铁、氮掺杂石墨烯/碳黑复合材料的制备及氧还原电催化性能

doi:10.13208/j.electrochem.150849

电化学（中英文） ›› 2016, Vol. 22 ›› Issue (1): 25-31. doi: 10.13208/j.electrochem.150849

铁、氮掺杂石墨烯/碳黑复合材料的制备及氧还原电催化性能

陈驰^1,2，周志有^2*，张新胜¹，孙世刚²

1. 华东理工大学化学工程联合国家重点实验室，化工学院，上海 200237；2. 厦门大学固体表面物理化学国家重点实验室，化学化工学院，福建厦门 361005

收稿日期:2015-12-08 修回日期:2016-01-04 出版日期:2016-02-29 发布日期:2016-01-06
通讯作者: 周志有 E-mail:zhouzy@xmu.edu.cn
作者简介:周志有
基金资助:
国家自然科学基金项目（No. 21373175）资助

Synthesis of Fe, N-doped Graphene/Carbon Black Composite with High Catalytic Activity for Oxygen Reduction Reaction

CHEN Chi^1,2, ZHOU Zhi-you^2*, ZHANG Xin-sheng¹, SUN Shi-gang²

1. State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China; 2. State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China

Received:2015-12-08 Revised:2016-01-04 Published:2016-02-29 Online:2016-01-06
Contact: ZHOU Zhi-you E-mail:zhouzy@xmu.edu.cn
About author:ZHOU Zhi-you

摘要/Abstract

摘要：

以高含氮量的2-氨基咪唑为氮源，三氯化铁为铁源，高比表面积的KJ600碳黑为载体，通过水热法制得氨基咪唑聚合物前驱体，再经二次高温热处理，制得石墨烯/碳黑复合材料. 透射电镜表征显示该材料为石墨烯纳米片与碳黑颗粒的复合结构. BET表征表明这是一种多孔结构，具有很高的比表面积（882 m²•g^-1），这有利于暴露更多活性位点，并促进传质. XRD证实催化剂中存在石墨烯，且石墨烯结构是在第一次热处理过程中形成的. 电化学测试表明，该催化剂在酸性和碱性介质中都具有很高的氧还原电催化活性和低H₂O₂产率，并且在碱性介质中对甲醇小分子的抗毒化性能明显优于商业Pt/C催化剂，展示出在实际燃料电池系统中的应用潜力.

关键词: 2-氨基咪唑, N掺杂石墨烯, 氧气还原反应, 石墨烯/碳黑复合结构

Abstract:

Oxygen reduction reaction (ORR) is a bottleneck for improving the efficiency of proton-exchange membrane fuel cells as a cathode reaction due to its sluggish kinetics. The exploitation of low cost and high performance non-precious metal catalysts such as Fe/N/C based materials toward ORR has attracted extensive attentions. In this work, the Fe, N-doped graphene nanosheets/carbon black composite was prepared by hydrothermal polymerization and followed by a twice-heat-treatment procedure using 2-aminoimidazole as an N precursor, FeCl₃ as an Fe precursor and KJ600 carbon black as a support. The TEM images revealed that the graphene nanosheets were separated by carbon black nanoparticles to form a robust composite architecture. This composite structure can provide high surface area and porous structure, facilitating the exposure of active sites and the mass transfer of O₂. The XRD patterns proved the existence of graphene nanosheets formed during the first heat treatment. The obtained AIZ-Fe/N/C catalyst exhibited high ORR activity and low H₂O₂ yield in an alkaline medium. Its methanol resistance was much better than that of commercial Pt/C catalyst. Furthermore, the ORR activity in an acid medium was also impressive. These results demonstrated that the AIZ-Fe/N/C catalyst is a promising candidate to replace Pt-based catalysts as a cathode catalyst in fuel cells.

Key words: 2-aminoimidazole, N-doped graphene, oxygen reduction reaction, graphene nanosheets/carbon black composite

中图分类号:

O646

陈驰，周志有*，张新胜，孙世刚. 铁、氮掺杂石墨烯/碳黑复合材料的制备及氧还原电催化性能[J]. 电化学（中英文）, 2016, 22(1): 25-31.

