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Highly dispersed L10-PtZn intermetallic catalyst for efficient oxygen reduction

高分散L10-PtZn金属间化合物高效催化氧还原

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Abstract

Highly active and durable electrocatalysts with minimal Pt usage are desired for commercial fuel cell applications. Herein, we present a highly dispersed L10-PtZn intermetallic catalyst for the oxygen reduction reaction (ORR), in which a Zn-rich metal-organic framework (MOF) is used as an in situ generated support to confine the growth of PtZn particles. Despite requiring high-temperature treatment, the intermetallic L10-PtZn particles exhibit a small mean size of 3.95 nm, which confers the catalysts with high electrochemical active surface area (81.9 m2 gPt−1) and atomic utilization. The Pt electron structure and binding strength between Pt and oxygen intermediates are optimized through ligand effect and compressive strain. These advantages result in ORR mass activity and specific activity of 0.926 A mgPt−1 and 1.13 mA cm−2, respectively, which are 5.4 and 4.0 times those of commercial Pt/C. The stable L10 structure provides the catalysts with superb durability; only a halfwave potential loss of 11 mV is observed after 30,000 cycles of accelerated stress tests, through which the structure evolves into a more stable PtZn-Pt core-shell structure. Therefore, the development of a Zn based MOF as a catalyst support is demonstrated, providing a synergy strategy to prepare highly dispersed intermetallic alloys with high activity and durability.

摘要

燃料电池商业化的关键在于实现低铂催化剂的高活性和高 耐久性. 本文通过使用一种富锌MOF作为原位生长的载体来限制 PtZn粒子增长, 成功制备了高分散的L10-PtZn金属间化合物氧还 原反应(ORR)催化剂. 该催化剂经过高温处理后平均粒径仅为 3.95 nm, 具有较高的电化学活性表面积(81.9 m2 gPt−1)和原子利用 率. 配体效应和压缩应变优化了铂的电子结构, 从而调节了铂与氧 中间体之间的结合强度. 催化剂表现出高的质量活性 (0.926 A mgPt−1)和比活性(1.13 mA cm−2), 分别为商业Pt/C催化剂 (0.172 A mgPt−1和0.28 mA cm−2)的5.4倍和4.0倍. 由于L10自身结构 更加稳定, 并且PtZn金属纳米粒子在耐久循环中逐步演变为PtZn-Pt核壳结构, 使得该催化剂在30,000圈加速老化测试中表现出优异 的稳定性(仅11 mV半波电位(E1/2)损耗).

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Acknowledgements

This work was supported by the National Science and Technology Major Project (2017YFB0102900), the National Natural Science Foundation of China (21633008, 21673221 and U1601211), and Jilin Province Science and Technology Development Program (20200201001JC, 20190201270JC and 20180101030JC).

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Authors and Affiliations

  1. State Key Laboratory of Electroanalytical Chemistry, Jilin Province Key Laboratory of Low Carbon Chemical Power, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China

    Tuo Zhao  (赵拓), Ergui Luo  (罗二桂), Yang Li  (李阳), Xian Wang  (王显), Changpeng Liu  (刘长鹏), Wei Xing  (邢巍) & Junjie Ge  (葛君杰)

  2. School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei, 230026, China

    Tuo Zhao  (赵拓), Ergui Luo  (罗二桂), Yang Li  (李阳), Xian Wang  (王显), Changpeng Liu  (刘长鹏), Wei Xing  (邢巍) & Junjie Ge  (葛君杰)

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  1. Tuo Zhao  (赵拓)
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  2. Ergui Luo  (罗二桂)
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  3. Yang Li  (李阳)
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  4. Xian Wang  (王显)
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  5. Changpeng Liu  (刘长鹏)
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  6. Wei Xing  (邢巍)
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  7. Junjie Ge  (葛君杰)
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Contributions

Ge J supervised the study. Zhao T designed the experiments, performed most of the experiments and characterizations. Luo E, Li Y and Wang X participated in the analyses of the results. Zhao T wrote the manuscript, and Ge J, Liu C and Xing W revised it. All the authors contributed to the general discussion.

Corresponding author

Correspondence to Junjie Ge  (葛君杰).

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Conflict of interest

The authors declare that they have no conflict of interest.

Tuo Zhao is a PhD candidate at the State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry (CIAC). He received his BSc degree in materials science and engineering from Hainan University in 2016. His current research interest is the development of efficient ORR catalysts in proton exchange membrane fuel cells.

Junjie Ge is a professor of chemistry at CIAC, Chinese Academy of Sciences (CAS). She received her PhD in physical chemistry from CIAC in 2010 and completed postdoctoral training at the University of South Carolina (2010–2012) and University of Hawaii (2012–2015). She joined CIAC in 2015 as a professor, where she was recruited in the Hundred Talents Program in CAS (2015). Her current research interests focus on hydrogen energy and fuel cells, basic electrochemistry, and electrocatalysis, mainly concentrating in proton exchange membrane-based energy conversion systems.

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Zhao, T., Luo, E., Li, Y. et al. Highly dispersed L10-PtZn intermetallic catalyst for efficient oxygen reduction. Sci. China Mater. 64, 1671–1678 (2021). https://doi.org/10.1007/s40843-020-1582-3

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