N-, S-Codoped Porous Carbon With Trace Single-Atom Fe for Enhanced Oxygen Reduction With Robust Poison Resistance and Efficient Rechargeable Zinc–Air Battery

Yu Sun , Lihui Wang , Haibo Li , Suyuan Zeng , Rui Li , Qingxia Yao , Hongyan Chen , Konggang Qu

Carbon Neutralization ›› 2025, Vol. 4 ›› Issue (2) : e196

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Carbon Neutralization ›› 2025, Vol. 4 ›› Issue (2) : e196 DOI: 10.1002/cnl2.196
RESEARCH ARTICLE

N-, S-Codoped Porous Carbon With Trace Single-Atom Fe for Enhanced Oxygen Reduction With Robust Poison Resistance and Efficient Rechargeable Zinc–Air Battery

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Abstract

Pt-based electrocatalysts in oxygen reduction reaction (ORR) have severely hindered large-scale application of relevant energy technologies. Carbon composites codoped with heteroatoms and transition metals are considered the most likely alternatives to Pt, but they still have the limitation of poor tolerance to poisons. Thus, exploration of advanced electrocatalysts with superior activity and high poison resistance is of great significance in practical applications. Herein, a low-cost lysozyme was first directly used to fabricate single-atomic Fe anchored on porous N-, S-codoped carbon (Fe-PNSC) using a simple “mix-and-pyrolyze” method, which has a honeycomb-like porous structure with a large surface area of 957.69 m2/g, adequate pores of 0.71 cm3/g, and rich heteroatom doping of 4.66 at.% N, 1.9 at.% S, and 0.18 wt.% single-atomic Fe. Accordingly, Fe-PNSC displays an onset potential of 1.08 V and a half-wave potential of 0.86 V for ORR, strong stability with 96.87% current retention, and robust resistance to methanol and various poisons, all outperforming Pt/C. Additionally, the Fe-PNSC–based zinc–air battery shows a high peak power density of 122.2mWcm-2, good specific capacity and energy density of 787 mAh gZn-1 and 975.9 Wh kgZn-1, respectively, and remarkable rechargeable stability for 300 h, superior to Pt/C-based ones.

Keywords

lysozyme / N, S codoping / oxygen reduction / single atomic Fe / zinc–air battery

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Yu Sun, Lihui Wang, Haibo Li, Suyuan Zeng, Rui Li, Qingxia Yao, Hongyan Chen, Konggang Qu. N-, S-Codoped Porous Carbon With Trace Single-Atom Fe for Enhanced Oxygen Reduction With Robust Poison Resistance and Efficient Rechargeable Zinc–Air Battery. Carbon Neutralization, 2025, 4(2): e196 DOI:10.1002/cnl2.196

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References

[1]

C. Fang, X. Tang, and Q. Yi, “Adding Fe/Dicyandiamide to Co-MOF to Greatly Improve Its ORR/OER Bifunctional Electrocatalytic Activity,” Applied Catalysis, B: Environmental 341 (2024): 123346.

[2]

R. Ma, X. Cui, X. Xu, et al., “Collaborative Integration of Ultrafine Fe2P Nanocrystals Into Fe, N, P-Codoped Carbon Nanoshells for Highly-Efficient Oxygen Reduction,” Nano Energy 108 (2023): 108179.

[3]

C. Chen, J. Chai, M. Sun, et al., “An Asymmetrically Coordinated Zncofe Hetero-Trimetallic Atom Catalyst Enhances the Electrocatalytic Oxygen Reaction,” Energy &Environmental Science 17 (2024):2298–2308.

[4]

Y. Guo, C. Wang, Y. Xiao, et al., “Increasing the Number of Modulated Fe Single-Atom Sites by Adjacent Nanoparticles for Efficient Oxygen Reduction With Spin-State Transition,” Nano Energy 117 (2023): 108895.

[5]

Y. Chen, Z. Li, Y. Zhu, et al., “Atomic Fe Dispersed on N-Doped Carbon Hollow Nanospheres for High-Efficiency Electrocatalytic Oxygen Reduction,” Advanced Materials 31 (2019): 1806312.

[6]

R. Xu, X. Wang, M. Sun, et al., “Promoting Oxygen Reduction Kinetics of Single Fe Sites for Robust Neutral Zn-Air Batteries via Engineering Synergistic Fe Nanocluster as Proton-Feeding Center,” Chemical Engineering Journal 475 (2023): 146065.

[7]

Z. Zhu, H. Yin, Y. Wang, et al., “Coexisting Single-Atomic Fe and Ni Sites on Hierarchically Ordered Porous Carbon as a Highly Efficient ORR Electrocatalyst,” Advanced Materials 32 (2020): 2004670.

