In-Situ Electrochemical Exfoliation and Methylation of Black Phosphorus into Functionalized Phosphorene Nanosheets

Two-dimensional black phosphorus (BP) has attracted great attention as a perspective material for various applications. The chemical functionalization of BP is an important pathway for the preparation of materials with improved stability and enhanced intrinsic electronic properties. Currently, most...

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Bibliographic Details
Published in:International journal of molecular sciences 2023-02, Vol.24 (4), p.3095
Main Authors: Kuchkaev, Aidar M, Kuchkaev, Airat M, Sukhov, Aleksander V, Saparina, Svetlana V, Gnezdilov, Oleg I, Klimovitskii, Alexander E, Ziganshina, Sufia A, Nizameev, Irek R, Asanov, Igor P, Brylev, Konstantin A, Sinyashin, Oleg G, Yakhvarov, Dmitry G
Format: Article
Language:English
Subjects:
Analysis
Chemical properties
Communication
Electrolytes
Exfoliation
Intermediates
Magnetic resonance spectroscopy
Methyl radicals
Methylation
Microscopy
Morphology
NMR
NMR spectroscopy
Nuclear magnetic resonance
Nuclear magnetic resonance spectroscopy
Oxidation
Phosphorene
Phosphorus
Spectrum analysis
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Summary:Two-dimensional black phosphorus (BP) has attracted great attention as a perspective material for various applications. The chemical functionalization of BP is an important pathway for the preparation of materials with improved stability and enhanced intrinsic electronic properties. Currently, most of the methods for BP functionalization with organic substrates require either the use of low-stable precursors of highly reactive intermediates or the use of difficult-to-manufacture and flammable BP intercalates. Herein we report a facile route for simultaneous electrochemical exfoliation and methylation of BP. Conducting the cathodic exfoliation of BP in the presence of iodomethane makes it possible to generate highly active methyl radicals, which readily react with the electrode's surface yielding the functionalized material. The covalent functionalization of BP nanosheets with the P-C bond formation has been proven by various microscopic and spectroscopic methods. The functionalization degree estimated by solid-state P NMR spectroscopy analysis reached 9.7%.
ISSN:1422-0067
1661-6596
1422-0067
DOI:10.3390/ijms24043095