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Optimizing spin arrangement by permeability modulation of high-entropy alloys to promote O-O formation for efficient water oxidation

调控磁导率以优化高熵合金的自旋电子排列实现高效析氧反应

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Abstract

Magnetic field-triggered spin arrangements have emerged as an intriguing and viable strategy for enhancing the oxygen evolution reaction. However, the magnetic field-enhanced mechanism in high-entropy alloy (HEA) catalysts with strong d-d Coulomb interactions remains incompletely understood. In this study, metal-sheet HEAs with excellent soft-magnetic properties that exhibit remarkable field-enhanced catalysis under a minute magnetic field were designed. The permeability of these HEAs serves as a descriptor for assessing the enhancement. Specifically, the drop in the overpotential of (FeCoNi)82.5Cr17.5 HEAs exceeds 36 mV@10 mA cm−2 when applying a field of only 50 mT. Furthermore, reduction in overpotential demonstrates a direct linear correlation with the magnetic permeability of the HEAs. Theoretical calculations coupled with in-situ Raman spectroscopy elucidate that applying a magnetic field substantially significantly increases spin density and improves the spin interaction between the 3d electrons of the catalyst and the 2p orbital of the *O intermediate. This effectively lowers the energy barrier of the rate-determining step (*O→*OOH), thereby facilitating O-O formation.

摘要

磁场触发的催化剂轨道电子自旋排列已成为促进析氧反应的一种有趣而可行的策略. 然而, 具有强d-d库仑相互作用的高熵合金(HEAs)催化剂中的磁场增强机制尚未得到充分挖掘. 在此, 我们设计了具有优异软磁性的高熵合金金属片, 在微小磁场下表现出显著的磁场增强催化作用, 其磁导率可作为评估磁场增强的描述因子. 具体地, 仅施加50 mT的磁场, (FeCoNi)82.5Cr17.5 HEAs的过电位下降就超过了36 mV@10 mA cm−2. 此外, 过电位的降低与HEA的磁导率呈线性关系. 原位拉曼光谱与理论计算结果表明, 施加磁场可显著提高自旋密度, 改善催化剂的3d电子与*O自由基的2p轨道之间的自旋相互作用, 从而有效降低速率决定步骤(*O→*OOH)的能量障碍, 进而促进O-O的形成.

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Acknowledgements

Thanks to Prof. Yonggang Yao at Huazhong University of Science and Technology for his guidance. The work was financially supported by the National Natural Science Foundation of China (52188101, Cheng HM; 22275205, Peng J), Shenzhen Basic Research Project (JCYJ20200109144616617, Cheng HM), the Science and Technology Foundation of Shenzhen (JCYJ20220530154404010, Peng J), Guangdong Basic and Applied Basic Research Foundation (2023B1515020102, Peng J; 2022A1515110408, Chen ZJ), China Postdoctoral Science Foundation (2022M713270, Chen ZJ), and the Cross Institute Joint Research Youth Team Project of SIAT (E25427, Peng J). The computing work associated with this paper supported by the public computing service platform provided by the Network and Computing Center of Huazhong University of Science and Technology.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Faculty of Materials Science and Energy Engineering, Institute of Technology for Carbon Neutrality, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055, China

    Zheng-Jie Chen  (陈正杰), Xinchun Yang  (杨新春), Yongping Zheng  (郑勇平), Yongbing Tang  (唐永炳), Jing Peng  (彭晶) & Hui-Ming Cheng  (成会明)

  2. Wuhan National High Magnetic Field Center & School of Physic, Huazhong University of Science and Technology, Wuhan, 430074, China

    Zheng-Jie Chen  (陈正杰), Tao Zhang  (张涛) & Hai-Bin Yu  (于海滨)

  3. Institute of Information Technology, Shenzhen Institute of Information Technology, Shenzhen, 518172, China

    Jiajing Wu  (吴佳静)

  4. Shenzhen Key Laboratory of Energy Materials for Carbon Neutrality, Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen, 518055, China

    Yongbing Tang  (唐永炳), Jing Peng  (彭晶) & Hui-Ming Cheng  (成会明)

  5. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China

    Hui-Ming Cheng  (成会明)

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  1. Zheng-Jie Chen  (陈正杰)
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Contributions

Author contributions Cheng HM, Peng J, and Yu HB conceived the idea. Chen ZJ and Zhang T designed and engineered the samples, and performed the experiments; Cheng HM, Peng J, Yu HB, and Chen ZJ wrote the paper with support from Yang X, Zheng Y, Tang Y. Other authors contributed to the general discussion.

Corresponding authors

Correspondence to Hai-Bin Yu  (于海滨), Jing Peng  (彭晶) or Hui-Ming Cheng  (成会明).

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

Additional information

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

Zheng-Jie Chen received his PhD degree in 2021 from Huazhong University of Science and Technology (Supervisor: Hai-Bin Yu). He is currently a postdoctoral fellow of Professor Jing Peng and Academician Hui-Ming Cheng at Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen. His research centers on OER&HER electrocatalysts and electrocatalytic biomass upgrade.

Tao Zhang is currently a PhD candidate under the supervision of professor Hai-Bin Yu at Huazhong University of Science and Technology. His research centers on HEA electrocatalysts for water splitting.

Hai-Bin Yu received his PhD degree in 2012 from the Institute of Physics, Chinese Academy of Sciences. He joined Huazhong University of Science and Technology in 2015. He was awarded the “Young Thousand Talents” program in 2017. His research interest mainly focuses on the relaxation dynamics of metallic glasses and OER&HER electrocatalysts.

Jing Peng obtained his Bachelor’s and PhD degrees from the University of Science and Technology of China and was mentored by Professor Changzheng Wu and Academician Yi Xie. In 2021, he joined Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences and Shenzhen Technology University. He is an associate researcher and awarded Guangdong Province Outstanding Young Scientist Fund. His primary research focuses on the investigation of two-dimensional materials and their electrocatalytic performance.

Hui-Ming Cheng is an internationally renowned carbon materials scientist, a member of Chinese Academy of Sciences, and a fellow of the Academy of Sciences for the Developing World. He joined Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences and Shenzhen Technology University in 2021. His primary research areas include carbon nanotubes, graphene, and energy conversion and storage materials.

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Optimizing Spin Arrangement by Permeability Modulation of High-entropy Alloys to Promote O-O Formation for Efficient Water Oxidation

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Chen, ZJ., Zhang, T., Wu, J. et al. Optimizing spin arrangement by permeability modulation of high-entropy alloys to promote O-O formation for efficient water oxidation. Sci. China Mater. 67, 598–607 (2024). https://doi.org/10.1007/s40843-023-2709-5

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