Citation: Ze Zhang, Lei Yang, Jin-Ru Liu, Hao Hu, Jian-Li Mi, Chao Su, Bei-Bei Xiao, Zhi-Min Ao. Improved oxygen electrocatalysis at FeN₄ and CoN₄ sites via construction of axial coordination[J]. Chinese Chemical Letters, ;2025, 36(2): 110013. doi: 10.1016/j.cclet.2024.110013 shu

Improved oxygen electrocatalysis at FeN₄ and CoN₄ sites via construction of axial coordination

Ze Zhang ^a ,
Lei Yang ^b ,
Jin-Ru Liu ^a ,
Hao Hu ^c ,
Jian-Li Mi ^c ,
Chao Su ^a ,
Bei-Bei Xiao ^{a, *,} ,
Zhi-Min Ao ^{d, *,}

a.
School of Energy and Power Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, China
b.
Institute for Computation in Molecular and Materials Science, School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China
c.
Institute for Advanced Materials, School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China
d.
Advanced Interdisciplinary Institute of Environment and Ecology, Beijing Normal University, Zhuhai 519087, China

xbb420@just.edu.cn

xiaobb11@mails.jlu.edu.cn

zhimin.ao@bnu.edu.cn

Received Date: 20 January 2024
Revised Date: 27 April 2024
Accepted Date: 14 May 2024
Available Online: 15 May 2024

Figures(4)

The quest for efficient and durable catalysts using abundant resources has garnered significant interest in the field of bifunctional oxygen electrocatalysis. In this contribution, we have designed a FeN₄ or CoN₄ embedded graphene-based bilayer as active layer and TMC₃ or TMN₃ doped graphene as supporting layer, named as FeN₄/TMC₃ or FeN₄/TMN₃ and CoN₄/TMC₃ or CoN₄/TMN₃, wherein TM strands for transition metal. Based on density functional theory calculations, our results demonstrate that the interaction formed between dual metal atoms in the bilayer interspace leads to the coordination environment altered from flat four-coordination to spatial five-coordination, further stabilizing the bilayer structure and impairing its affinity toward the O-containing intermediates. According to thermodynamic analysis, the bilayers of CoN₄/CoN₃, FeN₄/FeC₃, FeN₄/CoC₃, FeN₄/NiC₃, FeN₄/ZnC₃, FeN₄/FeN₃, FeN₄/CrN₃ and FeN₄/ZnN₃ are attractively promising for bifunctional oxygen electrocatalysis due to the small overpotential difference Δη between oxygen reduction and oxygen evolution that are less than 1 V. Density functional theory calculations combined with machine learning analysis directly identify the key role played by the inter-binding formed between bilayers, that boosts catalytic activity, which establishes a predictable framework for a fast screen for graphene-based bilayer vertical heterojunction. This work opens up a new path for designing the efficient electrocatalysts via modification of coordination environment.
- Oxygen electrocatalysis,
- Thermodynamic analysis,
- Density functional theory,
- Machine learning
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Improved oxygen electrocatalysis at FeN4 and CoN4 sites via construction of axial coordination

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通讯作者: 陈斌, bchen63@163.com

Improved oxygen electrocatalysis at FeN₄ and CoN₄ sites via construction of axial coordination