Citation: Hao XU, Ruopeng LI, Peixia YANG, Anmin LIU, Jie BAI. Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302 shu

Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study

Hao XU ^{1, 2, 3,,} ,
Ruopeng LI ⁴ ,
Peixia YANG ⁴ ,
Anmin LIU ⁵ ,
Jie BAI ^{1, 2, 3}

1.
College of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China
2.
Key Laboratory of Industrial Catalysis at Universities of Autonomous Region, Hohhot 010051, China
3.
Inner Mongolia Key Laboratory of Green Chemical Engineering, Hohhot 010051, China
4.
School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China
5.
School of Chemical Engineering, Ocean and Life Sciences, Dalian University of Technology, Panjin, Liaoning 124221, China

Corresponding author: Hao XU, xuhao@imut.edu.cn
Received Date: 30 December 2024
Revised Date: 18 February 2025

Figures(6)

A series of halogen axial coordination atoms-modified Fe-N₄ (Fe atoms coordinated with four N atoms on the same horizontal plane to form bonds) models (Fe-N₄-F/C, Fe-N₄-Cl/C, and Fe-N₄-Br/C) were constructed based on the density functional theory. All density functional theory (DFT) calculations were carried out using the Dmol³ code in the Materials Studio package. By calculating the partial density of states, Mulliken charge, adsorption energy of intermediates, and free energy of oxygen reduction reaction (ORR), the regulation mechanism of halogen axial coordination atoms on the electronic structure and adsorption behavior of Fe atoms was studied. The structure-activity relationship between halogen axial coordination atoms and the catalytic activity of the Fe-N₄ site was also investigated. The results of calculations reveal that the introduction of Br as the halogen axial coordination atoms can optimize the electronic structure of the Fe atom, thus weakening the bonding strength of OH* intermediates on the Fe center. As a result, the Fe-N₄-Br/C possesses a lower energy barrier of the rate-determining step (desorption of OH* intermediates) compared to Fe-N₄/C, indicating better ORR kinetics process and intrinsic activity of the Fe-N₄-Br/C. Therefore, it is speculated that the introduction of halogen axial coordination atoms can improve the catalytic activity of Fe-N₄ sites for ORR.
- oxygen reduction reaction,
- Fe-N₄ site,
- halogen axial coordination atom,
- electronic structure,
- density functional theory
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Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N4 site: A density functional theory study

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Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study