华南理工大学学报(自然科学版) ›› 2012, Vol. 40 ›› Issue (10): 121-127.doi: 1000-565X(2012)10-0121-07

• 校庆专辑 • 上一篇    下一篇

新型氮掺杂碳基非金属催化剂的制备及其氧还原性能

廖世军 彭洪亮 张丙青   

  1. 华南理工大学 化学化工学院,广东 广州 510640
  • 收稿日期:2012-07-10 出版日期:2012-10-25 发布日期:2012-09-01
  • 通信作者: 廖世军(1958-) ,男,教授,博士生导师,主要从事催化及燃料电池技术研究. E-mail:chsjliao@ scut.edu.cn
  • 作者简介:廖世军(1958-) ,男,教授,博士生导师,主要从事催化及燃料电池技术研究.
  • 基金资助:

    国家自然科学基金资助项目( 21076089, 20876062)

A Novel N-Doped Carbon-Based Metal-Free Catalyst Prepared and Its Oxygen Reduction Performance

Liao Shi-jun  Peng Hong-liang  Zhang Bing-qing   

  1. School of Chemistry and Chemical Engineering,South China University of Technology,Guangzhou 510640,Guangdong,China
  • Received:2012-07-10 Online:2012-10-25 Published:2012-09-01
  • Contact: 廖世军(1958-) ,男,教授,博士生导师,主要从事催化及燃料电池技术研究. E-mail:chsjliao@ scut.edu.cn
  • About author:廖世军(1958-) ,男,教授,博士生导师,主要从事催化及燃料电池技术研究.
  • Supported by:

    国家自然科学基金资助项目( 21076089, 20876062)

摘要: 以三聚氰胺和聚苯胺为前驱体,在Ar 气氛保护下采用高温碳化的方法制备了一种新型的用于燃料电池阴极氧还原反应的氮掺杂碳基非金属电催化剂.考察了前驱体组成、碳化温度等因素对催化剂性能的影响,并利用XRD、TEM、DSC-TGA、Raman 光谱及FT-IR 等对催化剂进行了表征.结果表明: 最佳的碳化温度为900℃; 采用两次热处理和一次酸处理的过程有利于提高催化剂的活性; 该催化剂在0.1 mol /L 的HClO4 电解液中具有良好的电化学活性和稳定性,10000 圈循环伏安扫描后,催化剂的电化学活性不但没有衰减反而有所增强,其氧还原反应的半波电位达到0.42 V( vs.Ag /AgCl) ,极限扩散电流则几乎与目前最先进的Pt /C 催化剂等同; Koutecky-Levich 方程分析表明,催化剂氧还原反应按四电子机理进行.

关键词: 非铂催化剂, 氧还原反应, 三聚氰胺, 聚苯胺

Abstract:

In Ar atmosphere,a novel N-doped carbon-based metal-free catalyst for the cathodic oxygen reduction reaction ( ORR) in fuel cells was prepared via the high-temperature carbonization of the hybrid precursors of melamine and polyaniline. Then,the effects of such factors as the precursors and the carbonization temperature on the catalyst performance were discussed,and the catalyst was characterized by means of XRD,TEM,DSC-TGA,Raman spectroscopy and FT-IR. The results show that ( 1) the optimal carbonization temperature is 900℃; ( 2) the process with the pyrolysis twice and with the acid treatment once benefits the enhancement of the catalyst activity; and ( 3) the catalyst is of excellent electrochemical activity and stability in the electrolyte with 0.1 mol /L of HClO4,that is.after 10000 voltammetry circles,its electrochemical activity does not decrease but increases,with a half-wave potential of ORR of 0.42 V ( vs.Ag /AgCl) and a limited diffusion current nearly equal to that of the state-of-the-art Pt /C catalyst. In addition,it is found from Koutecky-Levich plots that the oxygen reduction on the catalyst is controlled by the four-electron transfer mechanism.

Key words: platinum-free catalyst, oxygen reduction reaction, melamine, polyaniline