1007/s12274-021-4021-8

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