ＭＯＦを基盤としたカーボンアロイ触媒および高性能非白金燃料電池の設計・開発

MOF基碳合金催化剂及高性能非铂燃料电池的设计与开发

• 批准号: 15F15377
• 负责人: 山口 猛央
• 金额: $ 1.54万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for JSPS Fellows
• 财政年份: 2015
• 资助国家: 日本
• 起止时间: 2015-11-09 至 2018-03-31
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15F15377/
• 关键词: Solid Alkaline Fuel Cell; Oxygen Reduction; Metal Organic Framework; Electrocatalyst; ZIF; Fuel Cell; Pt-Free Catalysts; Imidazolate Framework

Development of cost-effective electrocatalyst for oxygen reduction reaction (ORR) for low-temperature fuel cells (Solid proton/alkaline conducting membrane fuel cells) is one of the major priority research worldwide. In the present case, we have synthesized trimetallic zeolitic imidazole framework (t-ZIF) and used it as a single precursor for the preparation of the precious metal-free catalyst. t-ZIF contain Co, Fe, and Zn as metal centres and 2-methylimidazole as a ligand. During carbonization, t-ZIF produces nitrogen and Fe/Co-Nx doped carbon/ carbon nanotubes alloyed with metal/metal oxide particles encased inside the carbon structures (FeCo-NCZ). Since the electrocatalyst developed from a single precursor, a uniform distribution of active reaction centres (Fe-Nx, Co-Nx, pyridinic/graphitic coordinated nitrogen, etc.) on the surface of the electrocatalyst is obtained. Highly porous nature of the carbon achieved by the leaching-out of Zn at high temperature. The peculiar morphology and reasonably good surface area assist better mass transport and fast electron transport. ORR performance of FeCo-NCZ in alkaline (0.1 M KOH) condition shows the onset potential and half-wave potential of 1.04 V and 0.91 V vs. RHE respectively, which is more positive to commercial Pt/C catalyst. FeCo-NCZ reduces oxygen molecule through direct 4 e- pathways and shows reaction kinetic similar to Pt/C. More importantly, FeCo-NCZ displays high fuel tolerance and electrochemical stability in alkaline condition even at 60 oC. Our study shows FeCo-NCZ is a suitable alternative to Pt/C.

低温燃料电池（Solid Proton/Alkaline Conductive Membrane Fuel Cells，简称SOFC）中氧还原反应（ORR）电催化剂的开发是目前国内外研究的重点之一。在这种情况下，我们合成了三金属沸石咪唑框架（t-ZIF），并将其用作制备无贵金属催化剂的单一前体。t-ZIF含有Co、Fe和Zn作为金属中心和2-甲基咪唑作为配体。在碳化过程中，t-ZIF产生氮和Fe/Co-Nx掺杂的碳/碳纳米管，其与包裹在碳结构内的金属/金属氧化物颗粒合金化（FeCo-NCZ）。由于电催化剂由单一前体形成，因此活性反应中心（Fe-Nx，Co-Nx，吡啶/石墨配位氮等）的均匀分布是可能的。在电催化剂的表面上获得。通过在高温下除去Zn而获得的碳的高度多孔性。独特的形态和相当好的表面积有助于更好的质量传输和快速的电子传输。FeCo-NCZ在碱性（0.1M KOH）条件下的ORR性能显示起始电位和半波电位分别为1.04 V和0.91 V（相对于RHE），这比商业Pt/C催化剂更积极。FeCo-NCZ通过直接4 e-途径还原氧分子，并显示出与Pt/C类似的反应动力学。更重要的是，FeCo-NCZ在碱性条件下，即使在60 oC下也显示出高的燃料耐受性和电化学稳定性。我们的研究表明FeCo-NCZ是Pt/C的合适替代物。

项目成果

Carbon alloy electrocatalysts derived from metal organic framework for oxygen reduction reaction

用于氧还原反应的金属有机骨架碳合金电催化剂

• 发表时间: 2016
• 作者: SREEKUTTAN M. Unni;G.M. Anilkumar;M. Matsumoto;T. Tamaki;T. Yamaguchi
• 通讯作者: T. Yamaguchi

Metal organic framework derived dual metal co-doped porous carbon for oxygen reduction reaction in alkaline condition

金属有机骨架衍生的双金属共掺杂多孔碳用于碱性条件下的氧还原反应

• 发表时间: 2016
• 作者: Alaa El-Din H. Sayed;SREEKUTTAN M. Unni
• 通讯作者: SREEKUTTAN M. Unni

Direct synthesis of a carbon nanotube interpenetrated doped porous carbon alloy as a durable Pt-free electrocatalyst for the oxygen reduction reaction in an alkaline medium

• DOI: 10.1039/c7se00249a
• 发表时间: 2017-08
• 期刊: Sustainable Energy and Fuels
• 影响因子: 5.6
• 作者: Sreekuttan M. Unni;G. Anilkumar;M. Matsumoto;Takanori Tamaki;H. Imai;Takeo Yamaguchi