Interface Amorphization of Two-Dimensional Black Phosphorus Upon Treatment with Diazonium Salts

Overview

Journal Chemistry

Specialty Chemistry

Date 2020 Oct 13

PMID 33047818

Citations 6

Authors

Aleksandra Mitrovic

Stefan Wild

Vicent Lloret

Michael Fickert

Mhamed Assebban

Bence G Markus

Ferenc Simon

Frank Hauke

Gonzalo Abellan

Andreas Hirsch

Affiliations

Soon will be listed here.

Abstract

Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction.

Citing Articles

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Covalent and non-covalent chemistry of 2D black phosphorus.

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