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Nitrogen-carbon-encapsulated Fe3C nanoparticles as highly efficient earth-abundant oxygen reduction electrocatalysts

氮碳包封Fe3C纳米颗粒作为高效富氧还原电催化剂

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Abstract

The design and synthesis of the highly active metal-organic framework (MOF)-based catalysts open new avenues to facilitate the kinetically unfavorable oxygen reduction reaction (ORR). In this paper, we elucidate the design and fabrication of an efficient electrocatalyst with a novel structure for the enhancement of the ORR performance by decorating the surface of the ZIF-8 precursor with ferrocene formic acid, followed by a two-step carbonization process, which is critical for the encapsulation of pyrolytic Fe3C nanoparticles (NPs) into carbon nanotubes (CNTs) and the isolation of Fe single atoms onto an N-doped carbon (NC) matrix. Moreover, the relative Fe content is vital to optimize the ORR performance of the catalysts. The resulting Fe3C@CNT/NC-M catalyst has an optimized structure. It shows great long-term stability and excellent electrocatalytic ORR performance in alkaline solution, with the half-wave potential and limiting current reaching 0.941 V and 6.31 mA cm−2, respectively. Furthermore, the electrocatalyst has a strong tolerance to and good stability in a methanol solution. The Fe3C@CNT/NC-M zinc-air battery delivers a large open-circuit potential of 1.525 V, a peak power density of 348 mW cm−2 at 420 mA cm−2, and a maximum capacity of 843 mA h gZn−1 at 10 mA cm−2. Thus, this synthetic strategy provides a promising pathway toward constructing MOF-based electrocatalytic materials with effective and stable ORR performance.

摘要

高活性MOF基催化剂的设计和合成为促进动力学不利的氧还原 反应(ORR)过程开辟了新的途径. 本研究通过在ZIF-8前驱体表面涂覆 二茂铁甲酸, 然后进行两步炭化工艺, 设计和制备了一种具有新型结构 的高效电催化剂, 以提高ORR性能. 两步炭化过程对于将热解Fe3C纳米 颗粒封装到碳纳米管(CNTs)中以及将Fe单原子隔离到N掺杂碳(NC)基 体上至关重要. 此外, Fe元素的相对含量对优化催化剂的ORR性能至关 重要. 所制得Fe3C@CNTs/NC-M催化剂结构先进, 在碱性溶液中表现出 良好的长期稳定性和电催化ORR性能, 其半波电位和极限电流分别达 到0.941 V和6.31 mA cm−2. 此外, 该电催化剂在甲醇溶液中具有较强的 耐受性和良好的稳定性. Fe3C@CNTs/NC-M锌空气电池(ZAB)具有 1.525 V的开路电位, 420 mA cm−2时的峰值功率密度为348 mW cm−2, 10 mA cm−2时的最大容量为843 mA h gZn−1. 因此, 这种合成策略为构 建具有有效和稳定的ORR性能的MOF基电催化材料提供了一条有效 途径.

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Acknowledgements

This work was supported by Anhui Provincial Natural Science Foundation (1908085J10), the National Natural Science Foundation of China (21671004), the Institute of Energy, Hefei Comprehensive National Science Center (21KZS216), and the Scientific Research Foundation for High-level Talents of Anhui University of Science and Technology (2022yjrc50).

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Authors and Affiliations

  1. School of Chemical Engineering, Anhui Province Key Laboratory of Specialty Polymers, Anhui University of Science and Technology, Huainan, 232001, China

    Cuiping Wang  (汪翠萍), Zhi Li  (李智), Jie Lei  (雷杰), Song Li  (李松) & Jinsong Hu  (胡劲松)

  2. Department of Chemistry, Energy Lancaster and Materials Science Lancaster, Lancaster University, Lancaster, LA1 4YB, UK

    Stijn F. L. Mertens

  3. Institute of Energy, Hefei Comprehensive National Science Center, Hefei, 230031, China

    Jinsong Hu  (胡劲松)

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  1. Cuiping Wang  (汪翠萍)
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  2. Zhi Li  (李智)
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Contributions

Author contributions Wang C performed experiments, analyzed data and wrote the original draft. Hu J carried out the administration of the project and provided supervision, review and editing of the paper. Li Z provided supervision, review and editing. Mertens SFL analyzed the data and revised the paper. Lei J and Li S performed data analysis. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Zhi Li  (李智), Stijn F. L. Mertens or Jinsong Hu  (胡劲松).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Cuiping Wang is a graduate student at the School of Chemical Engineering, Anhui University of Science and Technology (AUST). Her main research interest is the application of MOF materials and their derivatives in electrochemistry.

Zhi Li received a PhD degree in 2017 from the Department of Chemistry of KU Leuven under the supervision of Prof. Steven De Feyter and Prof. Stijn F. L. Mertens. Afterward, he joined Nanjing University as a postdoctoral fellow in 2019. He joined AUST in 2022 with research interests including the functionalization of 2D materials and electrocatalytic processes.

Stijn F. L. Mertens is a Professor of physical electrochemistry at Lancaster University, UK. He obtained a PhD degree in chemistry from Ghent University, Belgium, and a Habilitation in chemical physics from Vienna University of Technology, Austria. His research interests include in situ and in operando studies of well-defined electrochemical interfaces towards an atomic-scale understanding of catalysis, molecular self-assembly and single-molecule switching.

Jinsong Hu received his PhD degree in 2011. Then, he worked at AUST. After a postdoctoral career at AUST from November 2015 to August 2017, he began independent research as a Professor at AUST. His research interests include fluorescent sensors based on MOFs and MOFs-based nanomaterials.

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Wang, C., Li, Z., Lei, J. et al. Nitrogen-carbon-encapsulated Fe3C nanoparticles as highly efficient earth-abundant oxygen reduction electrocatalysts. Sci. China Mater. 67, 762–770 (2024). https://doi.org/10.1007/s40843-023-2768-3

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