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The proximity between hydroxyl and single atom determines the catalytic reactivity of Rh1/CeO2 single-atom catalysts

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Abstract

The local structure of the metal single-atom site is closely related to the catalytic activity of metal single-atom catalysts (SACs). However, constructing SACs with homogeneous metal active sites is a challenge due to the surface heterogeneity of the conventional support. Herein, we prepared two Rh1/CeO2 SACs (0.5Rh1/r-CeO2 and 0.5Rh1/c-CeO2, respectively) using two shaped CeO2 (rod and cube) exposing different facets, i.e., CeO2 (111) and CeO2 (100). In CO oxidation reaction, the T100 of 0.5Rh1/r-CeO2 SACs is 120 °C, while the T100 of 0.5Rh1/c-CeO2 SACs is as high as 200 °C. Via in-situ CO diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS), we found that the proximity between OH group and Rh single atom on the plane surface plays an important role in the catalytic activity of Rh1/CeO2 SAC system in CO oxidation. The Rh single atom trapped at the CeO2 (111) crystal surface forms the Rh1(OH)adjacent species, which is not found on the CeO2 (100) crystal surface at room temperature. Furthermore, during CO oxidation, the OH group far from Rh single atom on the 0.5Rh1/c-CeO2 disappears and forms Rh1(OH)adjacent species when the temperature is above 150 °C. The formation of Rh1(OH)adjacentCO intermediate in the reaction is pivotal for the excellent catalytic activity, which explains the difference in the catalytic activity of Rh single atoms on two different CeO2 planes. The formed Rh1(OH)adjacent-O-Ce structure exhibits good stability in the reducing atmosphere, maintaining the Rh atomic dispersion after CO oxidation even when pre-reduced at high temperature of 500 °C. Density functional theory (DFT) calculations validate the unique activity and reaction path of the intermediate Rh1(OH)adjacentCO species formed. This work demonstrates that the proximity between metal single atom and hydroxyl can determine the formation of active intermediates to affect the catalytic performances in catalysis.

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Acknowledgements

The work was financially supported by the National High-Level Talent Fund and the National Natural Science Foundation of China (Nos. 22072118, 22372138, 22388102, 21973013, and 22373017). We also thank financial support from State Key Laboratory of Physical Chemistry of Solid Surfaces of Xiamen University. Part of the fund was supported by Science and Technology Projects of Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM) (No. HRTP-[2022]-3) and the Fundamental Research Funds for the Central Universities (No. 20720220008). The computations were performed at the Hefei Advanced Computing Center and Supercomputing Center of Fujian. The XAS experiments used resources at the 8-ID beamline of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory (No. DE-SC0012704). J. Huang thank the National Natural Science Foundation of China (Nos. U20A20336 and 21935009) and the Natural Science Foundation of Hebei Province (No. B2020203037).

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  1. Haifeng Xiong

    Present address: State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

  2. Danfeng Wu and Shuyun Zhou contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

    Danfeng Wu & Congcong Du

  2. State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry, Fuzhou University, Fuzhou, 350002, China

    Shuyun Zhou, Juan Li & Sen Lin

  3. Clean Nano Energy Center, State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004, China

    Jianyu Huang

  4. College of Biology and Chemical Engineering, Jiaxing University, Jiaxing, 314000, China

    Hong-xia Shen

  5. Department of Chemical & Biological Engineering, University of New Mexico, Albuquerque, NM, 8731-0001, USA

    Abhaya K. Datye

  6. Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN, 47907-2100, USA

    Shan Jiang & Jeffrey T. Miller

  7. Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen, 361102, China

    Haifeng Xiong

  8. Fujian Key Laboratory of Rare-earth Functional Materials, Fujian Shanhai Collaborative Innovation Center of Rare-earth Functional Materials, Longyan, 366300, China

    Haifeng Xiong

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Wu, D., Zhou, S., Du, C. et al. The proximity between hydroxyl and single atom determines the catalytic reactivity of Rh1/CeO2 single-atom catalysts. Nano Res. 17, 397–406 (2024). https://doi.org/10.1007/s12274-023-6333-3

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