[8]

Z. Han, Y. Zhu, X. Yao, et al., “Boosting Oxygen Reduction of Single Atomic Iron Sites by Charge Redistribution,” Applied Catalysis, B: Environmental 337 (2023): 122961.

[9]

Y. Li, Y. Ding, B. Zhang, et al., “N, O Symmetric Double Coordination of an Unsaturated Fe Single-Atom Confined Within a Graphene Framework for Extraordinarily Boosting Oxygen Reduction in Zn–Air Batteries,” Energy &Environmental Science 16 (2023):2629–2636.

[10]

X. Xu, M. Liu, Y. Nie, et al., “Modulating Electronic Structure of Interfacial Fe Sites in Fe2N/CoFe2O4 Nano-Heterostructure for Enhancing Corrosion-Resistance and Oxygen Electrocatalysis in Zinc-Air Battery,” Chemical Engineering Journal 471 (2023): 144639.

[11]

Y. Zeng, E. Almatrafi, W. Xia, et al., “Nitrogen-Doped Carbon-Based Single-Atom Fe Catalysts: Synthesis, Properties, and Applications in Advanced Oxidation Processes,” Coordination Chemistry Reviews 475 (2023): 214874.

[12]

K. Song, B. Yang, X. Zou, W. Zhang, and W. Zheng, “Unified ORR Mechanism Criteriaviacharge–Spin–Coordination of Fe Functional Units,” Energy &Environmental Science 17 (2024):27–48.

[13]

Z. Yang, Y. Chen, S. Zhang, and J. Zhang, “Identification and Understanding of Active Sites of Non-Noble Iron-Nitrogen-Carbon Catalysts for Oxygen Reduction Electrocatalysis,” Advanced Functional Materials 33 (2023): 2215185.

[14]

S. Akula, M. Mooste, J. Kozlova, et al., “Transition Metal (Fe, Co, Mn, Cu) Containing Nitrogen-Doped Porous Carbon as Efficient Oxygen Reduction Electrocatalysts for Anion Exchange Membrane Fuel Cells,” Chemical Engineering Journal 458 (2023): 141468.

[15]

W. Song, C. Xiao, J. Ding, et al., “Review of Carbon Support Coordination Environments for Single Metal Atom Electrocatalysts (SACS),” Advanced Materials 36 (2024): 2301477.

[16]

K. Yuan, D. Lützenkirchen-Hecht, L. Li, et al., “Boosting Oxygen Reduction of Single Iron Active Sites via Geometric and Electronic Engineering: Nitrogen and Phosphorus Dual Coordination,” Journal of the American Chemical Society 142 (2020):2404–2412.

[17]

C. Chen, Y. Wu, X. Li, et al., “Modulating Fe Spin State in FeNC Catalysts by Adjacent Fe Atomic Clusters to Facilitate Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cell,” Applied Catalysis, B: Environmental 342 (2024): 123407.

[18]

L. Wu, R. Zhao, G. Du, et al., “Hierarchically Porous Fe/N/S/C Nanospheres With High-Content of Fe-Nx for Enhanced ORR and Zn-Air Battery Performance,” Green Energy &Environment 8 (2023):1693–1702.

[19]

Y. Wang, S. Wang, R. Li, et al., “A Simple Strategy for Tridoped Porous Carbon Nanosheet as Superior Electrocatalyst for Bifunctional Oxygen Reduction and Hydrogen Evolution Reactions,” Carbon 162 (2020):586–594.

[20]

S. Kumar and X. T. Cao, “Natural Bio-Sourced Polymers: Emerging Precursors for the Synthesis of Single Atom Catalysts,” Coordination Chemistry Reviews 499 (2024): 215524.

[21]

S. S. Sekhon, J. Lee, and J.-S. Park, “Biomass-Derived Bifunctional Electrocatalysts for Oxygen Reduction and Evolution Reaction: A Review,” Journal of Energy Chemistry 65 (2022):149–172.

[22]

H. Li, L. Zhang, L. Li, et al., “Two-in-One Solution Using Insect Wings to Produce Graphene-Graphite Films for Efficient Electrocatalysis,” Nano Research 12 (2019):33–39.

[23]

J. Liu, L. Wei, C. Chu, and J. Shen, “Tofu Gel-Derived Nitrogen and Trace Iron Co-Doped Porous Carbon as Highly Efficient Air-Cathode Electrocatalyst for Microbial Fuel Cells,” Journal of Power Sources 527 (2022): 230960.

[24]

L.-L. Ma, W.-J. Liu, X. Hu, P. K. S. Lam, J. R. Zeng, and H.-Q. Yu, “Ionothermal Carbonization of Biomass to Construct sp2/sp3 Carbon Interface in N-Doped Biochar as Efficient Oxygen Reduction Electrocatalysts,” Chemical Engineering Journal 400 (2020): 125969.