CHEN Chi, ZHOU Zhi-you*, ZHANG Xin-sheng, SUN Shi-gang. Synthesis of Fe, N-doped Graphene/Carbon Black Composite with High Catalytic Activity for Oxygen Reduction Reaction[J]. Journal of Electrochemistry, 2016, 22(1): 25-31.

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.150849

https://electrochem.xmu.edu.cn/CN/Y2016/V22/I1/25

参考文献

[1] Chen Z W, Higgins D, Yu A P, et al. A review on non-precious metal electrocatalysts for PEM fuel cells[J]. Energy & Environmental Science, 2011, 4(9): 3167-3192.

[2] Othman R, Dicks A L, Zhu Z H. Non precious metal catalysts for the PEM fuel cell cathode[J]. International Journal of Hydrogen Energy, 2012, 37(1): 357-372.

[3] Masa J, Xia W, Muhler M, et al. On the role of metals in nitrogen-doped carbon electrocatalysts for oxygen reduction[J]. Angewandte Chemie-International Edition, 2015, 54(35): 10102-10120.

[4] Jaouen F, Proietti E, Lefèvre M, et al. Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells[J]. Energy & Environmental Science, 2011, 4(1): 114-130.

[5] Banham D, Ye S, Pei K, et al. A review of the stability and durability of non-precious metal catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells[J]. Journal of Power Sources, 2015, 285: 334-348.

[6] Wang X W, Sun G Z, Routh P, et al. Heteroatom-doped graphene materials: syntheses, properties and applications[J]. Chemical Society Reviews, 2014, 43(20): 7067-7098.

[7] Geng D S, Chen Y, Chen Y G, et al. High oxygen-reduction activity and durability of nitrogen-doped graphene[J]. Energy & Environmental Science, 2011, 4(3): 760-764.

[8] Gong K P, Du F, Xia Z H, et al. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction[J]. Science, 2009, 323(5915): 760-764.

[9] Poh H L, Simek P, Sofer Z, et al. Sulfur-doped graphene via thermal exfoliation of graphite oxide in H₂S, SO₂, or CS₂ gas[J]. Acs Nano, 2013, 7(6): 5262-5272.

[10] Xu J X, Dong G F, Jin C H, et al. Sulfur and nitrogen co-doped, few-layered graphene oxide as a highly efficient electrocatalyst for the oxygen-reduction reaction[J]. ChemSusChem, 2013, 6(3): 493-499.

[11] Yang Z, Yao Z, Li G F, et al. Sulfur-doped graphene as an efficient metal-free cathode catalyst for oxygen reduction[J]. Acs Nano, 2012, 6(1): 205-211.

[12] Choi C H, Chung M W, Kwon H C, et al. B, N- and P, N-doped graphene as highly active catalysts for oxygen reduction reactions in acidic media[J]. Journal of Materials Chemistry A, 2013, 1(11): 3694-3699.

[13] Sheng Z H, Gao H L, Bao W J, et al. Synthesis of boron doped graphene for oxygen reduction reaction in fuel cells[J]. Journal of Materials Chemistry, 2012, 22(2): 390-395.

[14] Li R, Wei Z D, Gou X L, et al. Phosphorus-doped graphene nanosheets as efficient metal-free oxygen reduction electrocatalysts[J]. Rsc Advances, 2013, 3(25): 9978-9984.

[15] Zhang C Z, Mahmood N, Yin H, et al. Synthesis of phosphorus-doped graphene and its multifunctional applications for oxygen reduction reaction and lithium ion batteries[J]. Advanced Materials, 2013, 25(35): 4932-4937.

[16] Jin Z P, Nie H G, Yang Z, et al. Metal-free selenium doped carbon nanotube/graphene networks as a synergistically improved cathode catalyst for oxygen reduction reaction[J]. Nanoscale, 2012, 4(20): 6455-6460.

[17] Kong X K, Chen C L, Chen Q W. Doped graphene for metal-free catalysis[J]. Chemical Society Reviews, 2014, 43(8): 2841-2857.

[18] Huang C C, Li C, Shi G Q. Graphene based catalysts[J]. Energy & Environmental Science, 2012, 5(10): 8848-8868.

[19] Wang H B, Maiyalagan T, Wang X. Review on recent progress in nitrogen-doped graphene: Synthesis, characterization, and its potential applications[J]. ACS Catalysis, 2012, 2(5): 781-794.

