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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 |
| Author Name | Affiliation | E-mail | | XU Hao | College of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China
Key Laboratory of Industrial Catalysis at Universities of Autonomous Region, Hohhot 010051, China
Inner Mongolia Key Laboratory of Green Chemical Engineering, Hohhot 010051, China | xuhao@imut.edu.cn | | LI Ruopeng | School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China | | | YANG Peixia | School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China | | | LIU Anmin | School of Chemical Engineering, Ocean and Life Sciences, Dalian University of Technology, Panjin, Liaoning 124221, China | | | BAI Jie | College of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051, China
Key Laboratory of Industrial Catalysis at Universities of Autonomous Region, Hohhot 010051, China
Inner Mongolia Key Laboratory of Green Chemical Engineering, Hohhot 010051, China | |
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| Abstract: 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. |
| Keywords: oxygen reduction reaction Fe-N4 site halogen axial coordination atom electronic structure density functional theory |
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| XU Hao,LI Ruopeng,YANG Peixia,LIU Anmin,BAI Jie.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. |
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