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Encapsulated FeP nanoparticles with in-situ formed P-doped graphene layers: Boosting activity in oxygen reduction reaction

磷氮掺杂石墨烯层封装FeP纳米颗粒的增强ORR 催化性能

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Abstract

Nonprecious metal-based oxygen reduction reaction (ORR) electrocatalysts with high efficiency in both alkaline and acidic media are being intensively studied for the purpose of replacing expensive Pt-based catalysts; however, it is still a challenge to achieve superior ORR performances, especially in acidic media. Herein, by pyrolysis of mixed precursors of diammonium phosphate, melamine and hemin, we prepared a nanocomposite catalyst (denoted as FeP@PGL) composed of nitrogen-doped carbon nanosheets with embedded FeP nanoparticles (NPs), which were encapsulated by in-situ formed phosphorus-doped graphene layers. It is found that phosphorous was preferentially doped in the coating layers on FeP NPs, instead of in the carbon nanosheets. The FeP@PGL catalyst exhibited excellent ORR performance, with the onset and half-wave potential up to 1.01 and 0.90 V vs. the reversible hydrogen electrode (RHE) in alkaline media, and 0.95 and 0.81 V vs. RHE in acidic media, respectively. By thorough microscopy and spectroscopy characterizations, the interfacial charge transfer between the encapsulated FeP NPs and P-doped graphene layers was identified, and the local work function of the catalyst surface was also reduced by the interfacial interaction. The interfacial synergy between the encapsulated FeP and phosphorus-doped graphene layers was essential to enhance the ORR performance. This study not only demonstrates the promising ORR properties of the encapsulated-FeP-based nanocomposite catalyst, but also provides direct evidence of the interfacial charge transfer effect and its role in ORR process.

摘要

开发高效的非贵金属氧还原反应(ORR)催化剂来替代铂基 催化剂受到了广泛关注. 设计合成在碱性电解质和酸性电解质中 均表现出高催化活性的非贵金属催化剂仍然是一个挑战. 在本文 中, 我们通过前驱体热解法制备了一种纳米复合催化剂 (FeP@PGL), 该催化剂由氮掺杂的碳纳米片以及镶嵌在片层上的 磷掺杂石墨烯层封装磷化铁(FeP)纳米颗粒组成. FeP@PGL催化剂 表现出优异的ORR催化性能, 在碱性介质中的起始电位和半波电 势分别高达1.01 V 和0.90 V vs. RHE; 在酸性介质中的起始电位和 半波电势分别高达0.95 V和0.81 V vs. RHE. 通过详细的电子显微和 谱学表征, 我们发现碳纳米片基质与包裹纳米颗粒的碳包裹层存 在组成的差别, 磷掺杂主要发生在包裹FeP纳米颗粒的石墨烯层上. 封装的FeP纳米颗粒与外层磷掺杂石墨烯层之间存在界面电荷转 移, 并且通过界面相互作用降低了催化剂表面的功函数. FeP和磷 掺杂石墨烯层之间的界面协同作用对于增强催化剂ORR活性至关 重要. 本文不仅证明了封装型FeP基纳米复合催化剂在氧还原反应 上的应用价值, 而且为界面电荷转移效应及其在ORR过程中的作 用提供了实验证据.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21773128, 21534005, and 21421001).

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Authors and Affiliations

  1. Institute of New Catalytic Materials Science, School of Materials Science and Engineering, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai University, Tianjin, 300350, China

    Baoxia Ni  (倪保霞), Rui Chen  (陈睿), Luming Wu  (武鲁明) & Tiehong Chen  (陈铁红)

  2. Key Laboratory of Functional Polymer Materials (MOE), College of Chemistry, Nankai University, Tianjin, 300071, China

    Pingchuan Sun  (孙平川)

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  1. Baoxia Ni  (倪保霞)
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  2. Rui Chen  (陈睿)
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  5. Tiehong Chen  (陈铁红)
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Contributions

Ni B, Chen R and Wu L conducted the experiments. All authors contributed to experimental design, data analysis and interpretation. Ni B and Chen T wrote the manuscript.

Corresponding author

Correspondence to Tiehong Chen  (陈铁红).

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Conflict of interest

The authors declare no competing financial interests.

Supplementary information

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

Baoxia Ni received her PhD degree from Nankai University in 2020. Her research focuses on the design and synthesis of nanostructured carbon electrocatalysts.

Tiehong Chen received his BSc and PhD degrees from Nankai University in 1990 and 1996, respectively. He joined Nankai University in 1996. He is currently a professor at the School of Materials Science and Engineering. His current research interests include the syntheses of zeolites and mesoporous materials, heterogeneous catalysis and electrocatalysis.

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40843_2020_1525_MOESM1_ESM.pdf

Encapsulated FeP nanoparticles with in-situ formed P-doped graphene layers: Boosting activity in oxygen reduction reaction

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Ni, B., Chen, R., Wu, L. et al. Encapsulated FeP nanoparticles with in-situ formed P-doped graphene layers: Boosting activity in oxygen reduction reaction. Sci. China Mater. 64, 1159–1172 (2021). https://doi.org/10.1007/s40843-020-1525-7

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