一步热解核黄素制备高性能氧还原反应电催化剂

doi:10.1016/S1872-2067(17)62885-7

催化学报 ›› 2017, Vol. 38 ›› Issue (10): 1668-1679.DOI: 10.1016/S1872-2067(17)62885-7

一步热解核黄素制备高性能氧还原反应电催化剂

邓玉潇, 皇甫海新, 唐水花, 李杰

西南石油大学材料科学与工程学院油气藏地质与开发国家重点实验室, 四川成都 610500

收稿日期:2017-05-04 修回日期:2017-07-03 出版日期:2017-10-18 发布日期:2017-10-28
通讯作者: 唐水花
基金资助:
催化基础国家重点实验室开放项目（N-14-1）；教育部海外留学归国人员科研启动项目；成都科技局国际合作项目。

High performance ORR electrocatalysts prepared via one-step pyrolysis of riboflavin

Yuxiao Deng, Haixin Huangfu, Shuihua Tang, Jie Li

State Key Laboratory of Oil and Gas Reservoir Geology & Exploitation, School of Materials Science and Engineering, Southwest Petroleum University, Chengdu 610500, Sichuan, China

Received:2017-05-04 Revised:2017-07-03 Online:2017-10-18 Published:2017-10-28
Contact: 10.1016/S1872-2067(17)62885-7
Supported by:
This work was supported by Open Project from State Key Laboratory of Catalysis (N-14-1), Scientific Research Foundation for Returned Scholars, Ministry of Education of China, and International Technology Collaboration of Chengdu Science and Technology Division.

摘要/Abstract

摘要：

质子交换膜燃料电池具有零污染、能量密度高、操作温度低和超静低音等优点，因而广泛应用于新能源汽车动力电源.然而质子交换膜燃料电池阴极氧还原反应（ORR）过程缓慢且复杂，因此需要大量的高性能ORR电催化剂.商品铂基催化剂是目前最为广泛使用的ORR催化剂，然而其高昂的价格阻碍了燃料电池汽车的商业化进程.因此，近年来人们致力于研发高性能的非贵金属ORR催化剂，并成功获得了具有高ORR活性及优异稳定性的催化剂.然而开发贵金属替代催化剂还存在制备过程较为复杂、单体有毒等缺点.
核黄素具有成本低廉、无毒、氮含量高等优点，本文将其直接作为碳源和氮源，以无水氯化铁为铁前驱体，通过简单的一步热解法制备了高性能的Fe-N-C催化剂.表征结果表明，合成的催化剂表面由于氮的掺杂导致石墨烯存在较多的缺陷，其比表面积为301 m² g^-1且孔径分布主要位于45 nm处；催化剂由很薄、卷曲的石墨烯片层和一些颗粒组成，其中的碳材料高度石墨化且存在Fe₂O₃晶体.结合X射线光电子能谱和催化剂的ORR活性，推导出石墨化氮为ORR的主要活性位，铁在ORR反应中也起着重要作用.在氧气饱和的0.1 mol L^-1 KOH溶液中，Fe-N-C催化剂的ORR活性达到4.16 mA cm^-2，与商品Pt/C催化剂相当（4.46 mA cm^-2）.采用计时电流法在0.66 V（相对于RHE电位）下运行3 h后，Fe-N-C催化剂电流仅下降了3%，而Pt/C催化剂下降了40%，表明Fe-N-C催化剂与Pt/C催化剂具有相近的ORR活性，但稳定性比Pt/C催化剂更出色.测试结果表明，Fe-N-C催化剂的抗甲醇毒化性能远优于Pt/C催化剂.在酸性介质中，Fe-N-C催化剂的ORR活性比Pt/C催化剂低，但稳定性更高.总之，该Fe-N-C催化剂在碱性介质中有较高的活性和稳定性，在酸性介质中有较高的稳定性.因此，我们采用廉价、无毒的核黄素作为碳氮源，通过简单的一步热解法制备出的Fe-N-C催化剂能较好地满足燃料电池ORR催化剂高性能和低成本的要求，具有很好的应用前景.

