Effect of Fe/Co mass ratio on activity of non-noble metal catalyst for oxygen reduction reaction

doi:10.3969/j.issn.0438-1157.2014.06.023

Abstract

Abstract: Transition metal has an important effect on the electrocatalytic activity of non-noble metal catalysts for oxygen reduction reaction (ORR). In this work, the precursor containing MWCNTs, polyaniline, Fe and Co was firstly synthesized, and then the precursor was heated at 900℃ under N₂ to obtain the C-N catalysts with different Fe/Co mass ratios. The structure of the catalysts was investigated with SEM and X-ray diffraction. ORR activity of the catalysts in acidic and alkaline media was tested with voltammetry. The prepared catalyst with Fe/Co mass ratio of 6:1 presents the highest electrocatalytic activity for ORR. ORR current density at 2000 r·min^-1 was 12.5 mA·mg^-1@-0.3 V(vs SCE) in acidic solution and 7.8 mA·mg^-1@-0.8 V(vs SCE) in alkaline solution, and onset potential of ORR was 0.52 V(vs SCE) in acidic solution and-0.09 V(vs SCE) in alkaline solution. Fe/Co mass ratio played a great role in the electrocatalytic activity of these non-noble metal catalysts for ORR.

Key words: electrochemistry, fuel cell, catalysis, oxygen reduction reaction, non-noble metal catalyst

摘要： 中心金属离子在非贵金属C-N复合物对氧还原反应（ORR）的电催化活性方面有重要作用。通过将含有多壁碳纳米管（MWCNTs）、聚苯胺与过渡金属Fe和Co的前驱体在N₂气氛下于900℃下加热，得到了不同金属比例的C-N催化剂。采用SEM、XRD等对催化剂的结构进行了表征。利用电化学伏安技术，研究了催化剂对ORR的电催化活性及其稳定性。结果表明，当Fe与Co质量比为6：1时催化剂的催化活性最好，在酸性溶液中ORR起始电位达到0.52 V（vs SCE），电流密度为12.5 mA·mg^-1@-0.3 V （vs SCE）；在碱性溶液中ORR 起始电位为-0.09 V（vs SCE），电流密度为7.8 mA·mg^-1@-0.8 V （vs SCE）。结果表明，催化剂中Fe与Co的质量比对催化剂的活性有很大影响。

关键词: 电化学, 燃料电池, 催化, 氧还原, 非贵金属催化剂

CLC Number:

TQ152

ZHANG Yuhui, YI Qingfeng. Effect of Fe/Co mass ratio on activity of non-noble metal catalyst for oxygen reduction reaction[J]. CIESC Journal, 2014, 65(6): 2113-2119.

张玉晖, 易清风. 铁/钴质量比对MWCNT-聚苯胺复合物氧还原电活性的影响[J]. 化工学报, 2014, 65(6): 2113-2119.

