Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 5, Pages 1479-1483Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201813218
Keywords
2D nanosheets; azides; black phosphorus; covalent functionalization; nitrenes
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Funding
- National Key Research and Development Program of China [2017YFA0402800, 2016YFA0200604]
- National Natural Science Foundation of China [51572254, 21688102, 51672262, 51761145046]
- Major/Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology [2016FXZY003]
- Fundamental Research Funds for the Central Universities [WK3430000003, WK3430000023]
- Anhui Initiative in Quantum Information Technologies [AHY090400]
- 100 Talents Program of the Chinese Academy of Sciences
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Two-dimensional (2D) black phosphorus (BP) has a unique band structure, but it suffers from low ambient stability owing to its high reactivity to oxygen. Covalent functionalization has been demonstrated to passivate the reactive BP effectively, however the reported covalent functionalization methods are quite limited to aryl diazonium and nucleophilic additions affording P-C and P-O-C single bonds, for which the retaining of one unpaired electron in the Group 15 phosphorus atom hampers the passivation effect. Now, covalent azide functionalization of BP nanosheets (BPNSs) is reported, leading to significant enhancement of the ambient stability of BP as confirmed by UV/Vis spectro-scopic studies. The most stable configuration of the azide functionalized BPNSs (f-BPNSs) is predicted by theoretical calculations, featuring the grafting of benzoic acid moiety onto BPNSs via the unprecedented P=N double bonds formed through in situ nitrene as a reactive intermediate.
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