Abstract
Atomically dispersed metal has gained much attention because of the new opportunities they offer in catalysis. However, it is still crucial to understand the mechanism of single-atom catalysis at molecular level for expanding them to other more difficult catalytic reactions, such as ammonia synthesis from nitrogen. In fact, developing ammonia synthesis under ambient conditions to overcome the high energy consumption in well-established Haber-Bosch process has fascinated scientists for many years. Herein, we demonstrate that single Cu atom yields facile valence-electron isolation from the conjugated π electron cloud of p-CN. Electron spin resonance measurements reveal that these isolated valence electrons can be easily excited to generate free electrons under photo-illumination, thus inducing high efficient photo-induced ammonia synthesis under ambient conditions. The NH3 producing rate of copper modified carbon nitride (Cu-CN) reached 186 μmol g−1 h−1 under visible light irradiation with the quantum efficiency achieved 1.01% at 420 nm monochromatic light. This finding surely offers a model to open up a new vista for the ammonia synthesis at gentle conditions. The introduction of single atom to isolate the valence electron also represents a new paradigm for many other photocatalytic reactions, since the most photoinduced processes have been successfully exploited sharing the same origin.
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Acknowledgements
This work was supported by the National Key R&D Program of China (2017YFA0207301), the National Natural Science Foundation of China (21622107, 11621063, U1532265), the Key Research Program of Frontier Sciences (QYZDY-SSW-SLH011), the Youth Innovation Promotion Association CAS (2016392), the Fundamental Research Funds of Central University (WK2340000075), and the Major Program of Development Foundation of Hefei Center for Physical Science and Technology (2017FXZY003). We thank Prof. J.H. Su from the University of Science and Technology of China for his helpful discussion of the ESR results. The computational center of USTC is acknowledged for computational support.
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Huang, P., Liu, W., He, Z. et al. Single atom accelerates ammonia photosynthesis. Sci. China Chem. 61, 1187–1196 (2018). https://doi.org/10.1007/s11426-018-9273-1
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DOI: https://doi.org/10.1007/s11426-018-9273-1