[25]

X. Hu, L.-L. Ma, W.-J. Liu, H.-C. Li, M. Ma, and H.-Q. Yu, “Microalgae Biomass-Derived Nitrogen-Enriching Carbon Materials as an Efficient pH-Universal Oxygen Reduction Electrocatalyst for Zn-Air Battery,” Science of the Total Environment 782 (2021): 146844.

[26]

Z. Lu, J. Chen, W. Wang, et al., “Electrocatalytic, Kinetic, and Mechanism Insights Into the Oxygen-Reduction Catalyzed Based on the Biomass-Derived FeOx@N-Doped Porous Carbon Composites,” Small 17 (2021): 2007326.

[27]

S.-T. Huang, Y.-Q. Lei, P.-R. Guo, H.-X. Chen, S.-C. Gan, and Z.-H. Diao, “Electrocatalytic Degradation of Favipiravir by Heteroatom (P and S) Doped Biomass-Derived Carbon With High Oxygen Reduction Reaction Activity,” Chemical Engineering Journal 484 (2024): 149543.

[28]

Y. Wu, Y. Chen, H. Wang, et al., “Efficient ORR Electrocatalytic Activity of Peanut Shell-Based Graphitic Carbon Microstructures,” Journal of Materials Chemistry A 6 (2018):12018–12028.

[29]

L. Xu, D. Deng, Y. Tian, et al., “Dual-Active-Sites Design of CoNx Anchored on Zinc-Coordinated Nitrogen-Codoped Porous Carbon With Efficient Oxygen Catalysis for High-Stable Rechargeable Zinc-Air Batteries,” Chemical Engineering Journal 408 (2021): 127321.

[30]

C. Hu and L. Dai, “Doping of Carbon Materials for Metal-Free Electrocatalysis,” Advanced Materials 31 (2019): 1804672.

[31]

W. Kiciński, M. Szala, and M. Bystrzejewski, “Sulfur-Doped Porous Carbons: Synthesis and Applications,” Carbon 68 (2014):1–32.

[32]

B. Zhang, C. Wang, D. Liu, Y. Liu, X. Yu, and L. Wang, “Boosting ORR Electrocatalytic Performance of Metal-Free Mesoporous Biomass Carbon by Synergism of Huge Specific Surface Area and Ultrahigh Pyridinic Nitrogen Doping,” ACS Sustainable Chemistry &Engineering 6 (2018):13807–13812.

[33]

Y. Zhang, L. Lu, S. Zhang, et al., “Biomass Chitosan Derived Cobalt/Nitrogen Doped Carbon Nanotubes for the Electrocatalytic Oxygen Reduction Reaction,” Journal of Materials Chemistry A 6 (2018):5740–5745.

[34]

J. Wang, Q. Yu, H. Li, et al., “Natural DNA-Assisted RuP2on Highly Graphitic N, P-Codoped Carbon for pH-Wide Hydrogen Evolution,” Chemical Communications 57 (2021):7284–7287.

[35]

Q. Yu, H. Li, R. Li, et al., “Natural DNA-Assisted Ultrafine FeP Embedded in N, P-Codoped Carbons for Efficient Oxygen Reduction, Hydrogen Evolution and Rechargeable Zinc-Air Battery,” Carbon 186 (2022):171–179.

[36]

Q. Yu, J. Wang, H. Li, et al., “Natural DNA-Derived Highly-Graphitic N, P, S-Tridoped Carbon Nanosheets for Multiple Electrocatalytic Applications,” Chemical Engineering Journal 429 (2022): 132102.

[37]

Y. Ha, L. Shi, Z. Chen, and R. Wu, “Atomically Dispersed Co-Pyridinic N-C for Superior Oxygen Reduction Reaction,” Advancement of Science 6 (2019): 1900272.

[38]

Y. Ha, L. Shi, X. Yan, et al., “Multifunctional Electrocatalysis on a Porous N-Doped NiCo2O4@C Nanonetwork,” ACS Applied Materials &Interfaces 11 (2019):45546–45553.

[39]

N. Guo, H. Xue, R. Ren, et al., “Frontispiece: S-Block Potassium Single-Atom Electrocatalyst With K–N4Configuration Derived From K+/Polydopamine for Efficient Oxygen Reduction,” Angewandte Chemie International Edition 62 (2023): e202314124.

[40]

X. Guan, Y. Sun, S. Zhao, et al., “Selectively Nucleotide-Derived RuP on N, P-Codoped Carbon With Engineered Mesopores for Energy-Efficient Hydrogen Production Assisted by Hydrazine Oxidation,” SusMat 4 (2024):166–177.

[41]

K. Qu, Y. Zheng, Y. Jiao, X. Zhang, S. Dai, and S. Z. Qiao, “Polydopamine-Inspired, Dual Heteroatom-Doped Carbon Nanotubes for Highly Efficient Overall Water Splitting,” Advanced Energy Materials 7 (2016): 1602068.

