化学学报 ›› 2012, Vol. 70 ›› Issue (22): 2342-2346.DOI: 10.6023/A12070389 上一篇    下一篇

研究论文

碱性介质中Fe/N/C催化剂的氧气还原反应催化性能研究

郑龙珍, 陶堃, 熊乐艳, 叶丹, 韩奎, 纪忆   

  1. 华东交通大学 化学化工系 南昌 330013
  • 投稿日期:2012-07-24 发布日期:2012-10-23
  • 通讯作者: 郑龙珍 E-mail:zhenglongzhen@tsinghua.org.cn
  • 基金资助:
    项目受国家自然科学基金(Nos. 20965003, 21163007, 21165009, 21210102011)资助.

Electrocatalytic Activity of Fe/N/C Catalyst for the Oxygen Reduction Reaction in Alkaline Electrolyte

Zheng Longzhen, Tao Kun, Xiong Leyan, Ye Dan, Han Kui, Ji Yi   

  1. Department of Chemistry, East China Jiao Tong University, Jiang Xi, Nan Chang 330013
  • Received:2012-07-24 Published:2012-10-23
  • Supported by:
    Project supported by the National Natural Science Foundation of China (Nos. 20965003, 21163007, 21165009, 21210102011).

以氧化石墨烯(GO)为碳载体, K3Fe(CN)6同时作为N源和Fe源, 经热处理后构建了新型Fe/N/C结构的氧气还原催化剂. 在热处理过程中, 氧化石墨烯上的官能团分解脱离形成活性中心, Fe元素和N元素的同时掺杂是通过氧化石墨烯与K3Fe(CN)6之间的相互作用而实现的. 通过傅立叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)表征证明了这种非贵金属催化剂中N元素和Fe元素的成功掺杂, 在催化剂中N元素主要是以吡啶式氮、吡咯式氮和石墨式氮的形式存在, Fe(Ⅱ)和Fe(Ⅲ)则与其中的吡啶式氮配位形成Fe-Nx结构. 采用循环伏安法(CV)和旋转圆盘电极(RDE)技术, 研究其在碱性介质中对氧气还原反应(ORR)的电催化性能. 实验结果显示: Fe/N/C催化剂具有良好的ORR电催化活性, 在碱性溶液中的起始电位为-0.15 V, 同时有着良好的稳定性和抗甲醇性能.

关键词: 燃料电池, 氧气还原反应, 非贵金属催化剂, 电催化

Fuel cells have been recognized as one of the most promising power sources due to their high efficiency and low emissions. However, the high cost and scarcity of traditional Pt-based catalyst limit their commercialization. More intensive research have been focused on the development of non-noble-metal catalysts in order to replace Pt for catalyzing oxygen reduction reaction (ORR). Recently, it was reported that the Fe/N/C catalyst have high activity toward ORR. Chemical vapor deposition (CVD) is the most common method for the preparation of the Fe/N/C catalyst. However, the cost of CVD method is much higher. Here we report a facile method for the preparation of Fe/N/C catalyst for ORR in alkaline electrolyte. The catalyst is prepared by using graphene oxide as carbon support, and K3Fe(CN)6 as both nitrogen and iron sources. The precursors are then treated thermally at 800 ℃ under nitrogen atmosphere. In the process of heat treatment, the functional groups of graphene oxide are decomposed to form active center. Simultaneous doping of N and Fe can be realized by the interaction between graphene oxide and K3Fe(CN)6. The non-noble-metal catalyst is further characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). It shows that N and Fe elements are successively doped into the graphene substrate. In the catalyst, N elements exist mainly in the forms of pyridine N, pyrrole N and graphite N. Fe(Ⅱ) and Fe(Ⅲ) are coordinated with pyridine N to form Fe-Nx structure. The electrocatalytic activity of catalyst is evaluated by cyclic voltammetry (CV) and rotating disk electrode (RDE) experiments. The Fe/N/C catalyst shows high electrocatalytic activity toward ORR in an alkaline solution with an onset potential of -0.15 V vs. Ag/AgCl reference electrode. CVs of consecutive sweep for 2000 cycles are conducted to study the stability of the catalyst. The Fe/N/C catalyst exhibits excellent stability and methanol-tolerant ability.

Key words: fuel cells, oxygen reduction reaction, non-noble-metal catalyst, electrocatalysis