Fe-PPy-TsOH/C用作质子交换膜燃料电池氧电极催化剂的研究

doi:10.15541/jim20160399

摘要/Abstract

摘要：

氧电极催化剂是制约质子交换膜燃料电池(PEMFCs)发展和应用的一个重要因素, 开发低价高效的非贵金属催化剂对PEMFCs来说已成为当务之急。本研究选择氮掺杂的碳载过渡金属(M-N/C)类催化剂为研究对象, 以铁盐作为金属前驱体, BP2000为碳源, 聚吡咯(PPy)为氮源, 对甲基苯磺酸(TsOH)为掺杂剂, 合成了非贵金属催化剂Fe-PPy-TsOH/C, 探究了不同的热处理温度及钴原子的掺杂对其氧还原催化性能的影响。研究结果表明: 800℃制备的Fe-PPy-TsOH/C催化剂因结晶度高、颗粒大小适中且分布均匀而具有最佳的氧还原催化性能; 一定量的钴原子取代可以改善Fe-PPy-TsOH/C的氧还原催化性能, 当钴的掺杂量为33.33%时(铁钴原子比为2︰1), 催化剂的性能达到最优。

关键词: 质子交换膜燃料电池, 氧还原, Fe-PPy-TsOH/C催化剂, 热处理, 钴掺杂

Abstract:

Cathode catalyst is a dominant parameter hindering the development of proton exchange membrane fuel cells (PEMFCs), exploiting non-precious metal based catalysts with low cost and high activity has become an urgent task in recent decades. In this work, a non-precious metal based catalyst of heat-treated nitrogen doped carbon supported transition metal based catalyst (M-N/C catalyst) was chosen as the subject, and a series of Fe-PPy-TsOH/C catalysts were synthesized with iron salt as the metal precursor, BP 2000 carbon black as the carbon source, polypyrrole (PPy) as the nitrogen source, and methyl benzene sulfonic acid (TsOH) as the dopant. The effects of heat-treatment temperature and cobalt-doping on the phase structure, morphologyand catalytic performance towards oxygen reduction reaction (ORR) were comparatively investigated. It shows that 800℃ is the optimal heat-treatment temperature to prepare high performance Fe-PPy-TsOH/C catalyst. If the iron in the Fe-PPy-TsOH/C catalyst is replaced by appropriate amount of cobalt, its catalytic performance towards ORR could be further improved, and the best ORR performance could be achieved at a cobalt cotent of 33.33% (Fe:Co=2:1 in ratio) in the range of 0-50at%.

Key words: proton exchange membrane fuel cells, oxygen reduction reaction, Fe-PPy-TsOH/C catalyst, heat treatment, cobalt doping

中图分类号:

O646

李姝玲, 原鲜霞, 孔海川, 徐进, 马紫峰. Fe-PPy-TsOH/C用作质子交换膜燃料电池氧电极催化剂的研究[J]. 无机材料学报, 2017, 32(4): 393-399.

LI Shu-Ling, YUAN Xian-Xia, KONG Hai-Chuan, XU Jin, MA Zi-Feng. Fe-PPy-TsOH/C as Cathode Catalyst for Proton Exchange Membrane Fuel Cells[J]. Journal of Inorganic Materials, 2017, 32(4): 393-399.

图/表 9

表1 催化剂Fe1-xCox-PPy-TsOH/C中铁和钴的量

Table 1 Content of Fe and Co in Fe1-xCox-PPy-TsOH/C catalysts

Catalyst	Fe/mmol	Co/mmol	Fe:Co
Catalyst	Fe/mmol	Co/mmol	synthesis	ICP
1	1.000	0	1:0	1:0
2	0.750	0.250	3:1	3.127:1
3	0.667	0.333	2:1	2.066:1
4	0.500	0.500	1:1	1.077:1

图1 不同热处理温度制得Fe-PPy-TsOH/C催化剂的XRD图谱

Fig. 1 XRD patterns of Fe-PPy-TsOH/C catalysts synthesized at various temperatures

图2 不同温度热处理制得的催化剂Fe-PPy-TsOH/C的拉曼光谱图

Fig. 2 Raman spectra of Fe-PPy-TsOH/C catalysts synthesized at various temperatures

图3 不同热处理温度制得Fe-PPy-TsOH/C催化剂的TEM照片

Fig. 3 TEM images of Fe-PPy-TsOH/C catalysts synthesized at various temperatures(a) 600℃; (b) 700℃; (c) 800℃; (d) 900℃; (e) 1000℃

图4 不同热处理温度制得Fe-PPy-TsOH/C催化剂在氧气饱和的0.5 mol/L H2SO4溶液中的循环伏安曲线

Fig. 4 Cyclic voltammograms of Fe-PPy-TsOH/C catalysts synthesized at various temperatures in oxygen saturated 0.5 mol/L H2SO4 solution at a potential scanning rate of 5 mV/s

图5 不同钴掺杂量的催化剂Fe1-xCox-PPy-TsOH/C的XRD图谱

Fig. 5 XRD patterns of Fe1-xCox-PPy-TsOH/C catalysts with various Co contents

图6 不同钴掺杂量的催化剂Fe1-xCox-PPy-TsOH/C的TEM照片

Fig. 6 TEM images of Fe1-xCox-PPy-TsOH /C catalysts with various Co contents(a) Fe1Co0-PPy-TsOH/C; (b) Fe0.75:Co0.25-PPy-TsOH/C; (c) Fe0.666Co0.333- PPy-TsOH /C; (d) Fe0.5:Co0.5-PPy-TsOH/C

图7 不同钴掺杂量的催化剂Fe1-xCox-PPy-TsOH/C的氮气吸脱附曲线(a)和BET比表面积(b)

Fig. 7 N2 adsorption-desorption isotherms (a) and the calculated BET specific surface areas (b) of Fe1-xCox-PPy-TsOH /C catalysts

图8 不同钴掺杂量的催化剂Fe1-xCox-PPy-TsOH/C在氧气饱和的0.5 mol/L H2SO4溶液中的循环伏安曲线

Fig. 8 Cyclic voltammograms of Fe1-xCox-PPy-TsOH/C catalysts in oxygen saturated 0.5 mol/L H2SO4 solution at a potential scanning rate of 5 mV/s

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