Azide Passivation of Black Phosphorus Nanosheets: Covalent Functionalization Affords Ambient Stability Enhancement

Two‐dimensional (2D) black phosphorus (BP) has been attracting ever‐growing interest due to its unique band structure, but 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‐VA phosphorus atom hampers the passivation effect. Herein, we report for the first time covalent azide functionalization of BP nanosheets (BPNSs), 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.

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