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Nano Research 2022, 15(9): 7994-8000 https://doi.org/10.1007/s12274-022-4510-4
Research Article | Issue | Published: 21 June 2022

Dual-metal atoms embedded into two-dimensional covalent organic framework as efficient electrocatalysts for oxygen evolution reaction: A DFT study

Show Author's Information Yanan Zhou1,§,  Lanlan Chen1,2,§,  Li Sheng3,  Qiquan Luo4( ),  Wenhua Zhang2( ),  Jinlong Yang1( )
Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
Department of Material Science and Engineering, University of Science and Technology of China, Hefei 230026, China
Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China
Institutes of Physical Science and Information Technology, Anhui University, Hefei 230601, China

§ Yanan Zhou and Lanlan Chen contributed equally to this work.

Keywords:
density functional theory (DFT), oxygen evolution reaction (OER), covalent organic framework (COF), dual-atom catalysts (DACs)
Topics:
Catalysis
Cite this article:
Zhou Y, Chen L, Sheng L, et al. Dual-metal atoms embedded into two-dimensional covalent organic framework as efficient electrocatalysts for oxygen evolution reaction: A DFT study. Nano Research, 2022, 15(9): 7994-8000. https://doi.org/10.1007/s12274-022-4510-4
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Abstract Full text Electronic supplementary material About this article

The electrochemical oxygen evolution reaction (OER) is a half-reaction of water-splitting for hydrogen generation, yet suffers from its sluggish kinetics and large overpotential. It is highly desirable to develop efficient and stable OER electrocatalysts for the advancement of water-splitting. Herein, by means of density functional theory (DFT) calculations, we systematically investigated a series of two-dimensional (2D) dual-atom catalysts (DACs) on a novel synthesized covalent organic framework (COF) material as potential efficient catalysts toward the OER. The designed 6 homonuclear (2TM-COF) and 15 heteronuclear (TM1TM2-COF) DACs all exhibit good stability. There is a strong scaling relationship between the adsorption Gibbs free energies of HO* and HOO* intermediates, and the OER overpotential (ηOER) volcano curve can be plotted as a function of ΔGO* − ΔGHO*. RhIr-COF shows the best OER catalytic activity with a ηOER value of 0.29 V, followed by CoNi-COF (0.33 V), RuRh-COF (0.34 V), and NiIr-COF (0.37 V). These four OER DACs exhibit lower onset potential and higher current density than that of the IrO2(110) benchmark catalyst. Aided by the descriptor identification study, the Bader charge that correlated with the Pauling electronegativity of the embedded dual-metal atoms was found to be the most important factor governing the catalytic activity of the OER. Our work highlights a potentially efficient class of 2D COF-based DACs toward the OER.


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About this article

Dual-metal atoms embedded into two-dimensional covalent organic framework as efficient electrocatalysts for oxygen evolution reaction: A DFT study

Show Author's information Yanan Zhou1,§, Lanlan Chen1,2,§, Li Sheng3, Qiquan Luo4( ), Wenhua Zhang2( ), Jinlong Yang1( )
Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei 230026, China
Department of Material Science and Engineering, University of Science and Technology of China, Hefei 230026, China
Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, China
Institutes of Physical Science and Information Technology, Anhui University, Hefei 230601, China

§ Yanan Zhou and Lanlan Chen contributed equally to this work.

Abstract

The electrochemical oxygen evolution reaction (OER) is a half-reaction of water-splitting for hydrogen generation, yet suffers from its sluggish kinetics and large overpotential. It is highly desirable to develop efficient and stable OER electrocatalysts for the advancement of water-splitting. Herein, by means of density functional theory (DFT) calculations, we systematically investigated a series of two-dimensional (2D) dual-atom catalysts (DACs) on a novel synthesized covalent organic framework (COF) material as potential efficient catalysts toward the OER. The designed 6 homonuclear (2TM-COF) and 15 heteronuclear (TM1TM2-COF) DACs all exhibit good stability. There is a strong scaling relationship between the adsorption Gibbs free energies of HO* and HOO* intermediates, and the OER overpotential (ηOER) volcano curve can be plotted as a function of ΔGO* − ΔGHO*. RhIr-COF shows the best OER catalytic activity with a ηOER value of 0.29 V, followed by CoNi-COF (0.33 V), RuRh-COF (0.34 V), and NiIr-COF (0.37 V). These four OER DACs exhibit lower onset potential and higher current density than that of the IrO2(110) benchmark catalyst. Aided by the descriptor identification study, the Bader charge that correlated with the Pauling electronegativity of the embedded dual-metal atoms was found to be the most important factor governing the catalytic activity of the OER. Our work highlights a potentially efficient class of 2D COF-based DACs toward the OER.

Keywords: density functional theory (DFT), oxygen evolution reaction (OER), covalent organic framework (COF), dual-atom catalysts (DACs)

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Publication history
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Acknowledgements

Publication history

Received: 04 March 2022
Revised: 05 May 2022
Accepted: 08 May 2022
Published: 21 June 2022
Issue date: September 2022

Copyright

© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Nos. 22102167 and U21A20317), the China Postdoctoral Science Foundation (No. 2021M693060), and the National Synchrotron Radiation Laboratory (No. KY2340000135) from the University of Science and Technology of China. The calculations were performed on the Supercomputing Center of the University of Science and Technology of China.

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