长春应化所金属氮碳氧还原催化剂的研究进展

doi:10.13208/j.electrochem.200444

电化学（中英文） ›› 2020, Vol. 26 ›› Issue (4): 464-473. doi: 10.13208/j.electrochem.200444

长春应化所金属氮碳氧还原催化剂的研究进展

徐明俊¹^,², 刘杰¹^,², 葛君杰¹^,^*(), 刘长鹏¹^,^*(), 邢巍¹^,^*()

1.中国科学院长春应用化学研究所,先进化学电源实验室,电分析化学国家重点实验室,吉林长春 130022
2.中国科学技术大学应用化学与工程学院,安徽合肥 230026

收稿日期:2020-05-07 修回日期:2020-05-29 出版日期:2020-08-28 发布日期:2020-06-03
通讯作者: 葛君杰,刘长鹏,邢巍 E-mail:gejj@ciac.ac.cn;liuchp@ciac.ac.cn;xingwei@ciac.ac.cn
基金资助:
国家重点研发计划项目(2017YFB0102900);国家自然科学基金(21633008);国家自然科学基金(21875243);国家自然科学基金(21433003);中国科学院战略重点研究先导项目(XDA09030104);RFBR project number (Fateev Vladimir)(18-53-53025);吉林省科技发展项目(20170520150JH);吉林省科技发展项目(20170203003SF);吉林省科技发展项目(20180101030JC)

Research Progress of Metal-Nitrogen-Carbon Catalysts toward Oxygen Reduction Reaction inm Changchun Institute of Applied Chemistry

XU Ming-jun¹^,², LIU Jie¹^,², GE Jun-jie¹^,^*(), LIU Chang-peng¹^,^*(), XING Wei¹^,^*()

1. State Key Laboratory of Electroanalytica Chemistry, Changchun Institute of Applied Chemistry,Chinese Academy of Sciences University of Chinese Academy of Sciences, Changchun 130022,Jilin, China
2. University of Science and Technology of China, School of Applied Chemistry & Engineering, Hefei 230026, Anhui, China

Received:2020-05-07 Revised:2020-05-29 Published:2020-08-28 Online:2020-06-03
Contact: GE Jun-jie,LIU Chang-peng,XING Wei E-mail:gejj@ciac.ac.cn;liuchp@ciac.ac.cn;xingwei@ciac.ac.cn

摘要/Abstract

摘要：

氧还原反应是燃料电池的核心,开发高性能催化剂一直是燃料电池技术面临的严峻挑战. 近年来,热解M-N-C催化剂的发展和以金属有机骨架材料为前驱体的运用让非贵金属氧还原催化剂的性能大幅度提升,但催化活性位点、反应机理等方面仍不甚清晰,需要分子水平上进一步的研究. 在这里,作者总结了本课题组近些年来在氧还原方向上的研究成果,首先是对催化剂活性位点进行的相关探索,提出了新的活性位点结构,为开发新型催化剂提供了帮助,并对金属氮碳催化剂进行了细致的微观调控,探讨了最佳的合成方法;其次开发了高效的双原子Co₂N₅催化剂,并在理论计算的指导下合成出了更为高效的FeCo双原子催化剂,具备了替代铂基催化剂的性能;最后针对芬顿反应引发的稳定性问题而开发的低芬顿反应活性的单原子Cr和单原子Ru催化剂,表现出了较高的活性和稳定性,为解决催化剂实际应用问题开辟了新的研究思路与方向. 作者相信,通过对催化剂活性位点的不断认知和对新型催化剂的不断开发,终会让非贵金属催化的商业化应用成为现实.

关键词: 氧还原反应, 金属氮碳催化剂, 活性位点, 原子分散, 燃料电池

Abstract:

The development of highly active and stable catalysts toward oxygen reduction reaction (ORR) has been facing severe challenges. In recent years, pyrolytic M-N-C catalysts and metal-organic framework derived materials made the performance of non-noble metal catalysts greatly improved, however, the molecular and atomic level understanding in the reaction active sites and the mechanism are still lacking. Here, we summarize the recent research progress made in the Changchun Institute of Applied Chemistry. We present a microporous metal-organic-framework confined strategy toward the preferable formation of ORR catalysts. Firstly, we studied the active site and proposed a new active site structure for the Fe-N-C catalyst, which is helpful for the development of new catalyst. The M-N-C catalyst was carefully regulated and the best synthesis method was discussed; Secondly, a highly efficient binuclear Co₂N₅ catalyst was developed, which performs approximately 12 times higher activity than the conventional CoN₄ site and shows unprecedented catalytic activity in an acidic electrolyte with the half-wave potential of 0.79 V, presenting the best one among the Co-N-C catalysts, and a more efficient FeCo diatomic catalyst was synthesized under the guidance of theoretical calculation, indicating that the FeCoN₅—OH site enables the ORR onset potential and half-wave potential up to 1.02 and 0.86 V (vs. RHE), respectively, with an intrinsic activity over 20 times higher than the single-atom FeN₄ site; Finally, to overcome the stability problem caused by Fenton reaction, we developed novel single atomic Cr and Ru catalysts, showing low Fenton reaction activity, higher activity and stability after the accelerated degradation test for 20000 cycles, with the half-wave potentials being dropped only 15 and 17 mV, respectively, much lower than 31 mV of Fe-N-C catalysts. This offers a new way to solve the problem in catalyst application. We believe that upon further understanding in the active sites and the continuous development of new catalyst, the non-noble metal catalysts in PEMFCs will become truly applicable, which aids to solve the increasingly serious energy crisis environment.

