二硫化钼-还原氧化石墨烯复合材料用作高稳定性燃料电池阴极催化剂载体

doi:10.1016/S1872-2067(19)63365-6

催化学报 ›› 2019, Vol. 40 ›› Issue (8): 1160-1167.DOI: 10.1016/S1872-2067(19)63365-6

二硫化钼-还原氧化石墨烯复合材料用作高稳定性燃料电池阴极催化剂载体

Muhammad Tuoqeer Anwar^a,b, 闫晓晖^a, Muhammad Rehman Asghar^a, Naveed Husnain^c, 沈水云^a, 罗柳轩^a, 程晓静^a, 魏光华^d, 章俊良^a

a 上海交通大学机械与动力工程学院, 动力机械与工程教育部重点实验室, 燃料电池研究所, 上海 200240, 中国;
b COMSATS信息技术学院, 旁遮普 57000, 巴基斯坦;
c 上海交通大学机械与动力工程学院, 热能工程研究所, 上海 200240, 中国;
d 上海交通大学, 上海交大-巴黎高科卓越工程师学院, 上海 200240, 中国

收稿日期:2019-03-13 修回日期:2019-04-01 出版日期:2019-08-18 发布日期:2019-06-21
通讯作者: 章俊良
基金资助:
国家重点研发计划（2016YFB0101201）；国家自然科学基金（21706158，21533005）.

MoS₂-rGO hybrid architecture as durable support for cathode catalyst in proton exchange membrane fuel cells

Muhammad Tuoqeer Anwar^a,b, Xiaohui Yan^a, Muhammad Rehman Asghar^a, Naveed Husnain^c, Shuiyun Shen^a, Liuxuan Luo^a, Xiaojing Cheng^a, Guanghua Wei^d, Junliang Zhang^a

a Institute of Fuel Cells, School of Mechanical Engineering, MOE Key Laboratory of Power and Machinery Engineering, Shanghai Jiao Tong University, Shanghai 200240, China;
b COMSATS University Islamabad(Sahiwal Campus), Off G. T. Rd., Sahiwal, Punjab 57000, Pakistan;
c Institute of Thermal Energy Engineering, School of Mechanical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China;
d SJTU-ParisTech Elite Institute of Technology, Shanghai Jiao Tong University, Shanghai 200240, China

Received:2019-03-13 Revised:2019-04-01 Online:2019-08-18 Published:2019-06-21
Supported by:
This work was financially aided by the National Key R&D Program of China (2016YFB0101201) and the National Natural Science Foundation of China (21706158, 21533005).

