Citation: Chao WU, Qingxiu SHI, Tao XU, Zhengxi PENG, Zhongping XIONG, Yinglin ZHANG, Yujun SI, Chaozhong GUO. Enhancement of oxygen reduction reaction performance of iron-nitrogen doped carbon based catalysts by sodium carboxymethyl cellulose pre-deoxygenation[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(4): 737-746. doi: 10.11862/CJIC.20250305 shu

Enhancement of oxygen reduction reaction performance of iron-nitrogen doped carbon based catalysts by sodium carboxymethyl cellulose pre-deoxygenation

1.
School of Chemical and Environmental Engineering, Sichuan University of Science & Engineering, Zigong, Sichuan 643000, China
2.
College of Materials Science and Engineering, Chongqing University of Arts and Sciences, Chongqing 402160, China

Corresponding author: Yujun SI, syj08448@163.com Chaozhong GUO, guochaozhong1987@163.com
Received Date: 30 September 2025
Revised Date: 23 January 2026

Figures(6)

Iron-nitrogen co-doped carbon-based catalyst (180FeNC-2) was prepared using sodium carboxymethyl cellulose (CMC) as a precursor. The results indicate that pre-deoxygenation treatment of CMC induces cleavage of glycosidic bonds, which facilitates a higher nitrogen doping level in the catalyst obtained from co-carbonization with a nitrogen precursor. This process also promotes the formation of well-defined thin carbon sheets, constructing a hierarchical mesoporous structure that enhances mass transport and exposure of active sites during the catalytic reaction. The resulting catalyst (180FeNC-2) exhibited an oxygen reduction reaction half-wave potential of 0.887 V (vs RHE), an electrochemical active surface area of 11.26 mF·cm^-2, and a charge transfer resistance of 81 Ω in an alkaline electrolyte. Its catalytic performance surpasses that of the catalyst (0FeNC-2) derived from untreated CMC and was comparable to the standard Pt/C catalyst, while also demonstrating excellent stability and methanol tolerance. A zinc-air battery assembled based on 180FeNC-2 delivered an open-circuit voltage of 1.478 V, a maximum power density of 162 mW·cm^-2, and could stable discharge at 1.25 V under a current density of 10 mA·cm^-2.
- oxygen reduction reaction,
- carbon-based catalyst,
- sodium carboxymethyl cellulose,
- pre-deoxygenation treatment,
- nitrogen-doped carbon sheet
1. [1]
  HOU C, ZHAO J, HUANG B R, ZHOU X F, ZHANG Y L. Microalgae-based technologies for carbon neutralization and pollutant remediation: A comprehensive and systematic review[J]. Resour. Conserv. Recycl., 2024, 202: 107323 doi: 10.1016/j.resconrec.2023.107323
2. [2]
  NAEEM M A, APPIAH M, TADEN J, AMOASI R, GYAMFI B A. Transitioning to clean energy: Assessing the impact of renewable energy, bio-capacity and access to clean fuel on carbon emissions in OECD economies[J]. Energy Econ., 2023, 127: 107091 doi: 10.1016/j.eneco.2023.107091
3. [3]
  TAO W, SACHIN K M, WENG S, DENG X, CHEN X L, SONG M. Exploring the impact of energy saving and emission reduction fiscal policy on renewable energy development: Evidence from China[J]. Econ. Anal. Policy, 2025, 87: 463-483 doi: 10.1016/j.eap.2025.06.018
4. [4]
  PARK Y S, JUNG J, KOO M B, KIM J G, GU J, CHOI G H, KIM S H, KIM J F, AHN C H, HWANG S S, CHUNG H T, LEE A S. All protonated phosphonic acid membrane and ionomers for high powered intermediate temperature proton exchange membrane fuel cells[J]. Chem. Eng. J., 2025, 522: 167336 doi: 10.1016/j.cej.2025.167336