Key words: oxygen reduction reaction, metal-nitrogen-carbon catalyst, active site, atmotic dispersion, fuel cell

中图分类号:

O646

徐明俊, 刘杰, 葛君杰, 刘长鹏, 邢巍. 长春应化所金属氮碳氧还原催化剂的研究进展[J]. 电化学（中英文）, 2020, 26(4): 464-473.

XU Ming-jun, LIU Jie, GE Jun-jie, LIU Chang-peng, XING Wei. Research Progress of Metal-Nitrogen-Carbon Catalysts toward Oxygen Reduction Reaction inm Changchun Institute of Applied Chemistry[J]. Journal of Electrochemistry, 2020, 26(4): 464-473.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.200444

https://electrochem.xmu.edu.cn/CN/Y2020/V26/I4/464

图/表 6

图1

图2

图3

图4

图5

图6

参考文献 17

[1]	Shao M H, Chang Q W, Dodelet J P, et al. Recent advances in electrocatalysts for oxygen reduction reaction[J]. Chemical Reviews, 2016,116(6):3594-3657. URL pmid: 26886420
[2]	Hartmann P, Bender C L, Vracar M, et al. A rechargeable room-temperature sodium superoxide (NaO₂) battery[J]. Nature Materials, 2013,12(3):228-232. doi: 10.1038/nmat3486 URL pmid: 23202372
[3]	Wroblowa H S, Pan Y C, Razumney G. Electroreduction of oxygen - new mechanistic criterion[J]. Journal of Electroanalytical Chemistry, 1976,69:195-201.
[4]	J K Nörskov, J Rossmeisl, A Logadottir, et al. Origin of the overpotential for oxygen reduction at a fuel-cell cathode[J]. Journal of Physical Chemistry B, 2004,108(46):17886-17892.
[5]	Popov B N, Lee J W, Kriston A, et al. Review—Development of highly active and durable hybrid compressive platinum lattice catalysts for polymer electrolyte membrane fuel cells: mathematical modeling and experimental work[J]. Journal of The Electrochemical Society, 2020,167(5):054512.
[6]	Jasinski R. A new fuel cell cathode catalyst[J]. Nature, 1964,201:1212-1213. doi: 10.1038/2011212a0 URL
[7]	Jahnke H, Schonborn M, Zimmermann G. Organic dyestuffs as catalysts for fuel cells[J]. Topics in Current Chemistry, 1976,61:133-181. URL pmid: 7032
[8]	Proietti E, Jaouen F, Lefevre M, et al. Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells[J]. Nature Communications, 2011,2:416. URL pmid: 21811245
[9]	Wen Z H, Ci S Q, Zhang F, et al. Nitrogen-enriched coreshell structured Fe/Fe₃C-C nanorods as advanced electrocatalysts for oxygen reduction reaction[J]. Advanced Materials, 2012,24(11):1399-1404. doi: 10.1002/adma.201104392 URL pmid: 22311518
[10]	Zitolo A, Goellner V, Armel V, et al. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials[J]. Nature Materials, 2015,14(9):937-942. URL pmid: 26259106
[11]	Xiao M L, Zhu J B, Ma L, et al. Microporous framework induced synjournal 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(4):2824-2832. doi: 10.1021/acscatal.8b00138 URL
[12]	Gao L Q, Xiao M L, 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(6):1668-1673 doi: 10.1016/j.jechem.2018.06.008 URL
[13]	Gao L Q, Xiao M L, Jin Z, et al. Hydrogen etching induced hierarchical meso/micro-pore structure with increased active density to boost ORR performance of Fe-N-C catalyst[J]. Journal of Energy Chemistry, 2019,35:17-23. doi: 10.1016/j.jechem.2018.09.019 URL
[14]	Xiao M L, Zhang H, Chen Y T, et al. Identification of binuclear CO₂N₅ active sites for oxygen reduction reaction with more than one magnitude higher activity than single atom CoN₄ site[J]. Nano Energy 2018,46, 396-403.
[15]	Xiao M L, Chen Y T, Zhu J B, et al. Climbing the Apex of the ORR volcano plot via binuclear site construction: Electronic and geometric engineering[J]. Journal of The American Chemical Society, 2019,141(44):17763-17770. doi: 10.1021/jacs.9b08362 URL pmid: 31603677
[16]	Luo E G, Zhang H, Wang X, et al. Single-atom Cr-N₄ sites designed for durable oxygen reduction catalysis in acid media[J]. Angewandte Chemie International Edition, 2019,58(36):12469-12475. doi: 10.1002/anie.201906289 URL pmid: 31290248
[17]	Xiao M L, Gao L Q, Wang Y, et al. Engineering energy level of metal center: Ru single-atom site for efficient and durable oxygen reduction catalysis[J]. Journal of The American Chemical Society, 2019,141(50):19800-19806. doi: 10.1021/jacs.9b09234 URL pmid: 31763837

