物理化学学报 >> 2017, Vol. 33 >> Issue (9): 1811-1821.doi: 10.3866/PKU.WHXB201704264

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氮、硫共掺杂的碳负载的钴@碳化钴:一种高效的非贵金属氧还原电催化剂

申海波1,江浩1,刘易斯1,3,郝佳瑜1,李文章1,2,4,*(),李洁1,*()   

  1. 1 中南大学化学化工学院,长沙410083
    2 中南大学湖南省锰资源高效清洁利用重点实验室,长沙410083
    3 加拿大西安大略大学机械与材料工程系,安大略N6A5B9
    4 有色金属成矿预测与地质环境监测教育部重点实验室(中南大学),长沙410083
  • 收稿日期:2017-02-20 发布日期:2017-07-05
  • 通讯作者: 李文章,李洁 E-mail:liwenzhang@csu.edu.cn;lijieliu@csu.edu.cn
  • 基金资助:
    国家自然科学基金(51474255);湖南省科技计划项目(2016TP1007);中南大学有色金属成矿预测与地质环境监测教育部重点实验室开放基金和中南大学中央高校基本科研业务费专项资金

Cobalt@cobalt Carbide Supported on Nitrogen and Sulfur Co-Doped Carbon: an Efficient Non-Precious Metal Electrocatalyst for Oxygen Reduction Reaction

Hai-Bo SHEN1,Hao JIANG1,Yi-Si LIU1,3,Jia-Yu HAO1,Wen-Zhang LI1,2,4,*(),Jie LI1,*()   

  1. 1 School of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China
    2 Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources, Central South University, Changsha 410083, P. R. China
    3 Department of Mechanical and Materials Engineering, University of Western OntarioLondon, Ontario, N6A5B9, Canada
    4 Key Laboratory of Hunan Province for Metallurgy and Material Processing of Rare Metals, Changsha 410083, P. R. China
  • Received:2017-02-20 Published:2017-07-05
  • Contact: Wen-Zhang LI,Jie LI E-mail:liwenzhang@csu.edu.cn;lijieliu@csu.edu.cn
  • Supported by:
    the National Nature Science Foundation of China(51474255);the Hunan Provincial Science and Technology Plan Project, China(2016TP1007);the Open Research Fund Program of Key Laboratory of Metallogenic Prediction of Nonferrous Metals and Geological Environment Monitoring, China (Central South University), Ministry of Education, the Fundamental Research Funds for the Central Universities of Central South University, China

摘要:

规模化生产低成本和高效率的氧还原电催化剂在当今仍然是严峻的挑战。本文以三聚氰胺、三聚硫氰酸和硝酸钴作为原料,通过两步热解合成了一种新的氮、硫共掺杂的碳负载的钴@碳化钴(标记为MTC-0.1-900)氧还原催化剂。利用扫描电子显微镜、透射电子显微镜、X射线衍射、拉曼光谱、比表面分析和X射线光电子能谱分析对该催化剂进行了表征,并采用循环伏安和线性扫描伏安曲线等方法测试其在0.1 mol·L-1KOH中的氧还原性能。结果显示,与商业Pt/C催化剂相比,MTC-0.1-900的起始电位和半波电位分别高出了29和5 mV。在-0.3 V(vs Ag/AgCl)电位下工作12000 s后,MTC-0.1-900催化剂的电流可达到起始电流的97.1%,高于Pt/C催化剂的76.7%,显示出该催化剂具有更稳定的性能。抗甲醇实验表明,MTC-0.1-900的对氧还原的选择性也要优于Pt/C。该催化剂优良的性能为金属空气电池阴极材料提供了一种减少或者取代Pt的新选择。

关键词: 氮、硫共掺杂, 钴@碳化钴, 石墨化碳, 核壳结构, 氧还原

Abstract:

Development of high-efficiency and low-cost electrocatalysts for large-scale oxygen reduction reaction (ORR) remains a challenge. In this study, we employed melamine, trithiocyanuric acid, and cobaltous nitrate to fabricate a novel ORR electrocatalyst with cobalt and cobalt carbide supported on carbon co-doped with nitrogen and sulfur (hereafter referred to as MTC-0.1-900) by two-step pyrolysis. The MTC-0.1-900 was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, Brunauer-Emmett-Teller (BET) specific surface area analysis, and X-ray photoelectron spectroscopy (XPS). The electrochemical performance for ORR was investigated by cyclic voltammetry and linear sweep voltammetry in 0.1 mol·L-1 KOH solutions. The results showed that the onset potential and half-wave potential of MTC-0.1-900 were 29 and 5 mV superior to the commercial Pt/C catalyst, respectively. After 12000 s operation at the potential of -0.3 V (vs Ag/AgCl), the current retention capacities of MTC-0.1-900 and Pt/C were 97.1% and 76.7%, respectively. MTC-0.1-900 also showed better methanol tolerance than Pt/C. These unique properties of MTC-0.1-900 provide us with an alternative for replacing or reducing the use of Pt catalyst in metal-air battery cathode materials.

Key words: Nitrogen and sulfur co-doped carbon, Cobalt@cobalt carbide, Graphitic carbon, Core-shell, Oxygen reduction reaction

MSC2000: 

  • O646