5. [5]
  ZHANG R W, SUN J L, CHEN Y Z, SHEN Q, DING C, ZHANG S M, ZHANG J J. Advanced porous platinum group metal nano-structural electrocatalysts for water electrolysis, fuel cells and metal-air batteries[J]. Coord. Chem. Rev., 2025, 543: 216958 doi: 10.1016/j.ccr.2025.216958
6. [6]
  SARSENOV S, MOON C J, SENTHIL R A, KUMAR A, MAHESKUMAR V, UBAIDULLAH M, KANJANAPAPARKUL K, KHEAWHOM S, CHOI M Y. Harnessing the surface-stabilized high-entropy alloy and nitrogen-doped carbon interplay for superior Zn-air battery performance[J]. Energy Storage Mater., 2025, 81: 104507 doi: 10.1016/j.ensm.2025.104507
7. [7]
  GUO Y F, LIU X, YANG S J, WANG P F, LIU Z L, ZHANG J H, LI C S, SHU J, YI T F. Composition modulation of electrocatalysts based on 3d transition metal towards high-performance Zn-air batteries[J]. Chem. Eng. J., 2024, 498: 155537 doi: 10.1016/j.cej.2024.155537
8. [8]
  GAUTAM J, MAHAJAN R L, LEE S Y, PARK S J. Bifunctional electrocatalysts for Zn-air batteries: A comprehensive review of design optimization and in-situ characterization[J]. Mater. Sci. Eng. R Rep., 2025, 166: 101058 doi: 10.1016/j.mser.2025.101058
9. [9]
  ZHANG P F, WEI M H, WANG K L, WANG H W, ZUO Y Y, ZHANG M H. Performance optimization of zinc-air batteries via nanomaterials[J]. Energy Storage Mater., 2025, 75: 104109 doi: 10.1016/j.ensm.2025.104109
10. [10]
  ZENG X, SHAHGALDI S, MITRA S K, LI X G. Impact of carbon supports on the Pt-based catalyst activity and fuel cell performance under varied operational conditions[J]. Energy Conv. Manag., 2025, 326: 119496 doi: 10.1016/j.enconman.2025.119496
11. [11]
  WU W F, YAN X, ZHAN Y. Recent progress of electrolytes and electrocatalysts in neutral aqueous zinc-air batteries[J]. Chem. Eng. J., 2023, 451: 138608 doi: 10.1016/j.cej.2022.138608
12. [12]
  HOU X T, WANG H, JIA L M, LI M X, YU W C, BIAN Z Y. Nitrogen-doped carbon bilayer flow-through electrocatalytic membrane based on transition metal single atoms: Simultaneous generation and activation of H₂O₂ for ibuprofen degradation[J]. Chem. Eng. J., 2025, 513: 162950 doi: 10.1016/j.cej.2025.162950
13. [13]
  LI Y Q, CUI M, XU J L, YANG Z Z, CHEN S R. A universal procedure to prepare high density M-N₄ sites anchored in nitrogen doped porous carbon as efficient oxygen reduction reaction catalysts for flexible Zn-air batteries[J]. J. Colloid Interface Sci., 2025, 702(Pt 1): 138918
14. [14]
  WU Q H, JIANG J H, GAO H J, JIA H L, WU C Y, DENG C Y, XU G C, AMMAR M, JIANG H, ZHANG L. Carbon cloth-based nitrogen-doped carbon nanotube-encapsulated Co nanoparticles as bifunctional oxygen electrocatalysts for flexible Zn-air batteries[J]. J. Mater. Sci. Technol., 2025, 255: 65-74
15. [15]
  LI W Y, ZHOU W T, ZHOU J C, JIANG J J, ZHANG M M, XIE J M. CeO₂ regulates electronic structure of Co-Fe alloy surface Interface on nitrogen-doped carbon to enhance oxygen reduction reaction in zinc-air battery[J]. Chem. Eng. J., 2025, 518: 164633 doi: 10.1016/j.cej.2025.164633
16. [16]
  JIN Z Y, CHEN Y Z, SUN J L, ZHANG S M, ZHANG J J. Perceptions of metal-nitrogen-carbon catalysts for oxygen reduction reaction[J]. Mater. Sci. Eng. R‒Rep., 2025, 165: 101027 doi: 10.1016/j.mser.2025.101027
17. [17]
  PARK S, KIM J, KWON K. A review on biomass-derived N-doped carbons as electrocatalysts in electrochemical energy applications[J]. Chem. Eng. J., 2022, 446: 137116 doi: 10.1016/j.cej.2022.137116