长春应化所金属氮碳氧还原催化剂的研究进展

Research Progress of Metal-Nitrogen-Carbon Catalysts toward Oxygen Reduction Reaction inm Changchun Institute of Applied Chemistry

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 17

相关文章 15

Metrics

[1]	陈发东, 谢卓洋, 李孟婷, 陈四国, 丁炜, 李莉, 李静, 魏子栋. 系列综述（1/4）:重庆大学魏子栋教授课题组在电化学能源转换方面的研究进展：燃料电池高性能氧还原催化剂[J]. 电化学（中英文）, 2024, 30(7): 2314007-.
[2]	陈浩杰, 唐美华, 陈胜利. 质子交换膜燃料电池阴极催化层疏水性优化[J]. 电化学（中英文）, 2023, 29(9): 2207061-.
[3]	郑天龙, 欧明玉, 徐松, 毛信表, 王释一, 和庆钢. 一体式可再生燃料电池双功能氧催化剂的研究进展[J]. 电化学（中英文）, 2023, 29(7): 2205301-.
[4]	黄荣钦, 廖卫平, 晏梦璇, 刘石, 李远明, 康雄武. 磷掺杂的Ru-Pt合金催化剂及其电催化碱性析氢性能[J]. 电化学（中英文）, 2023, 29(5): 2203081-.
[5]	刘思淼, 周景娇, 季世军, 文钟晟. FeNi-CoP/NC双功能催化剂的制备及电催化性能研究[J]. 电化学（中英文）, 2023, 29(10): 211118-.
[6]	韦宗楠, 曹敏纳, 曹荣. 瓜环基金属纳米催化剂的电化学研究进展[J]. 电化学（中英文）, 2023, 29(1): 2215008-.
[7]	郭鸿波, 王亚妮, 郭凯, 雷海涛, 梁作中, 张学鹏, 曹睿. 吸电子和亲水性Co-卟啉促进电催化氧还原反应的研究[J]. 电化学（中英文）, 2022, 28(9): 2214002-.
[8]	张天恩, 颜雅妮, 张俊明, 瞿希铭, 黎燕荣, 姜艳霞. 调控Pt₃Zn合金化程度改善酸性氧还原活性与稳定性[J]. 电化学（中英文）, 2022, 28(4): 2106091-.
[9]	冯雅辰, 王翔, 王宇琪, 严会娟, 王栋. 电催化氧还原反应的原位表征[J]. 电化学（中英文）, 2022, 28(3): 2108531-.
[10]	黄龙, 徐海超, 荆碧, 李秋霞, 易伟, 孙世刚. 质子交换膜燃料电池铂基催化剂研究进展[J]. 电化学（中英文）, 2022, 28(1): 2108061-.
[11]	王睿卿, 隋升. PEMFC阴极催化层结构分析[J]. 电化学（中英文）, 2021, 27(6): 595-604.
[12]	袁会芳, 张越, 翟兴吾, 胡立兵, 葛桂贤, 王刚, 于锋, 代斌. 氮掺杂碳原位锚定铜纳米颗粒用于高效氧还原反应催化剂[J]. 电化学（中英文）, 2021, 27(6): 671-680.
[13]	朱从懿, 李笑晖, 甘全全. 乙二醇基冷却液污染对质子交换膜燃料电池电堆的影响及恢复措施[J]. 电化学（中英文）, 2021, 27(6): 698-704.
[14]	魏荣强, 李世安, 刘艺辉, 杨治, 沈秋婉, 杨国刚. 流道与肋宽比对气体扩散层性能影响的数值研究[J]. 电化学（中英文）, 2021, 27(5): 579-585.
[15]	林华, 吴艺津, 李君涛, 周尧. 一锅法制备Fe₂O₃@Fe-N-C氧还原电催化剂及其锌-空气电池的性能研究[J]. 电化学（中英文）, 2021, 27(4): 366-376.