氮/硫双杂化非贵金属碱性阴离子膜燃料电池阴极非铂催化剂

doi:10.7503/cjcu20131208

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (5): 1029.doi: 10.7503/cjcu20131208

氮/硫双杂化非贵金属碱性阴离子膜燃料电池阴极非铂催化剂

徐莉^1,², 潘国顺^1,²(), 梁晓璐^1,², 罗桂海^1,², 邹春莉^1,², 陈高攀^1,²

1. 清华大学摩擦学国家重点实验室, 北京 100084
2. 深圳清华大学研究院深圳市微纳制造重点实验室, 深圳 518057

收稿日期:2013-12-10 出版日期:2014-05-10 发布日期:2014-01-23
作者简介:联系人简介: 潘国顺, 男, 博士, 副研究员, 主要从事亚纳米级表面抛光和燃料电池关键技术研究. E-mail:pangs@tsinghua.edu.cn
基金资助:
国家自然科学基金(批准号: 91223202)、国家国际科技合作专项项目(批准号: 2011DFA73410)和清华大学自主科研计划项目(批准号: 20101081907)资助

N/S Co-doped Non-precious Metal as Non-platinum Cathode Catalyst for Alkaline Membrane Fuel Cells^†

XU Li^1,², PAN Guoshun^1,^2,^*(), LIANG Xiaolu^1,², LUO Guihai^1,², Zou Chunli^1,², CHEN Gaopan^1,²

1. State Key Laboratory of Tribology, Tsinghua University, Beijing 100084, China
2. Shenzhen Key Laboratory of Micro/nano Manufacturing, Research Institute of TsinghuaUniversity in Shenzhen, Shenzhen 518057, China

Received:2013-12-10 Online:2014-05-10 Published:2014-01-23
Contact: PAN Guoshun E-mail:pangs@tsinghua.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.91223202), the International Science & Technology Cooperation Program of China(No.2011DFA73410), and the Tsinghua University Initiative Scientific Research Program, China(No.20101081907)

摘要/Abstract

摘要：

以吡咯和对甲苯磺酸(TsOH)作为碳载过渡金属催化剂的掺杂剂, 经溶剂分散及600 ℃热处理制备了一种高效催化氧还原反应(ORR)的碳载双杂化过渡金属催化剂(Fe-N/C-TsOH-600). 利用X射线衍射(XRD)和X射线光电子能谱(XPS)对催化剂的结构进行表征. 运用旋转圆盘电极(RDE)技术研究了该催化剂在碱性介质中催化氧还原的电化学催化活性和稳定性, 探讨了不同浓度甲醇溶液对Fe-N/C-TsOH-600催化剂催化氧还原活性的影响. 结果表明, 以Fe-N/C-TsOH-600制备的气体扩散电极在0.1 mol/L KOH电解质溶液中对氧具有很高的选择催化还原活性和稳定性. 当电极经过4800圈循环伏安(CV)扫描测试后, 催化剂催化氧还原的性能基本保持稳定, 并以4电子途径将氧气催化还原. 此外, 研究还发现, Fe-N/C-TsOH-600在混有甲醇的碱性电解质溶液中对氧的催化还原选择性比商业Pt/C催化剂高. XPS结果表明, 吡咯氮是催化剂高效催化氧还原的主要活性中心, 提供氧还原的活性位, 而TsOH作为供硫掺杂剂对提高催化剂的活性具有重要作用, 其加入后形成的C—S—C有利于催化剂催化氧还原活性的提高, 从而使该催化剂对氧还原表现出很好的电催化性能和选择性.

关键词: 碳载双杂化过渡金属催化剂, 氧还原反应, 稳定性, 碱性阴离子膜燃料电池

Abstract:

N/S co-doped non-precious metal material for the oxygen reduction reaction(ORR) was prepared with ferrous sulfate heptahydrate(FeSO₄·7H₂O), pyrrole and p-toluenesulfonic acid(TsOH) as Fe, N and S precursors supported on vulcan XC 72R, and followed by heat treatment in an inert atmosphere at 600 ℃. The electrochemical techniques such as cyclic voltammetry(CV) and rotating disk electrode(RDE) were employed with the Koutechy-Levich theory to make clear the ORR kinetical constants and the reaction mechanism. It is found that the catalysts dual-doped with TsOH show significantly improved ORR activity relative to the TsOH-free one. The overall electron transfer numbers for the catalyzed ORR are determined to be 3.899 and 3.098, respectively, for the catalysts with and without TsOH-doping. And these catalysts exhibit superior methanol tolerance to commercial 40%Pt/C catalyst. The XRD results demonstrate the decomposition of the precursors because of pyrolysis and formation of Fe-N_x-C active surface groups and some less active species. XPS analysis indicate that the pyrrolic-N groups are the most active sites and sulfur species are also structurally bonded to carbon in the forms of C—S_n—C and oxidized —SO_n— bonds, which are beneficial for ORR.