关键词: 核黄素, 热解, 氧气还原反应, 氯化铁, 电催化剂

Abstract:

Efficient, cost-effective electrocatalysts for an oxygen reduction reaction (ORR) are currently required for fuel cells. In the present work, riboflavin was used as a cheap, nontoxic carbon and nitrogen precursor to prepare Fe-N-C catalysts via one-step pyrolysis in the presence of anhydrous iron chloride. Raman spectroscopy indicated that the catalyst containing nitrogen created a great quantity of defects in the carbon structures, while nitrogen adsorption-desorption isotherms showed that the catalyst was mesoporous. Transmission electron microscopy demonstrated that the Fe-N-C catalyst was composed of very thin, curved and porous graphene layers together with some Fe₂O₃ nanoparticles, and X-ray diffraction patterns confirmed that the carbon in the catalyst was highly graphitized. X-ray photoelectron spectroscopy indicated that the active sites for the ORR were primarily composed of graphitic nitrogen, although Fe sites also played an important role. The ORR activity of the Fe-N-C catalyst reached a maximum of 4.16 mA cm^-2, and its chronoamperometric response was found to decrease by only 3% after operating for 3 h at 0.66 V (vs RHE) in an O₂-saturated 0.1 mol L^-1 KOH solution. In contrast, a commercial 40 wt% Pt/C catalyst with a loading of 0.2 mg_Pt cm^-2 exhibited an activity of 4.46 mA cm^-2 and a 40% loss of response. The electrochemical performance of this new Fe-N-C catalyst was therefore comparable to that of the Pt/C catalyst while showing significantly better stability.

Key words: Riboflavin, Pyrolysis, Oxygen reduction reaction, FeCl₃, Electrocatalyst

邓玉潇, 皇甫海新, 唐水花, 李杰. 一步热解核黄素制备高性能氧还原反应电催化剂[J]. 催化学报, 2017, 38(10): 1668-1679.

Yuxiao Deng, Haixin Huangfu, Shuihua Tang, Jie Li. High performance ORR electrocatalysts prepared via one-step pyrolysis of riboflavin[J]. Chinese Journal of Catalysis, 2017, 38(10): 1668-1679.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(17)62885-7

