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Distinctly different active sites of ZnO-ZrO2 catalysts in CO2 and CO hydrogenation to methanol reactions

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  • Jieqiong Ding

    (University of Science and Technology of China
    University of Science and Technology of China)

  • Yao Peng

    (Fudan University)

  • Wei Xiong

    (University of Science and Technology of China)

  • Dongdong Wang

    (University of Science and Technology of China)

  • Ziran Xu

    (University of Science and Technology of China)

  • Qinxue Nie

    (University of Science and Technology of China)

  • Zheng Jiang

    (University of Science and Technology of China)

  • Zhi-Pan Liu

    (Fudan University
    Shanghai Qi Zhi Institute)

  • Cheng Shang

    (Fudan University
    Shanghai Qi Zhi Institute)

  • Weixin Huang

    (University of Science and Technology of China)

Abstract

The active site of a solid catalyst varies sensitively with the catalyzed reaction. Herein, using experimentally measured elementary surface reaction kinetics of CO2 or CO hydrogenation reactions over a ZnO-ZrO2 catalyst under working conditions in combinations with comprehensive structural characterizations and theoretical simulations, we unveil the distinctly different active sites in catalyzing the CO2 or CO hydrogenation to methanol reaction. Zn2+ cations with different local environments are present on the ZnO-ZrO2 surface, including Zn1 single atoms exclusively with a Zn-O-Zr local structure and Znn clusters with both Zn-O-Zr and Zn-O-Zn local structures. The -Zr-O-Zr- structure bonded to the Znn clusters is more easily to be reduced than that bonded to the Zn1 single atoms. The Zn1-single atom (-Zr-O-Zn-O-Zr-) is the active site for catalyzing the CO2 hydrogenation to methanol reaction, whereas the Znn cluster bonded to an in situ formed -Zr-Vo-Zr- structure (-Zn-O-Zn(-O-Zr-Vo-Zr-)-O-Zr-) is the active site for catalyzing the CO hydrogenation to methanol reaction. These results provide a reliable and effective methodology of elementary surface reaction kinetics for identifications of active sites of working catalysts in complex reactions and unveil how sensitively the active site structure varies with the catalyzed reaction.

Suggested Citation

  • Jieqiong Ding & Yao Peng & Wei Xiong & Dongdong Wang & Ziran Xu & Qinxue Nie & Zheng Jiang & Zhi-Pan Liu & Cheng Shang & Weixin Huang, 2025. "Distinctly different active sites of ZnO-ZrO2 catalysts in CO2 and CO hydrogenation to methanol reactions," Nature Communications, Nature, vol. 16(1), pages 1-17, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-59996-5
    DOI: 10.1038/s41467-025-59996-5
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    References listed on IDEAS

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    1. Zhenhua Zhang & Xuanye Chen & Jincan Kang & Zongyou Yu & Jie Tian & Zhongmiao Gong & Aiping Jia & Rui You & Kun Qian & Shun He & Botao Teng & Yi Cui & Ye Wang & Wenhua Zhang & Weixin Huang, 2021. "The active sites of Cu–ZnO catalysts for water gas shift and CO hydrogenation reactions," Nature Communications, Nature, vol. 12(1), pages 1-9, December.
    2. Yuhao Wang & Shyam Kattel & Wengui Gao & Kongzhai Li & Ping Liu & Jingguang G. Chen & Hua Wang, 2019. "Exploring the ternary interactions in Cu–ZnO–ZrO2 catalysts for efficient CO2 hydrogenation to methanol," Nature Communications, Nature, vol. 10(1), pages 1-10, December.
    3. Daniel Laudenschleger & Holger Ruland & Martin Muhler, 2020. "Identifying the nature of the active sites in methanol synthesis over Cu/ZnO/Al2O3 catalysts," Nature Communications, Nature, vol. 11(1), pages 1-10, December.
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