Abstract
Developing low-cost, high-performance electrocatalysts for the oxygen reduction reaction (ORR) is crucial for implementation of fuel cells and metal-air batteries into practical applications. Graphene-based catalysts have been extensively investigated for ORR in alkaline electrolytes. However, their performance in acidic electrolytes still requires further improvement compared to the Pt/C catalyst. Here we report a self-templating approach to prepare graphene-based sandwich-like porous carbon nanosheets for efficient ORR in both alkaline and acidic electrolytes. Graphene oxides were first used to adsorb m-phenylenediamine molecules which can form a nitrogen-rich polymer network after oxidative polymerization. Then iron (Fe) salt was introduced into the polymer network and transformed into ORR active Fe–N–C sites along with Fe, FeS, and FeN0.05 nanoparticles after pyrolysis, generating ORR active sandwich-like carbon nanosheets. Due to the presence of multiple ORR active sites. The as-obtained catalyst exhibited prominent ORR activity with a half-wave potential ∼30 mV more positive than Pt/C in 0.1 mol L−1 KOH, while the half-wave potential of the catalyst was only ∼40 mV lower than that of commercial Pt/C in 0.1 mol L−1 HClO4. The unique planar sandwich-like structure could expose abundant active sites for ORR. Meanwhile, the graphene layer and porous structure could simultaneously enhance electrical conductivity and facilitate mass transport. The prominent electrocatalytic activity and durability in both alkaline and acidic electrolytes indicate that these carbon nanosheets hold great potential as alternatives to precious metal-based catalysts, as demonstrated in zinc-air batteries and proton exchange membrane fuel cells.
摘要
开发低成本, 高性能氧还原反应(ORR)电催化剂对于燃料电池和金属空气电池的规模化应用至关重要. 基于石墨烯的碳催化剂已经被广泛用于碱性电解质中的ORR. 然而, 与Pt/C催化剂相比, 石墨烯基催化剂在酸性电解质中的性能仍然需要进一步提升. 在这个工作中, 我们发展了一种非常高效的模板方法来制备基于石墨烯的具有三明治结构的多孔碳纳米片电催化剂, 其在碱性和酸性电解质中均具有非常好的ORR催化性能. 首先, 被氧化石墨烯吸附的苯二胺分子通过氧化聚合形成富氮聚合物网络, 接着铁(Fe)盐被吸附到聚合物网络中, 并且在热解之后形成ORR活性位点Fe-N-C以及Fe, FeS和FeN0.05纳米颗粒, 最终得到类似三明治结构的碳纳米片ORR电催化剂. 由于这种结构中存在较高密度的ORR活性位点, 所获得的催化剂显示出非常高效的ORR活性, 在0.1 mol L-1 KOH中半波电位比Pt/C高30 mV. 更重要的是, 在0.1 mol L-1 HClO4中, 催化剂的半波电位仅比Pt/C低约40 mV. 这种独特的平面三明治结构可以在催化反应中暴露出丰富的ORR活性位点, 同时, 石墨烯层和多孔结构可以提高电导率以及促进传质, 这两者对于实现高活性ORR催化至关重要. 在碱性和酸性条件中, 突出的电催化活性和耐久性表明这些碳纳米片作为贵金属基ORR催化剂的替代物具有很大的潜力, 优秀的锌空气电池和质子交换膜燃料电池性能直接证实这种材料在实际电化学能源转化装置中也非常有应用前景.
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Acknowledgements
This work was supported by the National Basic Research Program of China (973 Program, 2015CB351903), the National Key Research and Development Program (2017YFA0207301), the National Natural Science Foundation of China (51402282, 21474095 and 21476104), CAS Key Research Program of Frontier Sciences (QYZDB-SSW-SLH018), and the Fundamental Research Funds for the Central Universities.
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Tao Wang received his BSc degree from Hefei University of Technology in 2015. He is currently a PhD candidate in the Department of Polymer Science and Engineering, University of Science and Technology of China. His current research is developing functional polymers for flexible energy devices.
Jianguo Liu received his PhD degree from Dalian Institute of Chemical Physics in China. Then he worked as post-doc in Hong Kong University of Science and Technology and University of Newcastle upon Tyne in UK. He joined Nanjing University as an associate professor in 2007, and become a professor in 2013. His research now focuses on fuel cells and Li-ion batteries.
Hangxun Xu received his BSc degree from University of Science and Technology of China and PhD in Materials Chemistry from the University of Illinois at Urbana-Champaign. Thereafter, he was a Postdoctoral Research Associate with Prof. John Rogers. He came back to the USTC as a Professor in 2013 through the “National 1000 Young Talents” program. His current research focuses on developing functional polymers for applications in energy conversion and flexible electronics.
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Wang, T., Wang, J., Wang, X. et al. Graphene-templated synthesis of sandwich-like porous carbon nanosheets for efficient oxygen reduction reaction in both alkaline and acidic media. Sci. China Mater. 61, 915–925 (2018). https://doi.org/10.1007/s40843-017-9191-5
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DOI: https://doi.org/10.1007/s40843-017-9191-5