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Mn-N-C催化剂的制备及其在碱性介质中对氧还原反应的电催化性能

张蓉,  张晶,  马飞,  王文洋,  李瑞丰

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文章导航 > 燃料化学学报（中英文）  > 2014 >  42(04): 467-475
张蓉, 张晶, 马飞, 王文洋, 李瑞丰. Mn-N-C催化剂的制备及其在碱性介质中对氧还原反应的电催化性能[J]. 燃料化学学报（中英文）, 2014, 42(04): 467-475.
引用本文: 张蓉, 张晶, 马飞, 王文洋, 李瑞丰. Mn-N-C催化剂的制备及其在碱性介质中对氧还原反应的电催化性能[J]. 燃料化学学报（中英文）, 2014, 42(04): 467-475.
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ZHANG Rong, ZHANG Jing, MA Fei, WANG Wen-yang, LI Rui-feng. Preparation of Mn-N-C catalyst and its electrocatalytic activity for the oxygen reduction reaction in alkaline medium[J]. Journal of Fuel Chemistry and Technology, 2014, 42(04): 467-475.
Citation: ZHANG Rong, ZHANG Jing, MA Fei, WANG Wen-yang, LI Rui-feng. Preparation of Mn-N-C catalyst and its electrocatalytic activity for the oxygen reduction reaction in alkaline medium[J]. Journal of Fuel Chemistry and Technology, 2014, 42(04): 467-475.
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Mn-N-C催化剂的制备及其在碱性介质中对氧还原反应的电催化性能

  • 太原理工大学 化学化工学院, 山西 太原 030024

基金项目: 山西省自然科学基金（2013011012-1）。
详细信息
    通讯作者:

    张蓉（1965-），博士，副教授，主要从事非贵金属氧还原催化剂的制备及电催化性能方面的研究，E-mail：zhangrong@tyut.edu.cn。

  • 中图分类号: O646

Preparation of Mn-N-C catalyst and its electrocatalytic activity for the oxygen reduction reaction in alkaline medium

  • College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China

    摘要
  • 摘要: 选用壳聚糖（CS）为原料制备了壳聚糖水杨醛席夫碱锰配合物（Mn-CS-sal）。将Mn-CS-sal配合物负载于石墨碳上得到碳载配合物（Mn-CS-sal/C），后经高温热处理得到Mn-N-C目标催化剂（Mn-N-C-t，t=200、400、600、800、1 000 ℃）。采用FT-IR、XRD、XPS和电化学等方法对催化剂的组成和结构进行了表征，对其在氧还原反应中的电催化性能进行了研究。结果表明，所得到的Mn-N-C催化剂对氧还原反应（ORR）具有很好的催化作用，但以600 ℃热处理制备的催化剂其活性最好。催化剂中Mn-N-C结构是催化ORR的活性位。采用循环伏安法获得了Mn-N-C-t催化ORR的动力学参数，即总的转移电子数n和电子传递系数αnα；具有最佳活性的Mn-N-C-600催化剂的总转移电子数为3.63，说明在此条件下，Mn-N-C-600催化ORR主要以4e转移途径为主，由此提出了可能的氧还原反应的机理。
    Abstract: Chitosan salicylaldehyde Schiff-base manganese complex (Mn-CS-sal) was synthesized by a simple chemical method and then supported on graphite carbon; the graphite-supported Mn-CS-sal (Mn-CS-sal/C) was heat-treated at different temperatures (t) to obtain the Mn-N-C catalysts (Mn-N-C-t, t=200, 400, 600, 800, 1 000 ℃). The electrocatalytic activity of Mn-N-C catalysts in the oxygen reduction reaction (ORR) was investigated and their structure and composition were characterized by Fourier Transform Infrared (FT-IR) spectrum, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results indicated that all the Mn-N-C catalysts are highly active in ORR, whereas the Mn-N-C-600 catalyst heat-treated at 600 ℃ exhibits the highest ORR activity. The excellent ORR activity of the Mn-N-C catalysts in alkaline media should be attributed to their Mn-N-C configuration. Two important kinetic parameters, i.e. the overall ORR electron transfer number (n) and electron transfer coefficiency (αnα), were determined by the cyclic voltammetry method. The Mn-N-C-600 catalyst shows an overall electron transfer number of 3.63 for ORR, suggesting that the catalytic ORR is via a mixture of 2- and 4-electron transfer pathways, but dominated by the 4-electron transfer process. Based on these observations, a possible mechanism for ORR over the surface of Mn-N-C modified electrode is proposed.
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出版历程
  • 收稿日期:  2013-11-20
  • 修回日期:  2014-01-16
  • 刊出日期:  2014-04-30

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