碱性溶液中不同微观结构的Fe-N/C催化剂氧还原性能的稳定性对比研究

Durability of Fe-N/C Catalysts with Different Nanostructures for Electrochemical Oxygen Reduction in Alkaline Solution

Fe-N/C催化剂在氧还原反应中的作用机理对于开发高效、可持续使用的非贵金属催化剂在聚合物电解质膜燃料电池中的应用至关重要,但目前仍存在很多的难以攻克的问题。为了揭示纳米结构与电化学活性的关系,本研究开发了一种具有高电化学活性的Fe-N/C氧还原催化剂,该催化剂含有Fe-Nx位点和被氮掺杂的碳纳米管包裹的Fe/Fe3C纳米晶体两种具有氧还原反应电化学活性的纳米结构。尽管不含贵金属铂,本研究合成的Fe-N/C催化剂在碱性条件下仍显示出较高的ORR活性,半波电势为0.86 V(vs RHE),质量活性为18.84 A/g(0.77 V(vs RHE),极限电流密度为–4.3 mA·cm–2。同时,电子转移数为3.7(0.2 V(vs RHE),说明Fe-N/C催化剂中4电子ORR反应的比例较高。石墨烯包覆的金属Fe/Fe3C纳米晶生长N-CNTs后,材料的导电性有所提高,并且Fe-Nx活性位点在Fe/Fe3C纳米颗粒表面分布均匀,改善了材料的电化学活性。本研究为非贵金属氧还原电催化剂的继续深入研究以及广泛应用于商业化生产提供了一定的借鉴和依据。

The mechanism of Fe-N/C catalysts in oxygen reduction reactions is critical to the development of efficient, sustainable non-noble metal catalysts in polymer electrolyte membrane fuel cells, but it is still in controversy. In order to understand the relationship between composition and the nanostructure of material and the electrochemical activity, this study developed a type of Fe-N/C catalyst with high electrochemical activity, which contained Fe-Nx active sites and Fe/Fe3C nanocrystals encapsulated with nitrogen-doped carbon nanotubes. Despite being free of precious metals, the as-prepared catalyst displays high oxygen reduction reactions(ORR) activity in alkaline medium with the half-wave potential of 0.86 V(vs RHE), the mass activity of 18.84 A/g at 0.77 V(vs RHE), and the maximum current density of –4.3 mA·cm–2. Meanwhile, the electron transfer number is 3.7 at 0.2 V(vs RHE), revealing that the 4-electron ORR reaction exists in the catalyst. The excellent electrochemical activity is attributed to the graphene-encapsulated metallic Fe/Fe3C nanocrystals which improves the conductivity after the growth of N-doped carbon nanotubes, and the relatively high proportion of Fe-Nx active sites distributed on the surface of Fe/Fe3C nanoparticles. This study provides a certain reference and basis for the further study of non-noble metal catalyst and their wide application in commercial production.