Key words: Dual-doped non-precious metal catalyst, Oxygen reduction reaction, Stability, Alkaline anion exchange membrane fuel cell

中图分类号:

O643
O614

TrendMD:

徐莉, 潘国顺, 梁晓璐, 罗桂海, 邹春莉, 陈高攀. 氮/硫双杂化非贵金属碱性阴离子膜燃料电池阴极非铂催化剂. 高等学校化学学报, 2014, 35(5): 1029.

XU Li, PAN Guoshun, LIANG Xiaolu, LUO Guihai, Zou Chunli, CHEN Gaopan. N/S Co-doped Non-precious Metal as Non-platinum Cathode Catalyst for Alkaline Membrane Fuel Cells^†. Chem. J. Chinese Universities, 2014, 35(5): 1029.

图/表 7

Fig.1 Polarization curves(A) and CVs(B) of catalysts Fe-N/C-TsOH-600(a) and Fe-N/C-600(b) in O2-saturated 0.1 mol/L KOH solution

Fig.2 Polarization curves for ORR on Fe-N/C-600(A) and Fe-N/C-TsOH-600(B) catalyst measured in O2-saturated 0.1 mol/L KOH electrolytes at various rotation rates^ω/(r·min-1) from top to bottom: 300, 600, 900, 1200, 1500, 1800, 2100, 2400.

Fig.3 Koutecky-Levich plots for Fe-N/C-600(A) and Fe-N/C-TsOH-600(B) in O2-saturated 0.1 mol/L KOH solution at the potential of -0.6, -0.4 and -0.2 V, respectively

Fig.4 Polarization curves for the oxygen reduction in O2-saturated 0.1 mol/L KOH on Fe-N/C-TsOH-600 before and after the potential cycling stability test(A) and iloss at different potential for the ORR in O2-saturated 0.1 mol/L KOH on Fe-N/C-TsOH-600 as a function of the number of potential cycling(B)^(A) Electrode rotating rate: 1500 r/min. Potential cycling was performed in N2-saturated 0.1 mol/L KOH with a scan rate of 50 mV/s between -0.76 and 0.14 V(vs. SHE) for 0, 1500, 4800 and 6000 cycles.

Fig.5 Polarization curves for O2 reduction on Pt/C electrode(A) and Fe-N/C-TsOH-600(B) in O2-saturated 0.1 mol/L KOH electrolyte without and with different concentrations of methanol solution^Potential scan rate: 5 mV/s. Electrode rotating rate: 1500 r/min. c(CH3OH)/(mol·L-1): a. 0; b. 0.5; c. 1.0; d. 5.0.

Fig.6 XRD patterns of Fe-N/C-TsOH-600(a) and Fe-N/C-TsOH(b) catalysts^Peaks 1—5: Fe3O4(022); Fe3O4(113); Fe(011), FeC(013); Fe3O4(115) and Fe3O4(044).

Fig.7 XPS spectra of deconvoluted N1s(A, B) and S2p(C, D) for catalyst Fe-N/C-TsOH before(A, C) and after(B, D) pyrolyzed at 600 ℃

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氮/硫双杂化非贵金属碱性阴离子膜燃料电池阴极非铂催化剂

N/S Co-doped Non-precious Metal as Non-platinum Cathode Catalyst for Alkaline Membrane Fuel Cells^†

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氮/硫双杂化非贵金属碱性阴离子膜燃料电池阴极非铂催化剂

N/S Co-doped Non-precious Metal as Non-platinum Cathode Catalyst for Alkaline Membrane Fuel Cells†

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N/S Co-doped Non-precious Metal as Non-platinum Cathode Catalyst for Alkaline Membrane Fuel Cells^†