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Going beyond atom visualization—Characterization of supported two-atom single-cluster catalysts with scanning transmission electron microscopy

超越原子可视化—利用扫描透射电子显微镜表征双原子单团簇催化剂

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Abstract

As an innovative development of single-atom catalysts (SACs), single-cluster catalysts (SCCs) such as dual-atom catalysts have attracted considerable interest due to their excellent performance in catalysis. As one of the most powerful and visualizable tools, scanning transmission electron microscopy (STEM) has been widely applied in the characterization of SCCs. Herein, the nitrogen-doped carbon-supported FeFe and CoFe, two representative examples of homonuclear and heteronuclear SCCs, are characterized by STEM. Furthermore, an image processing program is developed to analyze the STEM images and to obtain the locations of atoms, as well as the projected distances between atoms in possible dual-atom pairs. The dimer distances of both CoFe and FeFe catalysts exhibit a trimodal distribution, which can correspond to the energy-favorable atomic structures of the theoretical simulations. Our work offers an avenue for directly revealing the possible atomic configurations of dual-atom sites in SCCs via big data statistics of STEM images and strong theoretical simulations.

摘要

本研究利用扫描透射电子显微镜(STEM)表征了碳掺杂氮负载的FeFe和CoFe双原子单团簇催化剂. 同时本工作开发了一个STEM图像处理程序, 以精准识别原子的位置并得到可能的原子对中原子之间的投影距离. 大数据分析结果显示CoFe和FeFe原子对的距离均呈现三峰分布, 对应于模拟得到的多种稳定的原子结构. 我们的工作为通过STEM图像的大数据统计和相关理论模拟直接揭示双原子单团簇催化剂中双原子位点的可能原子构型提供了一条途径.

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Acknowledgements

This work was supported by the National Key Research and Development Project (2022YFA1503900, 2022YFA1503000, and 2022YFA1203400), Shenzhen Fundamental Research Funding (JCYJ20210324115809026, JCYJ20220818100212027, and JCYJ20200109141216566), Shenzhen Science and Technology Program (KQTD20190929173815000), Guangdong scientific program with contract no. 2019QN01L057, Guangdong Innovative and Entrepreneurial Research Team Program (2019ZT08C044) to Gu M and the computational study is supported by the National Natural Science Foundation of China (22033005) to Li J and is partially sponsored by Guangdong Provincial Key Laboratory of Catalysis (2020B121201002). We are grateful to the Pico Center at SUSTech CRF that receives support from Presidential fund and Development and Reform Commission of Shenzhen Municipality. The computational resource is supported by the Center for Computational Science and Engineering at SUSTech and the CHEM high-performance supercomputer cluster (CHEM-HPC) located at the Department of Chemistry, SUSTech.

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, 518055, China

    Cheng Li  (李铖) & Meng Gu  (谷猛)

  2. School of Physics and Astronomy, University of Birmingham, Birmingham, B15 2TT, UK

    Cheng Li  (李铖) & Wolfgang Theis

  3. Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China

    Jun-Chi Chen  (陈俊池) & Jun Li  (李隽)

  4. School of Materials Science and Engineering, Ocean University of China, Qingdao, 266100, China

    Xing-Kun Wang  (汪兴坤) & Ming-Hua Huang  (黄明华)

  5. Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Tsinghua University, Beijing, 100084, China

    Jun Li  (李隽)

Authors
  1. Cheng Li  (李铖)
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  6. Jun Li  (李隽)
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  7. Meng Gu  (谷猛)
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Contributions

Author contributions Wang XK designed and engineered the samples; Li C and Chen JC performed the characterization and DFT calculations; Li C, Chen JC, Li J, and Gu M co-wrote the paper with support from Huang MH and Theis W. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Wolfgang Theis, Jun Li  (李隽) or Meng Gu  (谷猛).

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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.

Cheng Li is currently a joint PhD student at Southern University of Science and Technology (SUSTech) and the University of Birmingham. He received his Master’s degree from the University of Science and Technology Beijing. His research interests focus on advanced electron microscopy characterization and analysis.

Jun-Chi Chen received his Master’s degree from the Department of Chemistry, SUSTech in 2022, under the supervision of Prof. Jun Li and Prof. Yang-Gang Wang. He is currently a research assistant at the TCCL (Theoretical and Computational Chemistry Lab), SUSTech. His research interests focus on computational catalysis science, especially the rational design and catalytic application of SACs (single-atom catalysts) and SCCs (single-cluster catalysts).

Wolfgang Theis is a senior lecturer at the Nanoscale Physics Research Laboratory of University of Birmingham. He qualified with a Diplom in physics at the Freie Universität Berlin in 1989. He completed his PhD project at the Fritz-Haber Institut, Berlin in 1992. His research interests are surface science and its application to nanoscale structures and high-resolution electron microscopy.

Jun Li received his PhD degree from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences in 1992. He did postdoctoral research at the University of Siegen and The Ohio State University from 1994 to 1997. He worked as a research scientist at The Ohio State University as well as Senior Research Scientist and Chief Scientist at the Pacific Northwest National Laboratory from 1997 to 2009. He is now a professor at Tsinghua University. His research involves theoretical chemistry, heavy-element chemistry, and computational catalysis science.

Meng Gu received his PhD degree in materials science from the University of California, Davis. He is now a professor at the SUSTech. His research focuses on the development of better catalysts, various rechargeable batteries, and advanced electron microscopy characterization and analysis.

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40843_2022_2416_MOESM1_ESM.pdf

Going beyond atom visualization—Characterization of supported two-atom single-cluster catalysts with scanning transmission electron microscopy

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Li, C., Chen, JC., Wang, XK. et al. Going beyond atom visualization—Characterization of supported two-atom single-cluster catalysts with scanning transmission electron microscopy. Sci. China Mater. 66, 2733–2740 (2023). https://doi.org/10.1007/s40843-022-2416-2

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