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
1. [1]
  YI X Y, YANG H J, YANG X X, LI X K, YAN C, ZHANG J H, CHEN L A, DONG J J, QIN J, ZHANG G N, WANG J J, LI W B, ZHOU Z Y, WU G, LI X F. Local single co sites at the second shell of Fe-N₄ active sites to boost oxygen reduction reaction[J]. Adv. Funct. Mater., 2023,34(9)2309728.
2. [2]
  WANG Y P, KATYAL N, TANG Y, LI H, SHIN K, LIU W Q, HE R L, XU M W, HENKELMAN G, BAO S J. One-step pyrolysis construction of bimetallic atom-cluster sites for boosting bifunctional catalytic activity in Zn-air batteries[J]. Small, 2023,20(11)2306504.
3. [3]
  SONG X K, SONG Y J, LI X P, WU X T, WANG Z Q, SUN X H, AN M, WEI X Q, ZHAO Y J, WEI J M, BI C L, SUN J H, NARA H, YOU J M, YAMAUCHI Y. Multi-scale engineered 2D carbon polyhedron array with enhanced electrocatalytic performance[J]. Small, 2023,20(11)2305459.
4. [4]
  SHEN M X, LIU J, LI J, DUAN C, XIONG C Y, ZHAO W, DAI L, WANG Q Y, YANG H, NI Y H. Breaking the N-limitation with N-enriched porous submicron carbon spheres anchored Fe single-atom catalyst for superior oxygen reduction reaction and Zn-air batteries[J]. Energy Storage Mater., 2023,59102790. doi: 10.1016/j.ensm.2023.102790
5. [5]
  LU X Y, YANG P X, WAN Y B, ZHANG H L, XU H, XIAO L H, LI R P, LI Y Q, ZHANG J Q, AN M Z. Active site engineering toward atomically dispersed M-N-C catalysts for oxygen reduction reaction[J]. Coord. Chem. Rev., 2023,495215400. doi: 10.1016/j.ccr.2023.215400
6. [6]
  LI L, LI N, XIA J W, ZHOU S L, QIAN X Y, YIN F X, DAI G H, HE G Y, CHEN H Q. A pH-universal ORR catalyst with atomic Fe-heteroatom (N, S) sites for high-performance Zn-air batteries[J]. Nano Res., 2023,16(7):9416-9425. doi: 10.1007/s12274-023-5625-y
7. [7]
  LIU M, WANG X M, CAO S F, LU X Q, LI W, LI N, BU X H. Ferredoxin-inspired design of S-synergized Fe-Fe dual-metal center catalysts for enhanced electrocatalytic oxygen reduction reaction[J]. Adv. Mater., 2024,36(19)2309231. doi: 10.1002/adma.202309231
8. [8]
  LI Z J, JI S Q, LIU H X, XU C, GUO C M, LU X, SUN H X, DOU S, XIN S X, HORTON J H, HE C. Constructing asymmetrical coordination microenvironment with phosphorus-incorporated nitrogen-doped carbon to boost bifunctional oxygen electrocatalytic activity[J]. Adv. Funct. Mater., 2024,34(18)2314444. doi: 10.1002/adfm.202314444
9. [9]
  CHEN C L, CHAI J, SUN M R, GUO T Q, LIN J, ZHOU Y R, SUN Z Y, ZHANG F, ZHANG L, CHEN W X, LI Y J. An asymmetrically coordinated ZnCoFe hetero-trimetallic atom catalyst enhances the electrocatalytic oxygen reaction[J]. Energy Environ. Sci., 2024,17(6):2298-2308. doi: 10.1039/D4EE00134F
10. [10]
  ZHAO C X, LIU X Y, LIU J N, WANG J, WAN X, WANG C D, LI X Y, SHUI J L, SONG L, PENG H J, LI B Q, ZHANG Q. Molecular recognition regulates coordination structure of single atom sites[J]. Angew. Chem.‒Int. Edit., 2023,62(48)202313028. doi: 10.1002/anie.202313028
11. [11]
  YU T, CHE Y T, FU H, MA D F, ZHAO W J, YAN S T, BIAN T, ZHANG L T. N, S dual-doped carbon aerogels-supported Co₉S₈ nanoparticles as efficient oxygen reduction reaction electrocatalyst for zinc-air battery[J]. J. Alloy. Compd., 2023,948169792. doi: 10.1016/j.jallcom.2023.169792
12. [12]
  LIU H, JIANG L Z, WANG Y M, WANG X X, KHAN J, ZHU Y L, XIAO J M, LI L N, HAN L. Boosting oxygen reduction with coexistence of single-atomic Fe and Cu sites decorated nitrogen-doped porous carbon[J]. Chem. Eng. J., 2023,452138938. doi: 10.1016/j.cej.2022.138938
13. [13]
  XU S R, YIN H B, XUE D P, XIA H C, ZHAO S Y, YAN W F, MU S C, ZHANG J N. Atomically dispersed metal-nitrogen-carbon catalysts for oxygen reduction reaction[J]. Chem. J. Chinese Universities, 2022,43(5)20220028.
