原子级铁锚定氮掺杂石墨烯的双功能氧电催化性能

doi:10.15541/jim20250519

无机材料学报 ›› 2026, Vol. 41 ›› Issue (6): 814-822.DOI: 10.15541/jim20250519

原子级铁锚定氮掺杂石墨烯的双功能氧电催化性能

汪加辉¹(), 刘晶晶¹, 邱毅¹, 王永霞¹(), 崔香枝²()

¹ 东华大学环境科学与工程学院, 上海 201620
² 中国科学院上海硅酸盐研究所, 关键陶瓷材料全国重点实验室, 上海 200050

收稿日期:2025-12-30 修回日期:2026-02-05 出版日期:2026-06-20 网络出版日期:2026-02-06
通讯作者: 王永霞, 副教授. E-mail: wyx912@dhu.edu.cn;
崔香枝, 研究员. E-mail: cuixz@mail.sic.ac.cn
作者简介:汪加辉(2001-), 男, 硕士研究生. E-mail: 18962019813@163.com
基金资助:
国家自然科学基金(52302084);中央高校基本科研业务费专项资金资助(2232025D-24)

Bifunctional Oxygen Electrocatalytic Performance of Atomically Dispersed Fe Anchored on N-doped Graphene

WANG Jiahui¹(), LIU Jingjing¹, QIU Yi¹, WANG Yongxia¹(), CUI Xiangzhi²()

¹ School of Environmental Science and Engineering, Donghua University, Shanghai 201620, China
² State Key Laboratory of High Performance Ceramics, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2025-12-30 Revised:2026-02-05 Published:2026-06-20 Online:2026-02-06
Contact: WANG Yongxia, associate professor. E-mail: wyx912@dhu.edu.cn;
CUI Xiangzhi, professor. E-mail: cuixz@mail.sic.ac.cn
About author:WANG Jiahui (2001-), male, Master candidate. E-mail: 18962019813@163.com
Supported by:
National Natural Science Foundation of China(52302084);Fundamental Research Funds for the Central Universities(2232025D-24)

摘要/Abstract

摘要：

随着对高效环保储能系统需求的日益增长, 锌空电池因其高能量密度、低成本及环境友好等特性, 成为极具前景的能源存储装置。然而, 空气阴极上缓慢的氧还原反应(ORR)和析氧反应(OER)动力学制约了电池性能的进一步提升, 故开发高性能、低成本的双功能氧电催化剂具有重要意义。本研究通过球磨辅助热解法, 制备了Fe单原子/团簇锚定石墨烯杂化催化剂(Fe-N/Gra)。通过调控前驱体金属酞菁与石墨烯的比例, 获得了系列Fe-N/Gra材料, 并考察了其双功能氧电催化性能。研究结果表明, 不同金属酞菁前驱体负载量对催化剂性能具有较大的影响。当酞菁铁负载量为0.02 g时, 所得催化剂Fe-N/Gra-0.02展现出最佳的ORR和OER催化活性: 其ORR半波电位高达0.911 V, OER在10 mA·cm^-2电流密度下的过电位为610 mV。以该催化剂作为空气电极组装的可充式锌空电池, 最大功率密度达315 mW·cm^-2, 在10 mA·cm^-2电流密度下可稳定放电210 h。Fe-N/Gra-0.02良好的双功能氧电催化活性主要归因于原子级分散Fe-N_x活性位点和载体石墨烯的高导电性, 另外高负载量催化剂中活性位点的团聚不利于展现其高效催化活性。本研究为高性能非贵金属双功能催化剂的可控制备及锌空电池的应用提供了实验依据。

关键词: 铁锚定氮掺杂石墨烯, 单原子/团簇, 氧还原反应, 析氧反应, 锌空电池

Abstract:

With the growing demand for efficient and environmental-friendly energy storage systems, zinc-air batteries have emerged as highly promising energy storage devices due to their high energy density, low cost, and environmental friendliness. The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), which suffer from sluggish kinetics, are critical factors limiting battery performance. Therefore, the development of high-performance and low-cost bifunctional oxygen electrocatalysts is of great significance. In this work, Fe single atoms/clusters anchored graphene hybrid catalysts (Fe-N/Gra) were prepared via a ball-milling assisted pyrolysis method. A series of Fe-N/Gra catalysts were obtained by adjusting the mass ratio of the metal phthalocyanine precursor to graphene, and their bifunctional oxygen electrocatalytic performances were systematically investigated. The results demonstrate that the loading amount of different metal phthalocyanine precursors exerts a significant influence on the catalytic performance of the catalysts. When the loading amount of iron phthalocyanine was 0.02 g, the resulting Fe-N/Gra-0.02 catalyst exhibited the optimal bifunctional catalytic activity for ORR and OER. The ORR half-wave potential reached as high as 0.911 V, and the OER overpotential was 610 mV at a current density of 10 mA·cm^-2. The rechargeable zinc-air batteries assembled with this catalyst as the air electrode achieved a maximum power density of 315 mW·cm^-2 and could sustain stable discharge for 210 h at 10 mA·cm^-2. The excellent bifunctional oxygen catalytic activity of Fe-N/Gra-0.02 is mainly attributed to the atomically dispersed Fe-N_x active sites and the high electrical conductivity of graphene support. In addition, the agglomeration of active sites in the catalysts with excessive loading amounts is detrimental to the manifestation of their high-efficiency catalytic activity. This work provides an experimental basis for the controllable preparation of high-performance non-noble metal bifunctional oxygen catalysts and their practical applications in rechargeable zinc-air batteries.

Key words: iron-anchored nitrogen-doped graphene, single-atom/cluster, oxygen reduction reaction, oxygen evolution reaction, Zn-air battery

中图分类号:

TB383

汪加辉, 刘晶晶, 邱毅, 王永霞, 崔香枝. 原子级铁锚定氮掺杂石墨烯的双功能氧电催化性能[J]. 无机材料学报, 2026, 41(6): 814-822.

WANG Jiahui, LIU Jingjing, QIU Yi, WANG Yongxia, CUI Xiangzhi. Bifunctional Oxygen Electrocatalytic Performance of Atomically Dispersed Fe Anchored on N-doped Graphene[J]. Journal of Inorganic Materials, 2026, 41(6): 814-822.

图/表 5

图1 Fe-N/Gra催化剂工艺制备图

Fig. 1 Schematic diagram of the preparation process for Fe-N/Gra catalysts

图2 Fe-N/Gra催化剂的物理表征

Fig. 2 Physical characterization of the synthesized Fe-N/Gra catalysts (a) TEM image of Fe-N/Gra-0.02; (b) AC-TEM image of Fe-N/Gra-0.02; (c) Elemental mappings of Fe-N/Gra-0.02; (d) XRD patterns and (e) Raman spectra of Fe-N/Gra catalysts with different Fe loadings after carbonization

图3 Fe-N/Gra催化剂中碳、氮和铁元素的XPS拟合分析

Fig. 3 XPS peak-fitting analyses of C, N, and Fe compositions in Fe-N/Gra catalysts (a, b, d) High-resolution XPS spectra of C1s, N1s, and Fe2p for Fe-N/Gra catalysts with different Fe loadings; (c) Comparison of the contents of pyridinic-N, pyrrolic-N, and graphitic-N for Fe-N/Gra catalysts with different Fe loadings. Colorful figures are available on website

图4 Fe-N/Gra催化剂的电化学性能分析(0.1 mol·L-1 KOH)

Fig. 4 Electrochemical performance characterization of Fe-N/Gra catalysts (0.1 mol·L-1 KOH) (a) LSV curves of Fe-N/Gra catalysts with different Fe loadings in O2-saturated 0.1 mol/L KOH electrolyte at a rotation speed of 1600 r/min; (b) Tafel slopes derived from ORR; (c) LSV curves of Fe-N/Gra-0.02 before and after 3000 cycles; (d) OER curves of Fe-N/Gra catalysts with different Fe loadings; (e) Tafel slopes derived from OER; (f) EIS spectra of Fe-N/Gra catalysts with different Fe loadings; (g) Comparative graph of half-wave potentials for different catalysts and the catalyst in this study[27-35]; (h) Comparison of charge transfer resistance for different catalysts[36-40]. Colorful figures are available on website

图5 锌空电池性能测试及反应机理示意图

Fig. 5 Performance tests of Zn-air battery and schematic illustration of reaction mechanism (a) Schematic diagram of self-assembled Zn-air battery; (b) Polarization curves of the Zn-air battery assembled with Fe-N/Gra-0.02; (c) Discharge performance test of Fe-N/Gra-0.02 at a current density of 10 mA·cm-2; (d) Long-term charge-discharge cycling stability test; (e) Comparative bar chart of apparent current density for different electrocatalysts[27,30 -34,41 -42]; (f) Schematic diagram of valence state changes for Fe2+ and Fe3+ in battery reactions

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原子级铁锚定氮掺杂石墨烯的双功能氧电催化性能

Bifunctional Oxygen Electrocatalytic Performance of Atomically Dispersed Fe Anchored on N-doped Graphene

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