References 23

[1]	Bashyam R, Zelenay P. A class of non-precious metal composite catalysts [J]. Nature, 2006, 443(7): 63-66
[2]	Jiang S P, Lin Z G, Tseung A C C. Homogeneous and heterogeneous catalytic reactions in cobalt oxide/graphite air electrodes [J]. Journal of the Electrochemical Society, 1990, 137(3): 759-764
[3]	Ladouceur M, Lalande G, Guay D,Dodelet J P,Dignard-Bailey L, Trudeau M L, Schulz R. Pyrolyzed cobalt phthalocyanine as electrocatalyst for oxygen reduction [J]. Journal of the Electrochemical Society, 1993, 140(7):1974-1981
[4]	Thomas S C, Ren X M, Gottesfeld S, Zelenay P. Direct methanol fuel cells: progress in cell performance and cathode research [J]. Electrochim. Acta, 2002, 47(22/23): 3741-3748
[5]	Yang Wei(杨伟),Chen Shengzhou(陈胜洲),Zou Hanbo(邹汉波),Lin Weiming(林维明). Progress in nitrogen-doped non-noble catalysts for oxygen reduction [J]. Chemical Industry and Engineering Progress(化工进展),2010, 29(11): 2085-2089
[6]	Ma Zifeng(马紫峰),Zhang Huijuan(张慧娟),Yuan Xianxia(原鲜霞),Jiang Qizhong(蒋淇忠). Research progress of non-precious metal oxygen reduction catalysts for low-temperature fuel cells [J]. Chemical Industry and Engineering Progress(化工进展),2011, 30(1): 150-154
[7]	Ren Qizhi(任奇志),Ma Xiaoxia(麻小霞),Xie Xianyu(谢先宇),Yan Tao(阎陶),Ma Zifeng(马紫峰). Heat-treated metalloporphyrin compounds supported on different carbons as electrocatalyst for oxygen reduction [J]. Journal of Chemical Industry and Engineering (China)(化工学报),2006, 57(11):2597-2603
[8]	Lefevre M,Dodelet J P,Bertrand P. O2 reduction in PEM fuel cells:activity and active site structural information for catalysts obtained by the pyrolysis at high temperature of Fe precursors [J]. Journal of Physical Chemistry B,2000,104(47):11238-11247
[9]	Bron M,Fiechter S,Hilgendorff M,Bogdanoff P. Catalysts for oxygen reduction from heat-treated carbon-supported iron phenantroline complexes [J]. Journal of Applied Electrochemistry,2002,32(2):211-216
[10]	Wu G, Nelson M, Ma S G, Meng H Cui G F, Shen P K. Synthesis of nitrogen-doped onion-like carbon and its use in carbon-based CoFe binary non-precious-metal catalysts for oxygen-reduction [J]. Carbon, 2011, 49(12): 3972-3982
[11]	Bezerra C W B, Zhang L, Lee K, Liu H, Marques A L B, Marques E P, Wang H J, Zhang J J. A review of Fe-N/C and Co-N/C catalysts for the oxygen reduction reaction [J]. Electrochim. Acta, 2008, 53(15): 4937-4951
[12]	Si Yujun(司玉军),Chen Changguo(陈昌国),Xiong Zhongping(熊中平),Yin Wei(尹伟),Cai Hui(蔡慧). Development of new type of carbon supported non-noble metal TM-N/C catalysts for oxygen reduction reaction [J]. Chinese Journal of Power Sources(电源技术),2010, 34(12): 1314 -1317
[13]	Nallathambi V, Lee J W, Kumaraguru S P, Wu G, Popov B N. Develepment of high performance carbon composite catalyst for oxygen reduction reaction in PEM fuel cells [J]. Journal of Power Sources, 2008, 183(1):34-42
[14]	Lalande G, Cote R, Tamizhmani G, Guay D, Dodelet J P, Dignard-Bailey L, Weng L P, Bertrand P. Physical, chemical and electrochemical characterization of heat-treated tetracarboxylic cobalt phthalocyanine adsorbed on carbon black as electrocatalyst for oxygen reduction in polymer electrolyte fuel cells [J]. Electrochim. Acta, 1995, 40(16):2635-2646
[15]	Faubert G, Cote R, Guay D,Dodelet J P, Denes G, Bertrandc P. Iron catalysts prepared by high-temperature pyrolysis of tetraphenylporphyrins adsorbed on carbon black for oxygen reduction in polymer electrolyte fuel cells [J].Electrochim. Acta, 1998(43): 341-353
[16]	Leferre M, Proietti E, Jaouen F, Dodelet J P. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells [J]. Science, 2009, 324(5923):71-74
[17]	Liu G, Li X G, Ganesan P, Popov B N. Development of non-precious metal oxygen-reduction catalysts for PEM fuel cells based on N-doped ordered porous carbon [J]. Applied Catalysis B: Environmental, 2009(93): 156-165
[18]	Morozan A, Jégou P, Jousselme B, Palacin S. Electrochemical performance of annealed cobalt-benzotriazole/CNTs catalysts towards the oxygen reduction reaction [J]. Physical Chemistry Chemical Physics, 2011, 13(48): 21600-21607
[19]	Deng L, Zhou M, Liu C, Liu L, Liu C Y, Dong S J. Development of high performance of Co/Fe/N/CNT nanocatalyst for oxygen reduction in microbial fuel cells [J]. Talanta, 2010, 81(1):444-448
[20]	Matsubara K, Waki K. The effect of O-functionalities for the electrochemical reduction of oxygen on MWCNTs in acid media [J]. Electrochemical and Solid-State Letters, 2010, 13(8): F7-F9
[21]	Lima F H B, de Castro J F R, Ticianelli Edson A. Silver-cobalt bimetallic particles for oxygen reduction in alkaline media[J]. Journal of Power Sources, 2006, 161(2): 806-812
[22]	Lide D R. CRC Handbook of Chemistry and Physics[M]. Boca Raton: CRC Press, 2001
[23]	Lobyntseva E, Kallio T, Alexeyeva N, Tammeveski K, Kontturi K. Electrochemical synthesis of hydrogen peroxide: rotating disk electrode and fuel cell studies [J]. Electrochim. Acta, 2007, 52(25): 7262-7269