14. [14]
  LIU Y R, YUAN S, SUN C T, WANG C L, LIU X J, LV Z H, LIU R, MENG Y Z, YANG W X, FENG X, WANG B. Optimizing Fe-3d electron delocalization by asymmetric Fe-Cu diatomic configurations for efficient anion exchange membrane fuel cells[J]. Adv. Energy Mater., 2023,13(46)2302719. doi: 10.1002/aenm.202302719
15. [15]
  LIU Z H, MA F X, FAN H S, LIU Z Q, DU Y, ZHEN L, XU C Y. Formulating N-doped carbon hollow nanospheres with highly accessible through-pores to isolate Fe single-atoms for efficient oxygen reduction[J]. Small, 2023,20(6)2305700.
16. [16]
  ZHOU Y Z, CHEN G B, WANG Q, WANG D, TAO X F, ZHANG T R, FENG X L, MüLLEN K. Fe-N-C Electrocatalysts with densely accessible Fe-N₄ sites for efficient oxygen reduction reaction[J]. Adv. Funct. Mater., 2021,31(34)2102420.
17. [17]
  ZHU P, XIONG X, WANG X L, YE C L, LI J Z, SUN W M, SUN X H, JIANG J J, ZHUANG Z B, WANG D S, LI Y D. Regulating the FeN₄ moiety by constructing Fe-Mo dual-metal atom sites for efficient electrochemical oxygen reduction[J]. Nano Lett., 2022,22(23):9507-9515.
18. [18]
  ZHAI W J, HUANG S H, LU C B, TANG X N, LI L B, HUANG B Y, HU T, YUAN K, ZHUANG X D, CHEN Y W. Simultaneously integrate iron single atom and nanocluster triggered tandem effect for boosting oxygen electroreduction[J]. Small, 2022,18(15)e2107225.
19. [19]
  XIN C C, SHANG W Z, HU J W, ZHU C, GUO J Y, ZHANG J W, DONG H P, LIU W, SHI Y T. Integration of morphology and electronic structure modulation on atomic iron-nitrogen-carbon catalysts for highly efficient oxygen reduction[J]. Adv. Funct. Mater., 2021,32(2)2108345.
20. [20]
  LIU J J, JIA J J, WEN H Y, LI S Q, WU Y J, WANG Q, KAN Z W, LI Y, WU X, ZHAO J X, LIU S, LI B. Axial optimization of biomimetic nanoenzyme catalysts applied to oxygen reduction reactions[J]. Chem. Commun., 2023,59(24)3550.
21. [21]
  TIAN H, SONG A L, ZHANG P, SUN K A, WANG J J, SUN B, FAN Q H, SHAO G J, CHEN C, LIU H, LI Y D, WANG G X. High durability of Fe-N-C single-atom catalysts with carbon vacancies toward the oxygen reduction reaction in alkaline media[J]. Adv. Mater., 2023,35(14)2210714.
22. [22]
  WU S W, JIANG S, LIU S Q, TAN X H, CHEN N, LUO J L, MUSHRIF S H, CADIEN K, LI Z. Single Cu-N₄ sites enable atomic Fe clusters with high-performance oxygen reduction reactions[J]. Energy Environ. Sci., 2023,16(8):3576-3586.
23. [23]
  HU C, XING G Y, HAN W T, HAO Y X, ZHANG C C, ZHANG Y, KUO C H, CHEN H Y, HU F, LI L L, PENG S J. Inhibiting demetalation of Fe-N-C via Mn sites for efficient oxygen reduction reaction in zinc-air batteries[J]. Adv. Mater., 2024,36(12)2405763.
24. [24]
  XU H, SUN W Y, LI R P, LU X Y, YANG P X, BAI J. Tailoring the electronic structure of Fe-N₄ sites via heteroatom modification strategy for boosting oxygen reduction in hydrogen fuel cells: A density functional theory study[J]. Int. J. Hydrogen Energy, 2024,72:220-225.
25. [25]
  WANG D, ZHA S J, LI Y Q, LI X S, WANG J B, CHU Y, MITSUZAKI N, CHEN Z D. A carboxylate linker strategy mediated densely accessible Fe-N₄ sites for enhancing oxygen electroreduction in Zn-air batteries[J]. J. Colloid Interface Sci., 2024,665:879-887.
26. [26]
  YANG B L, YU H F, JIA X D, CHENG Q, REN Y L, HE B, XIANG Z H. Atomically dispersed isolated Fe-Ce dual-metal-site catalysts for proton-exchange membrane fuel cells[J]. ACS Appl. Mater. Interfaces, 2023,15(19):23316-23327.
27. [27]
  HAMMER B, NØRSKOV J K. Electronic factors determining the reactivity of metal surfaces[J]. Surface Sci., 1995,343(3):211-220.
28. [28]
  XU H, WANG D, YANG P X, LIU A M, LI R P, LI Y, XIAO L H, REN X F, ZHANG J Q, AN M Z. Atomically dispersed M-N-C catalysts for oxygen reduction reaction[J]. J. Mater. Chem. A, 2020,8(44):23187-23201.
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南开大学师唯/华北电力大学（保定）刘景维：二维配位聚合物中有序的亲锂冠醚位点用于无枝晶锂沉积

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通讯作者: 陈斌, bchen63@163.com

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