Covalent Functionalization of Black Phosphorus Nanosheets with Dichlorocarbenes for Enhanced Electrocatalytic Hydrogen Evolution Reaction

• Published in: Nanomaterials (Basel, Switzerland) Vol. 13; no. 5; p. 826
• 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., Vakhitov, Iskander R., Dobrynin, Alexey B., Stoikov, Dmitry I., Evtugyn, Gennady A., Sinyashin, Oleg G., Kang, Xiongwu, Yakhvarov, Dmitry G.
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 23.02.2023; MDPI
• Subjects: Biomedical materials; black phosphorus; carbene; Carbon; Chemical bonds; Chemical tests and reagents; Communication; Covalence; covalent functionalization; Force and energy; Free radicals; Hydrogen; hydrogen evolution reaction; Hydrogen evolution reactions; Intermediates; Monocyte chemoattractant protein 1; Morphology; Nanosheets; NMR; Nuclear magnetic resonance; Optoelectronics; Organic compounds; phosphorene; Phosphorus; Photoelectron spectroscopy; Photoelectrons; Physical properties; Potassium; reactive intermediates; Scanning electron microscopy; X-ray spectroscopy; United States; Germany; Russia; hydrogen evolution reaction; covalent functionalization; black phosphorus; reactive intermediates; carbene; electrocatalysis; phosphorene
• ISSN: 2079-4991; 2079-4991
• DOI: 10.3390/nano13050826

Two-dimensional black phosphorus (BP) has emerged as a perspective material for various micro- and opto-electronic, energy, catalytic, and biomedical applications. Chemical functionalization of black phosphorus nanosheets (BPNS) is an important pathway for the preparation of materials with improved ambient stability and enhanced physical properties. Currently, the covalent functionalization of BPNS with highly reactive intermediates, such as carbon-free radicals or nitrenes, has been widely implemented to modify the material’s surface. However, it should be noted that this field requires more in-depth research and new developments. Herein, we report for the first time the covalent carbene functionalization of BPNS using dichlorocarbene as a functionalizing agent. The P–C bond formation in the obtained material (BP–CCl2) has been confirmed by Raman, solid-state 31P NMR, IR, and X-ray photoelectron spectroscopy methods. The BP–CCl2 nanosheets exhibit an enhanced electrocatalytic hydrogen evolution reaction (HER) performance with an overpotential of 442 mV at −1 mA cm−2 and a Tafel slope of 120 mV dec−1, outperforming the pristine BPNS.