18. [18]
  SRINIVASAN S B, DEVENDIRAN S, SAVUNTHARI KV, ARUMUGAM P, MUKERJEE S. Insights into multifarious heteroatom-doped/enriched carbon-based materials and their composites: Synthesis and Supercapacitor applications—A crucial review[J]. Prog. Mater. Sci., 2025, 153: 101470 doi: 10.1016/j.pmatsci.2025.101470
19. [19]
  GU J W, WANG H F, LI S, RIAZ M S, NING J Q, PU X, HU Y. Tuning pyridinic-N and graphitic-N doping with 4, 4′-bipyridine in honeycomb-like porous carbon and distinct electrochemical roles in aqueous and ionic liquid gel electrolytes for symmetric supercapacitors[J]. J. Colloid Interface Sci., 2023, 635: 254-264 doi: 10.1016/j.jcis.2022.12.127
20. [20]
  WU C X, YU Y H, SONG Y M, RAO P, HAN X Q, LIANG Y, LI J, ZHANG K, ZHANG Z J, DENG P L, TIAN X L, WU D X. Pyrrole-type TM-N₃ sites as high-efficient bifunctional oxygen reactions electrocatalysts: From theoretical prediction to experimental validation[J]. J. Energy Chem., 2025, 104: 472-481 doi: 10.1016/j.jechem.2025.01.002
21. [21]
  WU Y, CHEN L, SUN P, ZHANG Q R, CHEN Y G, ZHENG X. Heterogeneous catalytic reactions of in-situ generated bromide ions via hydrodehalogenation of tetrabromobisphenol A in advanced oxidation processes over palladium nanoparticles[J]. Appl. Catal. B‒Environ. Energy, 2024, 340: 123213 doi: 10.1016/j.apcatb.2023.123213
22. [22]
  REN J Y, LIU S J, ZHANG J, ZHAO X F, YU S M, YUAN Z P, GUO Q L, SHEN X D, YI X B. Mesoporous TiO₂-GO-Cu Aerogel synthesized via classical sol-gel/supercritical drying route: High specific surface area and enhanced visible light photodegradation[J]. J. Non-Cryst. Solids, 2025, 667: 123733 doi: 10.1016/j.jnoncrysol.2025.123733
23. [23]
  BI T, ZHANG J, LI J, CUI W, LIN Q. A CoS₂-loaded N-doped ultrathin-wall mesoporous carbon with three-dimensional fluffy network structure as desirable sulfur-loading host for lithium-sulfur battery[J]. J. Alloy. Compd., 2025, 1020: 179386
24. [24]
  ZHANG Z, DONG X Y, GU T L, LI Q Y, LIU M Z, LI M H, ZHU W, LIANG X. How the macrocyclic precursors influence the M-N-C catalysts? Preparation and their applications on the electrochemically catalyzed hydrogen evolutions[J]. J. Alloy. Compd., 2024, 991: 174518 doi: 10.1016/j.jallcom.2024.174518
25. [25]
  HUANG Y, CHEN Y, XU M, LY A, GILI A, MURPHY E, ASSET T, LIU Y, DE ANDRADE V, SEGRE C U, DERIY A L, DE CARLO F, KUNZ M, GURLO A, PAN X, ATANASSOV P, ZENYUK I V. Catalysts by pyrolysis: Transforming metal-organic frameworks (MOFs) precursors into metal-nitrogen-carbon (M-N-C) materials[J]. Mater. Today, 2023, 69: 66-78 doi: 10.1016/j.mattod.2023.08.007
26. [26]
  YANG C Y, LANG J P. Diverse MOFs-derived carbon-based materials for advanced electrochemical energy applications[J]. EnergyChem, 2025, 7(4): 100163 doi: 10.1016/j.enchem.2025.100163
27. [27]
  ARSHAD F, REN P, YANG X, SUN H, QIAO Y. Recent breakthroughs in sulfide-functionalized metal-organic frameworks for electrocatalytic carbon dioxide reduction and hydrogen evolution reactions and their life cycle assessment[J]. Coord. Chem. Rev., 2026, 546: 217029 doi: 10.1016/j.ccr.2025.217029
28. [28]
  TANG R Z, FENG Y H, LIU Y F, WU Y H, LIU Q, HU G Z, LIU X J. Recent advancements of biomass materials in aqueous zinc-ion batteries[J]. Chem. Eng. J., 2025, 523: 168559 doi: 10.1016/j.cej.2025.168559
29. [29]