https://www.cjcatal.com/CN/Y2017/V38/I10/1668

参考文献

[1] M. Lefèvre, E. Proietti, F. Jaouen, J. P. Dodelet, Science, 2009, 324, 71-74.
[2] K. P. Gong, F. Du, Z. H. Xia, M. Durstock, L. M. Dai, Science, 2009, 323, 760-764.
[3] W. Shi, Y. C. Wang, C. Chen, X. D. Yang, Z. Y. Zhou, S. G. Sun, Chin. J. Catal., 2016, 37, 754-759.
[4] M. Klingele, C. Van Pham, A. Fischer, S. Thiele, Fuel Cells, 2016, 16, 522-529.
[5] S. Zhang, Y. Y. Shao, G. P. Yin, Y. H. Lin, J. Mater. Chem., 2009, 19, 7995-8001.
[6] K. L. Wang, H. Q. Wang, S. Ji, H. Feng, V. Linkov, R. F. Wang, RSC Adv., 2013, 3, 12039-12042.
[7] Q. Zuo, P. P. Zhao, W. Luo, G. Z. Cheng, Nanoscale, 2016, 8, 14271-14277.
[8] Y. J. Sa, D. J. Seo, J. Woo, J. T. Lim, J. Y. Cheon, S. Y. Yang, J. M. Lee, D. Kang, T. J. Shin, H. Y. Jeong, C. S. Kim, M. G. Kim, T. Y. Kim, S. H. Joo, J. Am. Chem. Soc., 2016, 138, 15046-15056.
[9] H. J. Deng, Q. Li, J. J. Liu, F. Wang, Carbon, 2017, 112, 219-229.
[10] T. Palaniselvam, V. Kashyap, S. N. Bhange, J. Beak, S. Kurungot, Adv. Funct. Mater., 2016, 26, 2150-2162.
[11] J. Wei, Y. Liang, Y. X. Hu, B. Kong, G. P. Simon, J. Zhang, S. P. Jiang, H. J. Wang, Angew. Chem. Int. Ed., 2016, 55, 1355-1359.
[12] S. P. Wang, M. L. Zhu, X. B. Bao, J. Wang, C. H. Chen, H. R. Li, Y. Wang, ChemCatChem, 2015, 7, 2937-2944.
[13] Y. Nie, X. H. Xie, S. G. Chen, W. Ding, X. Q. Qi, Y. Wang, J. Wang, W. Li, Z. P. Wei, M. H. Shao, Electrochim. Acta, 2016, 187, 153-160.
[14] Z. W. Chen, D. Higgins, A. P. Yu, L. Zhang, J. J. Zhang, Energy Environ. Sci., 2011, 4, 3167-3192.
[15] N. A. Karim, S. K. Kamarudin, Appl. Energy, 2013, 103, 212-220.
[16] M. L. Dou, D. P. He, W. H. Shao, H. J. Liu, F. Wang, L. M. Dai, Chem. Eur. J., 2016, 22, 2896-2901.
[17] Y. F. Yao, Y. You, G. X. Zhang, J. G. Liu, H. R. Sun, Z. G. Zou, S. H. Sun, ACS Appl. Mater. Interfaces, 2016, 8, 6464-6471.
[18] X. J. Cui, J. P. Xiao, Y. H. Wu, P. P. Du, R. Si, H. X. Yang, H. F. Tian, J. Q. Li, W. H. Zhang, D. H. Deng, X. H. Bao, Angew. Chem. Int. Ed., 2016, 55, 6708-6712.
[19] S. Dresp, F. Luo, R. Schmack, S. Kuhl, M. Gliech, P. Strasser, Energy Environ. Sci., 2016, 9, 2020-2024.
[20] C. Santoro, A. Serov, R. Gokhale, S. Rojas-Carbonell, L. Stariha, J. Gordon, K. Artyushkova, P. Atanassov, Appl. Catal. B, 2017, 205, 24-33.
[21] C. Chen, Z. Y. Zhou, Y. C. Wang, X. Zhang, X. D. Yang, X. S. Zhang, S. G. Sun, Chin. J. Catal., 2017, 38, 673-682.
[22] R. J. Jasinski, Nature, 1964, 201, 1212-1213.
[23] H. W. Liang, W. Wei, Z. S. Wu, X. L. Feng, K. Mullen, J. Am. Chem. Soc., 2013, 135, 16002-16005.
