Atomic-scale Observation of the Generation and Dispersion of Iron Single Atoms

doi:10.1007/s40242-025-4259-x

高等学校化学研究 ›› 2025, Vol. 41 ›› Issue (2): 281-287.doi: 10.1007/s40242-025-4259-x

Atomic-scale Observation of the Generation and Dispersion of Iron Single Atoms

LIN Ting^1,2, SHEN Yang^1,3, GE Mengshu¹, LI Yangfan^1,3, JIANG Zhe^3,4, LYU Zhen-Hua^3,4, LIU Jian⁴, GU Lin², LIU Xiaozhi¹

1. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, P. R. China;
2. Beijing National Center for Electron Microscopy and Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, P. R. China;
3. University of Chinese Academy of Sciences, Beijing 100049, P. R. China;
4. Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China

收稿日期:2024-12-30 接受日期:2025-02-11 出版日期:2025-04-01 发布日期:2025-03-31
通讯作者: LIU Jian,liujian13@iccas.ac.cn;GU Lin,lingu@mail.tsinghua.edu.cn;LIU Xiaozhi,liuxz@iphy.ac.cn E-mail:liujian13@iccas.ac.cn;lingu@mail.tsinghua.edu.cn;liuxz@iphy.ac.cn
基金资助:
This work was supported by the National Key Research and Development Program of China (No. 2023YFB4006203), the National Natural Science Foundation of China (Nos. U21A20328, 22209202), the Strategic Priority Research Program B of Chinese Academy of Sciences (No. XDB33030200), and the Project Funded by China Postdoctoral Science Foundation (No. 2021M703457).

Atomic-scale Observation of the Generation and Dispersion of Iron Single Atoms

LIN Ting^1,2, SHEN Yang^1,3, GE Mengshu¹, LI Yangfan^1,3, JIANG Zhe^3,4, LYU Zhen-Hua^3,4, LIU Jian⁴, GU Lin², LIU Xiaozhi¹

1. Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, P. R. China;
2. Beijing National Center for Electron Microscopy and Laboratory of Advanced Materials, Department of Materials Science and Engineering, Tsinghua University, Beijing 100084, P. R. China;
3. University of Chinese Academy of Sciences, Beijing 100049, P. R. China;
4. Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China

Received:2024-12-30 Accepted:2025-02-11 Online:2025-04-01 Published:2025-03-31
Contact: LIU Jian,liujian13@iccas.ac.cn;GU Lin,lingu@mail.tsinghua.edu.cn;LIU Xiaozhi,liuxz@iphy.ac.cn E-mail:liujian13@iccas.ac.cn;lingu@mail.tsinghua.edu.cn;liuxz@iphy.ac.cn
Supported by:
This work was supported by the National Key Research and Development Program of China (No. 2023YFB4006203), the National Natural Science Foundation of China (Nos. U21A20328, 22209202), the Strategic Priority Research Program B of Chinese Academy of Sciences (No. XDB33030200), and the Project Funded by China Postdoctoral Science Foundation (No. 2021M703457).

摘要/Abstract

摘要： Single-atom catalysts (SACs) have shown great potential in catalysis and energy-related applications. Among these, iron SACs stand out for their exceptional performance and environmental friendliness. In this study, we investigated the transformation of iron oxide nanoparticles into iron single atoms, exemplifying a top-down synthesis strategy. Using in-situ transmission electron microscopy (TEM), we directly observed the dynamic behaviors during the pyrolysis-induced atomization of Fe₃O₄ nanoparticles along the [110], [111], and [112] zone axes at atomic-scale resolution. Reducing gases were supposed to release during the thermal pyrolysis of an organic reducing agent and facilitate the generation of Fe single atoms. The rate-limiting step was the reaction of these gases with atoms at surface steps and vertices of Fe₃O₄ nanoparticles. Electron energy loss spectroscopy revealed a reduction in the Fe valence state and a transition in the Fe-O coordination environment after in-situ thermal treatment. The high-density dispersion of Fe single atoms was facilitated by the weak repulsive interactions between Fe atoms. This study enriches the understanding of the gas-assisted atomization mechanism and offers valuable insights for optimizing the production of high-density SACs. The methodology and findings can be extended to other material systems, broadening the scope of single-atom engineering and catalysis applications.

关键词: Single atom recognition, In-situ heating, Atomic-scale dynamics, Nanoparticle decomposition, Gas-assisted solid-phase dissolution process

Abstract: Single-atom catalysts (SACs) have shown great potential in catalysis and energy-related applications. Among these, iron SACs stand out for their exceptional performance and environmental friendliness. In this study, we investigated the transformation of iron oxide nanoparticles into iron single atoms, exemplifying a top-down synthesis strategy. Using in-situ transmission electron microscopy (TEM), we directly observed the dynamic behaviors during the pyrolysis-induced atomization of Fe₃O₄ nanoparticles along the [110], [111], and [112] zone axes at atomic-scale resolution. Reducing gases were supposed to release during the thermal pyrolysis of an organic reducing agent and facilitate the generation of Fe single atoms. The rate-limiting step was the reaction of these gases with atoms at surface steps and vertices of Fe₃O₄ nanoparticles. Electron energy loss spectroscopy revealed a reduction in the Fe valence state and a transition in the Fe-O coordination environment after in-situ thermal treatment. The high-density dispersion of Fe single atoms was facilitated by the weak repulsive interactions between Fe atoms. This study enriches the understanding of the gas-assisted atomization mechanism and offers valuable insights for optimizing the production of high-density SACs. The methodology and findings can be extended to other material systems, broadening the scope of single-atom engineering and catalysis applications.

Key words: Single atom recognition, In-situ heating, Atomic-scale dynamics, Nanoparticle decomposition, Gas-assisted solid-phase dissolution process

LIN Ting, SHEN Yang, GE Mengshu, LI Yangfan, JIANG Zhe, LYU Zhen-Hua, LIU Jian, GU Lin, LIU Xiaozhi. Atomic-scale Observation of the Generation and Dispersion of Iron Single Atoms[J]. 高等学校化学研究, 2025, 41(2): 281-287.

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Atomic-scale Observation of the Generation and Dispersion of Iron Single Atoms

Atomic-scale Observation of the Generation and Dispersion of Iron Single Atoms

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