摘要/Abstract

摘要： 碳黑是质子交换膜燃料电池中最常用的电催化剂载体材料.然而，由于燃料电池内部环境苛刻（强酸性、强氧化性、湿度大、温度高、电位高等），碳材料易被氧化腐蚀，同时还可能进一步引起Pt催化剂颗粒脱落和团聚，造成催化剂性能衰减，继而影响电池性能与稳定性.为了克服碳载体腐蚀的问题，提高碳材料的石墨化程度是一种可行方法，然而，石墨化程度提高的同时伴随着含氧官能团的减少，这减少Pt离子的沉积位点，造成Pt团聚和颗粒过大等问题，导致催化剂质量比活性过低.另一种方法是开发金属氧化物（WO₃，TiO₂）、金属氮化物（Mo₂N，CrN）、金属碳化物（WC）和导电聚合物（PANI）等非碳载体.然而，这些载体材料的电导率远低于碳，造成催化剂活性较低，只适用于高温和使用强氧化剂（如纯氧、双氧水）等特殊工况.针对上述问题，本文设计合成了二硫化钼-还原氧化石墨烯（MoS₂-rGO）复合材料作为燃料电池阴极催化剂的载体材料，利用MoS₂的高稳定性及还原氧化石墨烯优异的导电性能与适量的含氧官能团，实现了Pt颗粒的均匀沉积并提高了催化剂活性与稳定性.
XRD表征结果显示，使用溶剂热法制备的复合材料同时具有石墨烯与二硫化钼的特征峰，证实MoS₂-rGO成功合成.XPS结果进一步证实了六价钼向四价钼及氧化石墨烯向还原氧化石墨烯的转变.TEM与HRTEM显示，MoS₂以多层形式存在并成功沉积在rGO表面，和rGO相互搭接形成了连续的电子传输网络，保证了载体良好的导电能力.使用改进的乙二醇还原法制得MoS₂-rGO负载Pt催化剂（Pt/MoS₂-rGO），TEM显示Pt颗粒均匀分布在载体表面，且Pt颗粒平均粒径为3.2nm.这主要归功于MoS₂充分暴露的活性边缘及rGO表面存在的适量含氧官能团为Pt离子提供了充足的沉积位点.电化学测试显示，在催化ORR反应中，Pt/MoS₂-rGO相比于碳载铂（Pt/C）具有更高的起始还原电位，表明MoS₂-rGO载体有助于Pt催化剂活性的提升.此外，经历10000圈加速衰减循环后，Pt/C电化学活性面积损失57.6%.相比之下，Pt/MoS₂-rGO活性面积损失为46.2%.同时，衰减后Pt/MoS₂-rGO半波电位高于Pt/C，进一步确认基于复合载体的Pt催化剂具有更好的稳定性.

关键词: 燃料电池, 复合催化剂载体, 碳腐蚀, 负载型催化剂, Pt电催化剂

Abstract: Carbon black is utilized as a conventional electrocatalyst support material for proton exchange membrane fuel cells. However, this support is prone to corrosion under oxidative and harsh environments, thus limiting the durability of the fuel cells. Meanwhile, carbon corrosion would also weaken the linkage between Pt and the support material, which causes Pt agglomeration, and consequently, deterioration of the cell performance. To overcome the drawbacks of a Pt/C electrocatalyst, a hybrid support material comprising molybdenum disulfide and reduced graphene oxide is proposed and synthesized in this study to exploit the graphitic nature of graphene and the availability of the exposed edges of MoS₂. TEM results show the uniform dispersion of Pt nanoparticles over the MoS₂-rGO surface. Electrochemical measurements indicate higher ECSA retention and better ORR activity after 10000 potential cycles for Pt/MoS₂-rGO as compared to Pt/C, demonstrating the improved durability for this hybrid support material.

Key words: Fuel cell, Hybrid catalyst support, Carbon corrosion, Supported catalyst, Pt-based electrocatalyst

Muhammad Tuoqeer Anwar, 闫晓晖, Muhammad Rehman Asghar, Naveed Husnain, 沈水云, 罗柳轩, 程晓静, 魏光华, 章俊良. 二硫化钼-还原氧化石墨烯复合材料用作高稳定性燃料电池阴极催化剂载体[J]. 催化学报, 2019, 40(8): 1160-1167.

Muhammad Tuoqeer Anwar, Xiaohui Yan, Muhammad Rehman Asghar, Naveed Husnain, Shuiyun Shen, Liuxuan Luo, Xiaojing Cheng, Guanghua Wei, Junliang Zhang. MoS₂-rGO hybrid architecture as durable support for cathode catalyst in proton exchange membrane fuel cells[J]. Chinese Journal of Catalysis, 2019, 40(8): 1160-1167.

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二硫化钼-还原氧化石墨烯复合材料用作高稳定性燃料电池阴极催化剂载体

MoS₂-rGO hybrid architecture as durable support for cathode catalyst in proton exchange membrane fuel cells

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二硫化钼-还原氧化石墨烯复合材料用作高稳定性燃料电池阴极催化剂载体

MoS2-rGO hybrid architecture as durable support for cathode catalyst in proton exchange membrane fuel cells

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MoS₂-rGO hybrid architecture as durable support for cathode catalyst in proton exchange membrane fuel cells