[20] Wei D C, Wu B, Guo Y L, et al. Controllable chemical vapor deposition growth of few layer graphene for electronic devices[J]. Accounts of Chemical Research, 2013, 46(1): 106-115.

[21] Gao X F, Jang J, Nagase S. Hydrazine and thermal reduction of graphene oxide: reaction mechanisms, product structures, and reaction design[J]. Journal of Physical Chemistry C, 2010, 114(2): 832-842.

[22] Deng D H, Pan X L, Yu L A, et al. Toward N-doped graphene via solvothermal synthesis[J]. Chemistry of Materials, 2011, 23(5): 1188-1193.

[23] Long D H, Li W, Ling L C, et al. Preparation of nitrogen-doped graphene sheets by a combined chemical and hydrothermal reduction of graphene oxide[J]. Langmuir, 2010, 26(20): 16096-16102.

[24] Wu G, Zelenay P. Nanostructured nonprecious metal catalysts for oxygen reduction reaction[J]. Accounts of Chemical Research, 2013, 46(8): 1878-1889.

[25] Wu M, Wang J, Wu Z X, et al. Synergistic enhancement of nitrogen and sulfur co-doped graphene with carbon nanosphere insertion for the electrocatalytic oxygen reduction reaction[J]. Journal of Materials Chemistry A, 2015, 3(15): 7727-7731.

[26] Liang H W, Wei W, Wu Z S, et al. Mesoporous metal-nitrogen-doped carbon electrocatalysts for highly efficient oxygen reduction reaction[J]. Journal of the American Chemical Society, 2013, 135(43): 16002-16005.

[27] Liang W, Chen J X, Liu Y W, et al. Density-functional-theory calculation analysis of active sites for four-electron reduction of O₂ on Fe/N-doped graphene[J]. ACS Catalysis, 2014, 4(11): 4170-4177.

[28] Li Y G, Zhou W, Wang H L, et al. An oxygen reduction electrocatalyst based on carbon nanotube-graphene complexes[J]. Nature Nanotechnology, 2012, 7(6): 394-400.

[29] Chung H T, Won J H, Zelenay P. Active and stable carbon nanotube/nanoparticle composite electrocatalyst for oxygen reduction[J]. Nature Communications, 2013, 4: 1922-1926.

[30] Lefevre M, Dodelet J P, Bertrand P. Molecular oxygen reduction in PEM fuel cells: Evidence for the simultaneous presence of two active sites in Fe-based catalysts[J]. Journal of Physical Chemistry B, 2002, 106(34): 8705-8713.

[31] Koslowski U I, Abs-Wurmbach I, Fiechter S, et al. Nature of the catalytic centers of porphyrin-based electrocatalysts for the ORR: A correlation of kinetic current density with the site density of Fe-N₄ centers[J]. The Journal of Physical Chemistry C, 2008, 112(39): 15356-15366.

[32] Zheng Y, Jiao Y, Ge L, et al. Two-step boron and nitrogen doping in graphene for enhanced synergistic catalysis[J]. Angewandte Chemie-International Edition, 2013, 52(11): 3110-3116.

[33] Liang J, Jiao Y, Jaroniec M, et al. Sulfur and nitrogen dual-doped mesoporous graphene electrocatalyst for oxygen reduction with synergistically enhanced performance[J]. Angewandte Chemie-International Edition, 2012, 51(46): 11496-11500.

铁、氮掺杂石墨烯/碳黑复合材料的制备及氧还原电催化性能

Synthesis of Fe, N-doped Graphene/Carbon Black Composite with High Catalytic Activity for Oxygen Reduction Reaction

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 3

Metrics

[1]	王雪, 张丽, 刘长鹏, 葛君杰, 祝建兵, 邢巍. 碱性介质中非贵金属氧还原催化剂的结构调控进展[J]. 电化学（中英文）, 2022, 28(2): 2108501-.
[2]	秦雪苹, 朱尚乾, 张露露, 孙书会, 邵敏华. 酸性和碱性溶液中金属氮碳材料氧还原和氢析出反应的理论研究[J]. 电化学（中英文）, 2021, 27(2): 185-194.
[3]	杨莉君，Dustin Banham, Elod Gyenge，叶思宇. Nafion含量与阴离子吸附对于铂单原子层核壳结构催化剂制备的影响[J]. 电化学（中英文）, 2017, 23(2): 170-179.