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Azide Passivation of Black Phosphorus Nanosheets: Covalent Functionalization Affords Ambient Stability Enhancement
Author(s) -
Liu Yajuan,
Gao Pengfei,
Zhang Taiming,
Zhu Xianjun,
Zhang Mengmeng,
Chen Muqing,
Du Pingwu,
Wang GuanWu,
Ji Hengxing,
Yang Jinlong,
Yang Shangfeng
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201813218
Subject(s) - surface modification , azide , covalent bond , chemistry , passivation , photochemistry , moiety , reactivity (psychology) , nitrene , nucleophile , aryl , polymer chemistry , combinatorial chemistry , organic chemistry , alkyl , catalysis , layer (electronics) , medicine , alternative medicine , pathology
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 spectroscopic 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.