[24] R. Gokhale, Y. C. Chen, A. Serov, K. Artyushkova, P. Atanassov, Electrochim. Acta, 2017, 224, 49-55.
[25] C. S. He, T. T. Zhang, F. Z. Sun, C. Q. Li, Y. Q. Lin, Electrochim. Acta, 2017, 231, 549-556.
[26] E. Proietti, F. Jaouen, M. Lefèvre, N. Larouche, J. Tian, J. Herranz, J. P. Dodelet, Nat. Commun., 2011, 1427, 1-9.
[27] G. Wu, K. L. More, C. M. Johnston, P. Zelenay, Science, 2011, 332, 443-447.
[28] L. Xu, G. S. Pan, X. L. Shi, C. L. Zou, Y. Zhou, G. H. Luo, G. P. Chen, Electrochim. Acta, 2015, 177, 57-64.
[29] S. J. Chao, Z. Y. Bai, Q. Cui, H. Y. Yan, K. Wang, L. Yang, Carbon, 2015, 82, 77-86.
[30] S. M. Unni, S. Ramadas, R. Lllathvalappil, S. N. Bhange, S. Kurungot, J. Mater. Chem. A, 2015, 3, 4361-4367.
[31] W. Yan, L. Wang, C. Chen, D. Zhang, A. J. Li, Z. Yao, L. Y. Shi, Electrochim. Acta, 2016, 188, 230-239.
[32] X. X. Liu, Y. H. Wang, L. Dong, X. Chen, G. X. Xin, Y. Zhang, J. B. Zang, Electrochim. Acta, 2016, 194, 161-167.
[33] W. J. Jiang, L. Gu, L. Li, Y. Zhang, X. Zhang, L. J. Zhang, J. Q. Wang, J. S. Hu, Z. Wei, L. J. Wan, J. Am. Chem. Soc., 2016, 138, 3570-3578.
[34] S. Lee, D. H. Kwak, S. B. Han, E. T. Hwang, M. C. Kim, J. Y. Lee, Y. W. Lee, K. W. Park, Electrochim. Acta, 2016, 191, 805-812.
[35] L. L. Feng, G. T. Yu, Y. Y. Wu, G. D. Li, H. Li, Y. H. Sun, T. Asefa, W. Chen, X. X. Zou, J. Am. Chem. Soc., 2015, 137, 14023-14026.
[36] N. Ahmad, M. Alam, M. A. N. Al-Otaibi, Prog. React. Kinet. Mechan., 2015, 40, 86-94.
[37] J. Mas?owska, M. Malicka, J. Therm. Anal., 1988, 34, 3-9.
[38] S. Karthikeyan, Arch. Phys. Res., 2011, 2, 72-79.
[39] S. J. Ye, F. Wei, Analyst, 2011, 136, 2489-2494.
[40] Z. L. Wang, X. B. Zhang, X. J. Liu, M. F. Lv, K. Y. Yang, J. Meng, Carbon, 2011, 49, 161-169.
[41] R. V. Jagadeesh, A. E. Surkus, H. Junge, M. M. Pohl, J. Radnik, J. Rabeah, H. Huan, V. Schünemann, A. Brückner, M. Beller, Science, 2013, 342, 1073-1076.
[42] L. Z. Gu, L. H. Jiang, X. N. Li, J. T. Jin, G. Q. Sun, Chin. J. Catal., 2016, 37, 539-548.
[43] Y. Zhang, L. B. Huang, W. J. Jiang, X. Zhang, Y. Y. Chen, Z. D. Wei, L. J. Wan, J. S. Hu, J. Mater. Chem. A, 2016, 4, 7781-7787.
[44] L. F. Lai, J. R. Potts, D. Zhan, L. Wang, C. K. Poh, C. H. Tang, H. Gong, Z. X. Shen, J. Y. Lin, R. S. Ruoff, Energy Environ. Sci., 2012, 5, 7936-7942.
[45] R. L. Liu, D. Q. Wu, X. L. Feng, K. Müllen, Angew. Chem. Int. Ed., 2010, 49, 2565-2569.
[46] Z. H. Wen, S. Q. Ci, F. Zhang, X. L. Feng, S. M. Cui, S. Mao, S. L. Luo, Z. He, J. H. Chen, Adv. Mater., 2012, 24, 1399-1404.
[47] L. Wang, J. Yin, L. Zhao, C. G. Tian, P. Yu, J. Q. Wang, H. G. Fu, Chem. Commun., 2013, 49, 3022-3024.

