ZIF-8衍生高效Fe-N-C催化剂的制备及其氧还原性能

张赛航; 姚赢赢; 李钊; 邹建新

doi:10.11868/j.issn.1001-4381.2023.000207

PDF(3938 KB)

材料工程 ›› 2025, Vol. 53 ›› Issue (3) : 135-142. DOI: 10.11868/j.issn.1001-4381.2023.000207

研究论文

ZIF-8衍生高效Fe-N-C催化剂的制备及其氧还原性能

张赛航 ¹^,²^,³ ,
姚赢赢 ¹^,²^,³ ,
李钊 ¹^,²^,³ ,
邹建新 ¹^,²^,³

作者信息 +

Synthesis of ZIF-8 derived high-efficiency Fe-N-C catalyst and its oxygen reduction reaction performance

Saihang ZHANG ¹^,²^,³ ,
Yingying YAO ¹^,²^,³ ,
Zhao LI ¹^,²^,³ ,
Jianxin ZOU ¹^,²^,³

Author information +

History +

摘要

为推动燃料电池的大规模商业化应用，开发高效、稳定和低成本的氧还原（ORR）催化剂具有重要意义。本工作以Fe掺杂ZIF-8为前驱体，通过球磨、高温氩气气氛下煅烧、酸洗后，在氨气气氛下进行二次煅烧，得到Fe-N-C非贵金属催化剂，多种表征手段的结果显示Fe原子均匀分散在氮掺杂的碳骨架上，从而形成丰富的Fe-N _x 催化活性位点。电化学性能测试结果表明，通过制备工艺和金属比例优化后的Fe-N-C-5%催化剂，在0.1 mol/L HClO₄的酸性溶液中表现出优异的ORR活性，半波电位为0.845 V，同时兼具良好的稳定性，在20000次循环后半波电位没有明显下降，这些结果为合理设计非贵金属ORR催化剂提供了有效的策略。

Abstract

To promote the large-scale commercial application of fuel cells， efficient， stable， and low-cost oxygen reduction reaction （ORR） catalysts should be developed. In this study， a Fe-doped ZIF-8 is used as the precursor， and the Fe-N-C non-precious metal catalyst is obtained by ball milling， calcination under a high-temperature argon atmosphere， pickling， and secondary calcination under an ammonia atmosphere. The results of various characterization methods show that Fe atoms are uniformly dispersed on the nitrogen-doped carbon framework， thus forming abundant Fe-N _x active sites. The electrochemical performance test results show that the Fe-N-C-5% catalyst with optimized preparation process and metal contents exhibits excellent ORR activity in 0.1 mol/L HClO₄ acidic solution， with a half-wave potential of 0.845 V. Meantime， it has good stability， and the half-wave potential does not drop significantly after 20000 cycles. These results provide an effective strategy for the rational design of precious metal-free ORR catalysts in the future.

关键词

氧还原反应 / 非贵金属催化剂 / 质子交换膜燃料电池 / 电催化 / 金属有机框架材料

Key words

oxygen reduction reaction / non-precious metal catalyst / proton exchange membrane fuel cell / electrocatalysis / metal-organic framework

中图分类号

TB34 / TQ426

引用本文

EndNote

Ris (Procite)

Bibtex

导出引用

张赛航 , 姚赢赢 , 李钊 , 等. ZIF-8衍生高效Fe-N-C催化剂的制备及其氧还原性能. 材料工程. 2025, 53(3): 135-142 https://doi.org/10.11868/j.issn.1001-4381.2023.000207

Saihang ZHANG, Yingying YAO, Zhao LI, et al. Synthesis of ZIF-8 derived high-efficiency Fe-N-C catalyst and its oxygen reduction reaction performance[J]. Journal of Materials Engineering. 2025, 53(3): 135-142 https://doi.org/10.11868/j.issn.1001-4381.2023.000207

参考文献

列表( 原文顺序 | 文献年度倒序 | 文中引用次数倒序 ) 可视化分析

[1]	孙鹏，李忠芳，王传刚，等. 燃料电池用高温质子交换膜的研究进展［J］. 材料工程， 2021， 49（1）： 23-34. SUN P， LI Z F， WANG C G， et al. Research progress of high temperature proton exchange membranes applied in fuel cells ［J］. Journal of Materials Engineering， 2021， 49（1）： 23-34. 本文引用 [1]

[2]	GASTEIGER H A， MARKOVIĆ N M. Just a dream-or future reality？［J］. Science， 2009，324： 48-49.

