多级孔结构Ni-Zn/N,S-rGO催化剂的可控构筑及其肼氧化机理研究

Direct hydrazine fuel cell (DHFC) is a kind of environmental friendly power generation technology, which has high energy density, however its application is inhibited by the high cost and short service life of the catalyst for hydrazine oxidation reaction (HzOR). To solve these problems, a novel idea and a new method are proposed to prepare low cost and high performance HzOR catalyst...In this project, we plan to design and prepare a novel Ni-Zn catalyst with superaerophobic surface and hierarchically porous structure by the combined bubble dynamic template method during electrodeposition and subsequent delloying of Zn. The attention will be paid to identify the electrodeposition and etching parameters with controllable structure and composition, and to propose the kinetic model for the macroporous Ni-Zn alloy co-deposition. The hydrothermal method is used to synthesize the nitrogen and sulfur co-doped three-dimensional graphene (N,S-rGO), which is suitable to load Ni-Zn alloy. Then, the novel Ni-Zn/N,S-rGO catalyst is obtained. The attention will be paid to clarify the synergistic mechanism between N,S-rGO and Ni-Zn alloy, to reveal the catalytic mechanism towards hydrazine electrooxidation, and to investigate the relationship between the structure and properties of Ni-Zn/N,S-rGO systematically. On this basis, the single fuel cell will be assembled, and the HzOR performance of Ni-Zn/N,S-rGO catalyst will be further evaluated by the single fuel cell tests...The implementation of this project will provide the theoretical basis for the preparation and application of non-precious metal hydrazine oxidation catalysts, moreover, contribute somewhat to the development of the electrochemical catalytic theory.

直接肼燃料电池（DHFC）是一种能量密度高、环境友好的发电技术，但其应用受到肼氧化催化剂成本高和寿命短的制约。针对这一问题，本项目提出了一种制备低成本、高性能肼氧化催化剂的新思路和新方法。.本项目拟采用电沉积过程中气泡模板法结合去合金化方法，可控构筑具有疏气性表面的多级孔结构Ni-Zn合金，确定结构与组成可控的电沉积及浸蚀工艺参数，提出大孔Ni-Zn合金共沉积动力学模型；采用水热法制备适合于担载Ni-Zn合金的氮硫共掺杂三维石墨烯（N,S-rGO），得到新型Ni-Zn/N,S-rGO催化剂；揭示Ni-Zn/N,S-rGO催化剂的肼氧化机理，系统研究催化剂结构与性能之间的构效关系。在此基础上，组装单体电池，进行单电池性能测试。.本项目的研究为非贵金属肼氧化催化剂的制备及应用提供理论基础，对发展电催化理论具有重要意义。

直接肼燃料电池（DHFC）具有较高的能量密度和理论电压，反应条件温和，被成为是最具应用前景的液体燃料电池之一。肼氧化反应（HzOR）是直接肼燃料电池的核心反应过程，但对贵金属催化剂的依赖已成为制约燃料电池发展的瓶颈。针对这一问题，本项目取得结果如下：1）成功制备得到多级孔结构Ni-Zn合金催化剂，明确了其最佳电沉积和去合金化工艺路径和参数，在一定程度上可以替代贵金属Pt等，作为肼氧化反应的电催化剂；2）制备得到了少层的氮掺杂三维石墨烯，随后得到了氮硫共掺杂三维石墨烯(N,S-rGO)，并在此基础上结合量子化学计算，明确了Ni-Zn合金催化剂的肼氧化机理；3）以氮硫共掺杂三维石墨烯为基体，制备得到Ni-Zn/N,S-rGO电催化剂，用作肼氧化反应电催化剂，表现出优异的肼氧化活性和稳定性，并对Ni-Zn和N,S-rGO的协同作用进行了研究。本项目的顺利完成，达到了替代贵金属催化剂用于肼氧化反应、降低生产成本的目的，对燃料电池电催化剂的设计合成及相关机理研究具有重要意义。