TY  - JOUR
AU  - Sredojević, Dušan
AU  - Vukoje, Ivana
AU  - Trpkov, Đorđe
AU  - Brothers, Edward N.
PY  - 2024
UR  - https://vinar.vin.bg.ac.rs/handle/123456789/12995
AB  - In addition to providing a sustainable route to green alternative energy and chemical supplies from a cheap and abundant carbon source, recycling CO2 offers an excellent way to reduce net anthropogenic global CO2 emissions. This can be achieved via catalysis on 2D materials. These materials are atomically thin and have unique electrical and catalytic properties compared to bigger nanoparticles and conventional bulk catalysts, opening a new arena in catalysis. This paper examines the efficacy of hexagonal boron nitride (h-BN) lattices with vacancy defects for CO2 electroreduction (CO2RR). We conducted in-depth investigations on different CO2RR electrocatalytic reaction pathways on various h-BN vacancy sites using a computational hydrogen model (CHE). It was shown that CO binds to h-BN vacancies sufficiently to ensure additional electron transfer processes, leading to higher-order reduction products. For mono-atomic defects VN (removed nitrogen), the electrochemical path of (H+ + e−) pair transfers that would lead to the formation of methanol is most favorable with a limiting potential of 1.21 V. In contrast, the reaction pathways via VB (removed boron) imposes much higher thermodynamic barriers for the formation of all relevant species. With a divacancy VBN, the hydrogen evolution reaction (HER) would be the most probable process due to the low rate-determining barrier of 0.69 eV. On the tetravacancy defects VB3N the pathways toward the formation of both CH4 and CH3OH impose a limiting potential of 0.85 V. At the same time, the HER is suppressed by requiring much higher energy (2.15 eV). Modeling the edges of h-BN reveals that N-terminated zigzag conformation would impose the same limiting potential for the formation of methanol and methane (1.73 V), simultaneously suppressing the HER (3.47 V). At variance, the armchair conformation favors the HER, with a rate-determining barrier of 1.70 eV. Hence, according to our calculations, VB3N and VN are the most appropriate vacancy defects for catalyzing CO2 electroreduction reactions.
T2  - Physical Chemistry Chemical Physics
T1  - A DFT study of CO2 electroreduction catalyzed by hexagonal boron-nitride nanosheets with vacancy defects
VL  - 26
IS  - 10
SP  - 8356
EP  - 8365
DO  - 10.1039/D3CP06186H
ER  - 

@article{
author = "Sredojević, Dušan and Vukoje, Ivana and Trpkov, Đorđe and Brothers, Edward N.",
year = "2024",
abstract = "In addition to providing a sustainable route to green alternative energy and chemical supplies from a cheap and abundant carbon source, recycling CO2 offers an excellent way to reduce net anthropogenic global CO2 emissions. This can be achieved via catalysis on 2D materials. These materials are atomically thin and have unique electrical and catalytic properties compared to bigger nanoparticles and conventional bulk catalysts, opening a new arena in catalysis. This paper examines the efficacy of hexagonal boron nitride (h-BN) lattices with vacancy defects for CO2 electroreduction (CO2RR). We conducted in-depth investigations on different CO2RR electrocatalytic reaction pathways on various h-BN vacancy sites using a computational hydrogen model (CHE). It was shown that CO binds to h-BN vacancies sufficiently to ensure additional electron transfer processes, leading to higher-order reduction products. For mono-atomic defects VN (removed nitrogen), the electrochemical path of (H+ + e−) pair transfers that would lead to the formation of methanol is most favorable with a limiting potential of 1.21 V. In contrast, the reaction pathways via VB (removed boron) imposes much higher thermodynamic barriers for the formation of all relevant species. With a divacancy VBN, the hydrogen evolution reaction (HER) would be the most probable process due to the low rate-determining barrier of 0.69 eV. On the tetravacancy defects VB3N the pathways toward the formation of both CH4 and CH3OH impose a limiting potential of 0.85 V. At the same time, the HER is suppressed by requiring much higher energy (2.15 eV). Modeling the edges of h-BN reveals that N-terminated zigzag conformation would impose the same limiting potential for the formation of methanol and methane (1.73 V), simultaneously suppressing the HER (3.47 V). At variance, the armchair conformation favors the HER, with a rate-determining barrier of 1.70 eV. Hence, according to our calculations, VB3N and VN are the most appropriate vacancy defects for catalyzing CO2 electroreduction reactions.",
journal = "Physical Chemistry Chemical Physics",
title = "A DFT study of CO2 electroreduction catalyzed by hexagonal boron-nitride nanosheets with vacancy defects",
volume = "26",
number = "10",
pages = "8356-8365",
doi = "10.1039/D3CP06186H"
}

Sredojević, D., Vukoje, I., Trpkov, Đ.,& Brothers, E. N.. (2024). A DFT study of CO2 electroreduction catalyzed by hexagonal boron-nitride nanosheets with vacancy defects. in Physical Chemistry Chemical Physics, 26(10), 8356-8365.
https://doi.org/10.1039/D3CP06186H

Sredojević D, Vukoje I, Trpkov Đ, Brothers EN. A DFT study of CO2 electroreduction catalyzed by hexagonal boron-nitride nanosheets with vacancy defects. in Physical Chemistry Chemical Physics. 2024;26(10):8356-8365.
doi:10.1039/D3CP06186H .

Sredojević, Dušan, Vukoje, Ivana, Trpkov, Đorđe, Brothers, Edward N., "A DFT study of CO2 electroreduction catalyzed by hexagonal boron-nitride nanosheets with vacancy defects" in Physical Chemistry Chemical Physics, 26, no. 10 (2024):8356-8365,
https://doi.org/10.1039/D3CP06186H . .