化学学报 ›› 2013, Vol. 71 ›› Issue (09): 1225-1238.DOI: 10.6023/A13030262 上一篇    下一篇

综述

直接甲醇燃料电池Pt基阳极催化剂的研究进展

王宗花a,b, 史国玉a,b, 夏建飞a,b, 张菲菲a,b, 夏延致a, 李延辉a, 夏临华a   

  1. a 青岛大学纤维新材料与现代纺织实验室 国家重点实验室培育基地 青岛 266071;
    b 青岛大学化学化工与环境学院 山东省中日碳纳米材料合作研究中心 青岛 266071
  • 投稿日期:2013-03-10 发布日期:2013-06-13
  • 通讯作者: 王宗花,E-mail:wangzonghua@qdu.edu.cn;Tel.:0532-85950873 E-mail:wangzonghua@qdu.edu.cn
  • 基金资助:

    项目受国家自然科学基金(Nos. 20975056, 81102411, 21275082)、山东省自然科学基金(Nos. ZR2011BZ004, ZR2011BQ005)、日本科学促进协会和中国国家自然科学基金中日合作与交流(No. 21111140014)、生命分析化学国家重点实验室开放基金(No. SKLACLS1110)及国家重点基础研究发展计划(973计划, No. 2012CB722705)资助.

Research Progress on Pt-Based Anode Catalysts in the Direct Methanol Fuel Cell

Wang Zonghuaa,b, Shi Guoyua,b, Xia Jianfeia,b, Zhang Feifeia,b, Xia Yanzhia, Li Yanhuia, Xia Linhuaa   

  1. a Laboratory of Fiber Materials and Modern Textile, The Growing Base for State Key Laboratory, Qingdao University, Qingdao, 266071;
    b College of Chemical and Environment Engineering, Shandong Sino-Japanese Center for Collaborative Research of Carbon Nanomaterials, Qingdao University, Qingdao 266071
  • Received:2013-03-10 Published:2013-06-13
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 20975056, 81102411, 21275082), the Natural Science Foundation of Shandong Province (Nos. ZR2011BZ004, ZR2011BQ005), the Japan Society for the Promotion of Science and National Natural Science Foundation of China under the Japan-China Scientific Cooperation Program (No. 21111140014), the State Key Laboratory of Analytical Chemistry for Life Science (No. SKLACLS1110) and the National Key Basic Research Development Program of China (973 special preliminary study plan, No. 2012CB722705).

作为未来能源储存和转换装置的理想选择, 直接甲醇燃料电池具有能量密度高、携带方便以及环境友好等特点. 直接甲醇燃料电池欲实现商业化关键在于如何降低其催化剂成本, 构建高效稳定催化层, 尤其是阳极催化层. 由于非Pt催化剂对于甲醇催化氧化效率太低, 远远达不到商业化应用的要求, 因此对于Pt基改性催化剂的研究具有更重要的现实意义. 对于催化剂而言, 其微观电子结构以及能级密度分布很大程度上决定着催化剂的本征催化活性. 因此通过对其宏观特性的调控以改变Pt的微观结构, 是提高Pt基催化剂催化活性的有力方向. 本文着重从催化剂的组成、形貌和粒度等方面就近几年对Pt基催化剂的改性研究进行了综述, 并对其改性机理进行了相关讨论.

关键词: 直接甲醇燃料电池, Pt基催化剂, 协同效应, 电子效应, 溢流效应

In the past decades, fuel cells have emerged as an ideal device for energy storage and conversion owing to their high-energy conversion efficiency and low pollutant emission. Among various fuel cells, direct methanol fuel cells (DMFCs) appear to be one of the most promising systems because of their low operating temperatures, high energy density and easy transportation. However, it is known that the widespread commercial application of these cells is hindered by the high cost due to the exclusive use of platinum and platinum alloy catalysts. Thus, it is of great scientific and practical importance to exploit relatively inexpensive and highly active electrocatalysts for methanol oxidation. Although the utilization of non-noble catalysts may bring cost reduction to a certain degree, the excessively low performance is far below the commercial standard. Additionally, the formation and accumulation of intermediate species, such as COad and CHOad, which strongly adsorbed on the Pt surface, can substantially limit the efficience of the catalyst. Two main mechanisms are widely accepted to explain this improved tolerance to CO. As to the bifunctional mechanism model, a second metal can provide oxygenated species at lower potentials for oxidative removal of adsorbed CO. According to the intrinsic or ligand mechanism, the integrated metal modifies the electronic structure of Pt atoms, lowering the adsorption energy of COads and facilitating the oxidation of COads at a lower potential. Therefore, it seems that the modification or optimization based on monometallic Pt catalyst may be more practical. To our best understanding, the macroscopic structure of the catalyst plays a significant role in determining its intrinsic electronic construction. Hence, it is reasonable to improve the performance of the catalyst through monitoring its macroscopic properties to change the microscopic structure. In this paper, recent research progresses on the various approaches for the performance elevation of the anode catalyst have been summarized, mainly focusing on the composition, the morphology and the granularity. Especially the modification mechanisms have also been discussed.

Key words: direct methanol fuel cell, Pt based catalyst, synergistic effect, electronic effect, spillover effect