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Porous nitrogen/halogen dual-doped nanocarbons derived from imidazolium functionalized cationic metal-organic frameworks for highly efficient oxygen reduction reaction

咪唑鎓盐官能化阳离子型金属-有机框架衍生的多孔氮/卤素双掺杂纳米碳高效氧还原催化剂

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Abstract

Heteroatom-doped carbon materials as alternative catalysts for oxygen reduction reaction (ORR) have drawn increasing attention due to their tunable chemical and electronic structures for achieving high activity and stability. However, there still remains a great challenge to fabricate porous heteroatoms dual-doped carbons with uniformly doping in a facile and controllable way. Herein, imidazole/imidazolium-functionalized metal-organic frameworks (MOFs) are employed as precursors and templates to achieve porous nitrogen and halogen dual-doped nanocarbons. Among these carbon materials, the as-prepared nitrogen/bromine dual-doped catalyst BrNC-800 exhibits the best ORR performance with a positive half-wave potential at 0.80 V (vs. RHE) in 0.1 mol L−1 KOH, which is comparable to the benchmark commercial 20 wt% Pt/C catalyst. BrNC-800 shows excellent long term stability and methanol tolerance. This work provides a facile approach to fabricate highly efficient heteroatoms dual-doped carbon catalysts for energy conversion.

摘要

低成本、高效稳定的非金属材料作为氧还原反应(ORR)的电催化剂对于燃料电池的规模化应用至关重要. 杂原子掺杂的多孔碳材料具有可调的化学组成和电子结构, 能显著提升氧还原催化活性. 基于此, 我们采用咪唑鎓盐功能化的金属-有机框架(MOFs)作为前驱体 和自牺牲模板, 制备了氮和卤素双掺杂多孔纳米碳催化剂. 其中氮/溴双掺杂催化剂BrNC-800在碱性条件下具有优异的电催化性能、稳定 性和抗甲醇毒化能力. 其优异的电催化活性归因于: (1) 大量吡啶氮和石墨氮的掺杂产生丰富的碳活性位点, 同时高的石墨化程度有助于 提高导电性, 促进氧还原活性; (2) 溴的存在改变了催化剂的化学组分和结构特征, 并活化相邻碳产生额外活性位点; (3) 高比表面和多级 孔结构有助于传质与增加暴露的氧还原活性位的数量, 而提高催化效率. 这项工作为以MOFs为前驱体制备高效的杂原子双掺杂碳材料提供了一种简便的方法.

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Acknowledgements

We acknowledge the financial support from the National Key Research and Development Program of China (2018YFA0208600), National Basic Research Program of China (973 Program, 2014CB845605), Key Research Program of Frontier Science, Chinese Academy of Sciences (QYZDJ-SSW-SLH045), Strategic Priority Research Program of the Chinese Academy of Sciences (XDB20000000), National Natural Science Foundation of China (21671188, 21871263, 21521061 and 21331006) and Youth Innovation Promotion Association, Chinese Academy of Sciences (2014265).

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Authors and Affiliations

  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, China

    Qiao Wu  (伍巧), Jun Liang  (梁均), Jun-Dong Yi  (伊俊东), Peng-Chao Shi  (石鹏超), Yuan-Biao Huang  (黄远标) & Rong Cao  (曹荣)

  2. College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, 350007, China

    Qiao Wu  (伍巧)

  3. University of Chinese Academy of Sciences, Beijing, 100049, China

    Rong Cao  (曹荣)

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  1. Qiao Wu  (伍巧)
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  2. Jun Liang  (梁均)
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  3. Jun-Dong Yi  (伊俊东)
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  4. Peng-Chao Shi  (石鹏超)
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Correspondence to Yuan-Biao Huang  (黄远标) or Rong Cao  (曹荣).

Additional information

Qiao Wu received her bachelor’s degree from the School of Chemistry and Chemical Engineering, Henan Normal University in 2016. She is currently a master candidate in the College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, China. Her current research interests focus on designing high-performance electrode materials for energy storage systems.

Yuan-Biao Huang obtained his PhD in 2009 under the supervision of Prof. GX Jin from Fudan University. In the same year, he joined Prof. Rong Cao’s group at Fujian Institute of Research on the Structure of Matter (FJIRSM), Chinese Academy of Sciences (CAS). In 2014, he joined Prof. Qiang Xu’s group at the National Institute of Advanced Industrial Science and Technology as a JSPS (Japan Society for the Promotion of Science) fellow. In 2015, he moved back to Prof. Cao’s research group at FJIRSM. His research interest focuses on porous MOF and COF based materials for catalysis.

Rong Cao was born in Fujian province, China. He obtained his PhD from FJIRSM, CAS, in 1993. Following post-doctoral experience in the Hong Kong Polytechnic University and JSPS Fellowship in Nagoya University, he became a professor at FJIRSM in 1998. Now, he is the director of FJIRSM. His main research interests include supramolecular chemistry, inorganic–organic hybrid materials and nanocatalysis.

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Porous nitrogen/halogen dual-doped nanocarbons derived from imidazolium functionalized cationic metal-organic frameworks for highly efficient oxygen reduction reaction

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Wu, Q., Liang, J., Yi, JD. et al. Porous nitrogen/halogen dual-doped nanocarbons derived from imidazolium functionalized cationic metal-organic frameworks for highly efficient oxygen reduction reaction. Sci. China Mater. 62, 671–680 (2019). https://doi.org/10.1007/s40843-018-9364-5

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