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
Affiliations
Aidar M. Kuchkaev
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Street 8, 420088 Kazan, Russia
Airat M. Kuchkaev
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Street 8, 420088 Kazan, Russia
Aleksander V. Sukhov
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Street 8, 420088 Kazan, Russia
Svetlana V. Saparina
Institute of Physics, Kazan Federal University, Kremlyovskaya Street 18, 420008 Kazan, Russia
Oleg I. Gnezdilov
Institute of Physics, Kazan Federal University, Kremlyovskaya Street 18, 420008 Kazan, Russia
Alexander E. Klimovitskii
Alexander Butlerov Institute of Chemistry, Kazan Federal University, Kremlyovskaya Street 18, 420008 Kazan, Russia
Sufia A. Ziganshina
Zavoisky Physical-Technical Institute, FRC Kazan Scientific Center of RAS, Sibirsky Tract 10/7, 420029 Kazan, Russia
Irek R. Nizameev
Department of Nanotechnologies in Electronics, Kazan National Research Technical University Named after A.N. Tupolev-KAI, K. Marx Street 10, 420111 Kazan, Russia
Iskander R. Vakhitov
Institute of Physics, Kazan Federal University, Kremlyovskaya Street 18, 420008 Kazan, Russia
Alexey B. Dobrynin
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Street 8, 420088 Kazan, Russia
Dmitry I. Stoikov
Alexander Butlerov Institute of Chemistry, Kazan Federal University, Kremlyovskaya Street 18, 420008 Kazan, Russia
Gennady A. Evtugyn
Alexander Butlerov Institute of Chemistry, Kazan Federal University, Kremlyovskaya Street 18, 420008 Kazan, Russia
Oleg G. Sinyashin
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Street 8, 420088 Kazan, Russia
Xiongwu Kang
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
Dmitry G. Yakhvarov
Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov Street 8, 420088 Kazan, Russia
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.