[3]	WANG X X， SWIHART M T， WU G. Achievements， challenges and perspectives on cathode catalysts in proton exchange membrane fuel cells for transportation ［J］. Nature Catalysis， 2019，2： 578-589. 本文引用 [1]

[4]	SHAO Y， DODELET J P， WU G， et al. PGM-free cathode catalysts for pem fuel cells： a mini-review on stability challenges ［J］. Advanced Materials， 2019，31： 1807615. 本文引用 [1]

[5]	杜真真，王珺，王晶，等. 质子交换膜燃料电池关键材料的研究进展［J］. 材料工程， 2022， 50（12）： 35-50. DU Z Z， WANG J， WANG J， et al. Research progress of key materials in proton exchange membrane fuel cell ［J］. Journal of Materials Engineering， 2022， 50（12）： 35-50. 本文引用 [1]

[6]	YAN X， LIU K， WANG T， et al. Atomic interpretation of high activity on transition metal and nitrogen-doped carbon nanofibers for catalyzing oxygen reduction ［J］. Journal of Materials Chemistry A， 2017，5： 3336-3345. 本文引用 [1]

[7]	CHONG L， WEN J G， KUBAL J， et al. Ultralow-loading platinum-cobalt fuel cell catalysts derived from imidazolate frameworks ［J］. Science， 2018，362： 1276-1281. 本文引用 [1]

[8]	XIAO F， WANG Q， XU G L， et al. Atomically dispersed Pt and Fe sites and Pt-Fe nanoparticles for durable proton exchange membrane fuel cells ［J］. Nature Catalysis， 2022，5： 503-512.

[9]

李茂辉，杨智，潘廷仙，等. 铁氮掺杂活性炭载体增强碳载铂基催化剂氧还原反应稳定性［J］. 材料工程， 2022， 50（4）： 132-138.

M H

， YANG

， PAN

T X

， et al. Enhanced stability for oxygen reduction reaction of supported platinum-based catalyst with Fe-N doped activated carbon as carbon support ［J］. Journal of Materials Engineering， 2022， 50（4）： 132-138.

本文引用 [1]

[10]	AKINPELU A， MERZOUGUI B， BUKOLA S， et al. A Pt-free electrocatalyst based on pyrolized vinazene-carbon composite for oxygen reduction reaction ［J］. Electrochimica Acta， 2015，161： 305-311. 本文引用 [1]

[11]	WU G， MORE K L， JOHNSTON C M， et al. High-performance electrocatalysts for oxygen reduction derived from polyaniline， iron， and cobalt ［J］. Science， 2011，332： 443-447. 本文引用 [1]

[12]	YIN P， YAO T， WU Y， et al. Single cobalt atoms with precise N-coordination as superior oxygen reduction reaction catalysts ［J］. Angewandte Chemie International Edition， 2016，55： 10800-10805. 本文引用 [1]

[13]	ZHANG H， OSGOOD H， XIE X， et al. Engineering nanostructures of PGM-free oxygen-reduction catalysts using metal-organic frameworks ［J］. Nano Energy， 2017，31： 331-350. 本文引用 [1]

[14]	GAO L， XIAO M， JIN Z， et al. Correlating Fe source with Fe-N-C active site construction： guidance for rational design of high-performance ORR catalyst ［J］. Journal of Energy Chemistry， 2018，27： 1668-1673. 本文引用 [1]

[15]	WANG X， ZHANG H， LIN H， et al. Directly converting Fe-doped metal-organic frameworks into highly active and stable Fe-N-C catalysts for oxygen reduction in acid ［J］. Nano Energy， 2016，25： 110-119. 本文引用 [1]