  WU H Y, ZHAO Q Q, JIANG S, LIU W, XIAO H N, WU W B. Research advances in doped carbon electrocatalysts derived from biomass[J]. Chem. Eng. J., 2025, 505: 159694 doi: 10.1016/j.cej.2025.159694
30. [30]
  HE C W J, LI B, YANG G J, HE S J, JIANG S H, YANG H Q, HAN J Q, LI X, WU F D, ZHANG Q. Progress of 0D biomass-derived porous carbon materials produced by hydrothermal assisted synthesis for advanced supercapacitors[J]. J. Colloid Interface Sci., 2025, 685: 487-508 doi: 10.1016/j.jcis.2025.01.163
31. [31]
  LI Z J, CHEN G Z, GUAN J Z, HUANG C L, GAO Z Y, CHEN X, YU H Y, LIU Y N. Confined graphitization of cellulose polymorphs enables high performance piezoresistive electronics[J]. Chem. Eng. J., 2025, 523: 168681 doi: 10.1016/j.cej.2025.168681
32. [32]
  ZHANG Q, DING Z T, LI Y, WANG X, HUANG J T. Conformational regulation and aggregation structure evolution during cellulose regeneration process[J]. Carbohydr. Polym., 2025, 370: 124332 doi: 10.1016/j.carbpol.2025.124332
33. [33]
  KONG Q Y, YANG G J, HE C W J, CHEN J X, HE S J, LI P, JIANG L J, YANG H Q, ZHANG C M, ZHANG Q. Sodium carboxymethyl cellulose derived carbon aerogels synthesized by zinc nitrate hexahydrate and urea for supercapacitor electrodes[J]. J. Energy Storage, 2024, 86: 111300 doi: 10.1016/j.est.2024.111300
34. [34]
  DA SILVA A H, MACUVELE D L P, RIELLA H G, SOARES C, PADOIN N. Polymeric blends of carboxymethyl cellulose and sodium alginate containing functionalized carbon dots result in stable and efficient fluorescent films for silver and iron􀃮 sensing[J]. J. Environ. Chem. Eng., 2021, 9(4): 105728 doi: 10.1016/j.jece.2021.105728
35. [35]
  HAN H, NOH Y, KIM Y, JUNG W S, PARK S, KIM W B. An N-doped porous carbon network with a multidirectional structure as a highly efficient metal-free catalyst for the oxygen reduction reaction[J]. Nanoscale, 2019, 11(5): 2423-2433 doi: 10.1039/C8NR10242B
36. [36]
  COLLARD F X, BLIN J. A review on pyrolysis of biomass constituents: Mechanisms and composition of the products obtained from the conversion of cellulose, hemicelluloses and lignin[J]. Renew. Sust. Energ. Rev., 2014, 38: 594-608 doi: 10.1016/j.rser.2014.06.013
37. [37]
  HU X X, LIU Y F, ZHU D D, JIN Y G, JIN H B, SHENG L. Preparation and characterization of edible carboxymethyl cellulose films containing natural antibacterial agents: Lysozyme[J]. Food Chem., 2022, 385: 132708 doi: 10.1016/j.foodchem.2022.132708
38. [38]
  LIN Y, DU Z Y, ZE H J, WANG X T, ZHANG Y, ZHANG H, ZHENG Q N, DONG J C, TIAN J H, LI J F. Understanding the molecular mechanism of oxygen reduction reaction using in-situ Raman spectroscopy[J]. Curr. Opin. Electyrochem., 2023, 42: 101381 doi: 10.1016/j.coelec.2023.101381
39. [39]
  LUO M S, SHAO C K, SONG H Q, XIA L M, GU J X. Effect of structure of metal-free nitrogen-doped coal-based carbon on catalytic oxygen reduction[J]. Fuel, 2025, 381: 133306 doi: 10.1016/j.fuel.2024.133306
40. [40]
  YU M, LI J, WANG L J. KOH-activated carbon aerogels derived from sodium carboxymethyl cellulose for high-performance supercapacitors and dye adsorption[J]. Chem. Eng. J., 2017, 310: 300-306 doi: 10.1016/j.cej.2016.10.121
41. [41]
  HAN Y L, LI Q K, YE K, LUO Y, JIANG J, ZHANG G Z. Impact of active site density on oxygen reduction reactions using monodispersed Fe-N-C single-atom catalysts[J]. J. Am. Chem. Soc., 2020, 12: 15271-15278
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