一步热解核黄素制备高性能氧还原反应电催化剂

High performance ORR electrocatalysts prepared via one-step pyrolysis of riboflavin

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	周波, 石建巧, 姜一民, 肖磊, 逯宇轩, 董帆, 陈晨, 王特华, 王双印, 邹雨芹. 强化脱氢动力学实现超低电池电压和大电流密度下抗坏血酸电氧化[J]. 催化学报, 2023, 50(7): 372-380.
[2]	欧阳玲, 梁杰, 罗永嵩, 郑冬冬, 孙圣钧, 刘倩, Mohamed S. Hamdy, 孙旭平, 应斌武. 电催化合成氨的研究进展[J]. 催化学报, 2023, 50(7): 6-44.
[3]	孟帅奇, 李忠玉, 张鹏, Francisca Contreras, 季宇, Ulrich Schwaneberg. 深度学习指导的热裂褐藻角质酶工程用于促进PET解聚[J]. 催化学报, 2023, 50(7): 229-238.
[4]	李静静, 张锋伟, 詹新雨, 郭河芳, 张涵, 昝文艳, 孙振宇, 张献明. 酞菁镍分子结构的精确设计: 优化电子和空间效应用于CO₂电还原[J]. 催化学报, 2023, 48(5): 117-126.
[5]	张文静, 李静, 魏子栋. 碳基氧还原电催化剂: 机理研究和多孔结构[J]. 催化学报, 2023, 48(5): 15-31.
[6]	Enara Fernandez, Laura Santamaria, Irati García, Maider Amutio, Maite Artetxe, Gartzen Lopez, Javier Bilbao, Martin Olazar. 不同固定床位置生物质热解挥发物蒸汽催化重整反应中焦炭的形成和演化[J]. 催化学报, 2023, 48(5): 101-116.
[7]	吴则星, 高玉肖, 王子璇, 肖卫平, 王新萍, 李彬, 李镇江, 刘晓斌, 马天翼, 王磊. 表面富集的超小铂纳米颗粒耦合缺陷磷化钴用于高效的电催化水分解和柔性锌空气电池[J]. 催化学报, 2023, 46(3): 36-47.
[8]	刘小妮, 刘晓斌, 李彩霞, 杨波, 王磊. 缺陷工程在金属基电池中的研究进展[J]. 催化学报, 2023, 45(2): 27-87.
[9]	逯宇轩, 杨柳, 姜一民, 原甑然, 王双印, 邹雨芹. 局域静电环境工程用于增强电催化生物质转化过程中羟基活性[J]. 催化学报, 2023, 53(10): 153-160.
[10]	乔玉彦, 潘艳秋, 张江威, 王彬, 武婷婷, 范文俊, 曹雨程, Rashid Mehmood, 张飞, 章福祥. 多碳界面工程用于促进NiFe纳米复合电催化剂的产氧反应[J]. 催化学报, 2022, 43(9): 2354-2362.
[11]	崔彤, 翟雪君, 郭莉莉, 迟京起, 张昱, 朱家伟, 孙雪梅, 王磊. 自组装百合花状超低Ru, Ni掺杂的Fe₂O₃用于大电流碱性海水电解双功能电催化[J]. 催化学报, 2022, 43(8): 2202-2211.
[12]	钱秀, 魏艳娇, 孙梦洁, 韩野, 张晓俐, 田健, 邵敏华. 在Ti₃C₂T_x MXene上原位生长2D TiO₂纳米片的异质结构用于改善电催化氮气还原[J]. 催化学报, 2022, 43(7): 1937-1944.
[13]	王慧宁, 关安翔, 张俊波, 米玉莹, 李思, 袁涛涛, 静超, 张丽娟, 张林娟, 郑耿锋. 铜掺杂的羟基氧化镍用于高效电催化乙醇氧化[J]. 催化学报, 2022, 43(6): 1478-1484.
[14]	牛慧婷, 夏琛沣, 黄磊, Shahid Zaman, Thandavarayan Maiyalagan, 郭巍, 游波, 夏宝玉. 一维铂基纳米结构氧还原电催化剂的设计与合成[J]. 催化学报, 2022, 43(6): 1459-1472.
[15]	张利利, 蒋苏毓, 马炜, 周震. 铂基催化剂的氧还原反应路径调控[J]. 催化学报, 2022, 43(6): 1433-1443.