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Bimetal-organic framework-derived carbon nanocubes with 3D hierarchical pores as highly efficient oxygen reduction reaction electrocatalysts for microbial fuel cells

双金属有机骨架衍生的3D等级孔结构纳米立方碳在微生物燃料电池中的应用

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Abstract

Noble metal-free and highly efficient electro-catalytic materials with hierarchically porous structures continue to be studied for the oxygen reduction reaction (ORR) in microbial fuel cells (MFCs). We report bimetal-organic framework (bi-MOF)-derived nanocubic Swiss cheese-like carbons with a novel three-dimensional hierarchically porous structure (3D Co-N-C) prepared by utilizing cetyltrimethylammonium bromide (CTAB) as a structure-directing agent to control the formation of a nanocubic skeleton, and silica spheres as a template to form a mesoporous structure. The elemental composition and chemical morphology of this material can be tuned through the Zn/Co ratio to optimize its ORR catalytic activity. The optimized 3D Co-N-C displays excellent ORR catalytic performance (half-wave potential as high as 0.754 V vs. reversible hydrogen electrode and diffusion-limiting current density of 5.576 mA cm−2) in 0.01 mol L−1 phosphate-buffered saline (PBS electrolyte), showing it can compete with the commercial 20 wt% Pt/C catalysts. The catalytic capability and long-term durability of 3D Co-N-C as an air-filled cathode electrocatalyst in an MFC device are tested, showing that the 3D CoNC-MFC can reach a high power density of 1257 mW m−2 and provide a competitive voltage during a periodic feeding operation for 192 h; these values are much higher than those of the Pt/C-MFC.

摘要

多级孔结构的非贵金属高性能催化剂在微生物燃料电池(MFC)氧化还原反应(ORR)中的应用, 是近年来备受关注的话题.在此, 我们报道了一种在双金属MOFs中衍生出的奶酪状三维多级孔结构立方碳材料. 该材料通过十六烷基三甲基溴化铵(CTAB)作为结构导向剂来控制形成纳米立方骨架, 同时采用二氧化硅微球作模板形成介孔结构, 并通过调节双金属MOFs的Co/Zn比例来优化材料的物理化学性质, 从而提升催化剂的ORR电化学性能. 经过优化的3D Co-N-C在中性0.01 mol L−1 磷酸盐缓冲液电解质中具有优异的ORR催化性能(相对于可逆氢电极的半波电势高达0.754 V,扩散极限电流密度为5.576 mA cm−2), 可与商用20 wt% Pt/C的催化性能相匹敌. 同时, 这种催化剂与Pt/C相比具有更长的寿命. 将三维多级孔材料(3D CoNC-MFC)作为MFC装置中阴极的催化剂, 测试了其功率密度和长期耐用性, 结果表明3D CoNC-MFC能到达1257 mW m−2的高功率密度, 并且在192 h的常规加料操作下仍然保持较高的电压, 性能远高于Pt/C-MFC.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (51976143), the National Key Research and Development Program of China (2018YFA0702001), and Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory (XHD2020-002).

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Authors and Affiliations

  1. Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Xianhu Hydrogen Valley, Foshan, 528200, China

    Neng Chen  (陈能), Zihan Meng  (孟子寒) & Haolin Tang  (唐浩林)

  2. State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan, 430070, China

    Neng Chen  (陈能), Zihan Meng  (孟子寒), Rui Wang  (王锐), Shichang Cai  (蔡世昌), Weibin Guo  (郭伟斌) & Haolin Tang  (唐浩林)

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  1. Neng Chen  (陈能)
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Contributions

Tang H conceived the idea of the subject and supervised the progress of the research. Chen N performed the experiments with support from Meng Z, Wang R, Cai S, and Guo W. Chen N wrote the manuscript, and Tang H revised the manuscript. All authors contributed to the general discussion.

Corresponding author

Correspondence to Haolin Tang  (唐浩林).

Additional information

Neng Chen obtained his bachelor’s degree from Guangdong University of Petroleum and Chemical Technology in 2015. He obtained a master’s degree from China University of Petroleum, Beijing in 2018. And he has been a scientific research assistant at the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing at Wuhan University of Technology until now. His research interests focus on electrocatalysts, fuel cells and metal-air batteries.

Haolin Tang earned his PhD degree in materials science from Wuhan University of Technology in 2007. Then he worked as a research fellow at Nanyang Technological University for one year, and in 2011 he was appointed as a full professor of the State Key Laboratory of Advanced Technology for Materials Synthesis and Processing at Wuhan University of Technology. His research interests include fuel cells, electrochemistry of nanomaterials, and self-assembly of nanocomposites.

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The authors declare that they have no conflict of interest.

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Supporting data are available in the online version of the paper.

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40843_2021_1700_MOESM1_ESM.pdf

Bimetal-organic framework-derived carbon nanocubes with 3D hierarchical pores as highly efficient oxygen reduction reaction electrocatalysts for microbial fuel cells

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Chen, N., Meng, Z., Wang, R. et al. Bimetal-organic framework-derived carbon nanocubes with 3D hierarchical pores as highly efficient oxygen reduction reaction electrocatalysts for microbial fuel cells. Sci. China Mater. 64, 2926–2937 (2021). https://doi.org/10.1007/s40843-021-1700-5

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