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

Aidar M Kuchkaev; Airat M Kuchkaev; Aleksander V Sukhov; Svetlana V Saparina; Oleg I Gnezdilov; Alexander E Klimovitskii; Sufia A Ziganshina; Irek R Nizameev; Iskander R Vakhitov; Alexey B Dobrynin; Dmitry I Stoikov; Gennady A Evtugyn; Oleg G Sinyashin; Xiongwu Kang; Dmitry G Yakhvarov

doi:10.3390/nano13050826

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

Nanomaterials (Basel). 2023 Feb 23;13(5):826. doi: 10.3390/nano13050826.

Authors

Aidar M Kuchkaev^{1

2}, Airat M Kuchkaev^{1

2}, Aleksander V Sukhov^{1

2}, Svetlana V Saparina³, Oleg I Gnezdilov³, Alexander E Klimovitskii², Sufia A Ziganshina⁴, Irek R Nizameev⁵, Iskander R Vakhitov³, Alexey B Dobrynin¹, Dmitry I Stoikov², Gennady A Evtugyn², Oleg G Sinyashin¹, Xiongwu Kang⁶, Dmitry G Yakhvarov^{1

2}

Affiliations

¹ Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Street 8, 420088 Kazan, Russia.
² Alexander Butlerov Institute of Chemistry, Kazan Federal University, Kremlyovskaya Street 18, 420008 Kazan, Russia.
³ Institute of Physics, Kazan Federal University, Kremlyovskaya Street 18, 420008 Kazan, Russia.
⁴ Zavoisky Physical-Technical Institute, FRC Kazan Scientific Center of RAS, Sibirsky Tract 10/7, 420029 Kazan, Russia.
⁵ Department of Nanotechnologies in Electronics, Kazan National Research Technical University Named after A.N. Tupolev-KAI, K. Marx Street 10, 420111 Kazan, Russia.
⁶ New Energy Research Institute, School of Environment and Energy, South China University of Technology, Higher Education Mega Center, 382 East Waihuan Road, Guangzhou 510006, China.

Abstract

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.

Keywords: black phosphorus; carbene; covalent functionalization; electrocatalysis; hydrogen evolution reaction; phosphorene; reactive intermediates.

Abstract

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