[16]	GAUTAM J， THANH T D， MAITI K， et al. Highly efficient electrocatalyst of N-doped graphene-encapsulated cobalt-iron carbides towards oxygen reduction reaction ［J］. Carbon， 2018， 137： 358-367. 本文引用 [1]

[17]	PAN Y， SUN K， LIU S， et al. Core-shell ZIF-8@ZIF-67-derived CoP nanoparticle-embedded N-doped carbon nanotube hollow polyhedron for efficient overall water splitting ［J］. Journal of the American Chemical Society， 2018，140： 2610-2618. 本文引用 [1]

[18]	GUO D， SHIBUYA R， AKIBA C， et al. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts ［J］. Science， 2016，351： 361-365. 本文引用 [1]

[19]	PENG H L， MO Z Y， LIAO S J， et al. High performance Fe- and N-doped carbon catalyst with graphene structure for oxygen reduction ［J］. Scientific Reports， 2013，3： 1765.

[20]	SONG P， ZHANG Y， PAN J， et al. Cheap carbon black-based high-performance electrocatalysts for oxygen reduction reaction ［J］. Chemical Communications， 2015，51： 1972-1975.

[21]	ZHU H， SUN Z， CHEN N， et al. A non-precious-metal catalyst derived from a Cp₂-Co⁺-PBI composite for cathodic oxygen reduction under both acidic and alkaline conditions ［J］. ChemElectroChem， 2017，4： 1117-1123. 本文引用 [1]

[22]	XIAO F， XU G L， SUN C J， et al. Nitrogen-coordinated single iron atom catalysts derived from metal organic frameworks for oxygen reduction reaction ［J］.Nano Energy，2019，61： 60-68. 本文引用 [1]

[23]	ZHANG B， WANG L， CAO Z， et al. High-valence metals improve oxygen evolution reaction performance by modulating 3d metal oxidation cycle energetics ［J］. Nature Catalysis， 2020，3： 985-992. 本文引用 [1]

[24]	XIAO M， ZHU J， MA L， et al. microporous framework induced synthesis of single-atom dispersed Fe-N-C acidic ORR catalyst and its in situ reduced Fe-N₄ active site identification revealed by X-ray absorption spectroscopy ［J］. ACS Catalysis， 2018，8： 2824-2832. 本文引用 [1]

[25]	HE Y， GUO H， HWANG S， et al. Single cobalt sites dispersed in hierarchically porous nanofiber networks for durable and high-power PGM-free cathodes in fuel cells ［J］. Advanced Materials， 2020，32： 2003577. 本文引用 [2]

[26]	XIE X， HE C， LI B， et al. Performance enhancement and degradation mechanism identification of a single-atom Co-N-C catalyst for proton exchange membrane fuel cells ［J］. Nature Catalysis， 2020，3： 1044-1054. 本文引用 [1]

[27]	WANG J， HUANG Z， LIU W， et al. Design of N-coordinated dual-metal sites： a stable and active pt-free catalyst for acidic oxygen reduction reaction ［J］. Journal of the American Chemical Society， 2017，139： 17281-17284. 本文引用 [1]

[28]	YIN S H， YANG J， HAN Y， et al. Construction of highly active metal-containing nanoparticles and FeCo-N₄ composite sites for the acidic oxygen reduction reaction ［J］. Angewandte Chemie International Edition， 2020，59： 21976-21979. 本文引用 [2]

[29]	ZHAO C， YU M， YANG Z， et al. Oxygen reduction reaction catalytic activity enhancement over mullite SmMn₂O₅ via interfacing with perovskite oxides ［J］. Nano Energy， 2018，51： 91-101. 本文引用 [1]

[30]	LIANG Y， LI Y， WANG H， et al. Co₃O₄ nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction ［J］. Nature Materials， 2011，10： 780-786. 本文引用 [1]

基金

国家重点研发计划项目(2022YFB3803700)

国家自然科学基金项目(52171186)

PDF(3938 KB)

Accesses

Citation

Detail

段落导航

Received	Revised	Published
2023-03-21	2024-10-11	2025-03-20
Issue Date
2025-06-18

选择文件类型/文献管理软件名称

选择包含的内容