[42]

C. Fu, X. Qi, L. Zhao, et al., “Synergistic Cooperation Between Atomically Dispersed Zn and Fe on Porous Nitrogen-Doped Carbon for Boosting Oxygen Reduction Reaction,” Applied Catalysis B: Environment 335 (2023): 122875.

[43]

R. Zhou, Y. Zheng, M. Jaroniec, and S.-Z. Qiao, “Determination of the Electron Transfer Number for the Oxygen Reduction Reaction: From Theory to Experiment,” ACS Catalysis 6 (2016):4720–4728.

[44]

K. Qu, Y. Zheng, S. Dai, and S. Z. Qiao, “Graphene Oxide-Polydopamine Derived N, S-Codoped Carbon Nanosheets as Superior Bifunctional Electrocatalysts for Oxygen Reduction and Evolution,” Nano Energy 19 (2016):373–381.

[45]

Q. Zhou, S. Hou, Y. Cheng, et al., “Interfacial Engineering Co and MnO Within N, S Co-Doped Carbon Hierarchical Branched Superstructures Toward High-Efficiency Electrocatalytic Oxygen Reduction for Robust Zn-Air Batteries,” Applied Catalysis, B: Environmental 295 (2021): 120281.

[46]

J. Guan, S. Yang, T. Liu, et al., “Intermetallic FePt@PtBi Core–Shell Nanoparticles for Oxygen Reduction Electrocatalysis,” Angewandte Chemie International Edition 60 (2021):21899–21904.

[47]

X. Zhang, Y. Liu, J. Gao, et al., “Defect-Rich (Co–CoS2)x@Co9S8 Nanosheets Derived From Monomolecular Precursor Pyrolysis With Excellent Catalytic Activity for Hydrogen Evolution Reaction,” Journal of Materials Chemistry A 6 (2018):7977–7987.

[48]

X. Chen, X. Zhen, H. Gong, et al., “Cobalt and Nitrogen Codoped Porous Carbon as Superior Bifunctional Electrocatalyst for Oxygen Reduction and Hydrogen Evolution Reaction in Alkaline Medium,” Chinese Chemical Letters 30 (2019):681–685.

[49]

X. Guan, Q. Wu, H. Li, et al., “Ultrafine Fe2C in Porous N-Doped Carbon by Polydopamine–Silane Co-Deposition for Efficient Oxygen Reduction Reaction and Zinc-Air Battery,” International Journal of Hydrogen Energy 48 (2023):9659–9668.

[50]

D. Malko, T. Lopes, E. Symianakis, and A. R. Kucernak, “The Intriguing Poison Tolerance of Non-Precious Metal Oxygen Reduction Reaction (ORR) Catalysts,” Journal of Materials Chemistry A 4 (2016):142–152.

[51]

X. Guan, H. Li, R. Li, et al., “An Organic-Inorganic Hybrid Strategy to Fabricate Highly Dispersed Fe2C in Porous N-Doped Carbon for Oxygen Reduction Reaction and Rechargeable Zinc-Air Battery,” Carbon 195 (2022):123–130.

[52]

N. Yang, L. Li, J. Li, W. Ding, and Z. Wei, “Modulating the Oxygen Reduction Activity of Heteroatom-Doped Carbon Catalystsviathe Triple Effect: Charge, Spin Density and Ligand Effect,” Chemical Science 9 (2018):5795–5804.

[53]

L. Zhang and Z. Xia, “Mechanisms of Oxygen Reduction Reaction on Nitrogen-Doped Graphene for Fuel Cells,” Journal of Physical Chemistry C 115 (2011):11170–11176.

[54]

L. Zhang, J. Niu, M. Li, and Z. Xia, “Catalytic Mechanisms of Sulfur-Doped Graphene as Efficient Oxygen Reduction Reaction Catalysts for Fuel Cells,” Journal of Physical Chemistry C 118 (2014):3545–3553.

[55]

Z. Yang, Z. Yao, G. Li, et al., “Sulfur-Doped Graphene as an Efficient Metal-Free Cathode Catalyst for Oxygen Reduction,” ACS Nano 6 (2012):205–211.

[56]

B. Ricciardi, W. da Silva Freitas, B. Mecheri, et al., “Hierarchical Porous Fe/Ni-Based Bifunctional Oxygen Electrocatalysts for Rechargeable Zinc-Air Batteries,” Carbon 219 (2024): 118781.

[57]

X. Wei, S. Song, W. Cai, et al., “Pt Nanoparticle–Mn Single-Atom Pairs for Enhanced Oxygen Reduction,” ACS Nano 18 (2024):4308–4319.

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2025 The Author(s). Carbon Neutralization published by Wenzhou University and John Wiley & Sons Australia, Ltd.

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