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Planar chlorination engineering induced symmetry-broken single-atom site catalyst for enhanced CO2 electroreduction

Author

Listed:
  • Shengjie Wei

    (Beijing University of Technology
    Nankai University)

  • Jiexin Zhu

    (Xi’an Jiaotong University
    Wuhan University of Technology)

  • Xingbao Chen

    (Wuhan University of Technology)

  • Rongyan Yang

    (College of Environmental Science and Engineering of Nankai University)

  • Kailong Gu

    (Xi’an Jiaotong University)

  • Lei Li

    (University of Science and Technology of China)

  • Ching-Yu Chiang

    (National Synchrotron Radiation Research Center)

  • Liqiang Mai

    (Wuhan University of Technology)

  • Shenghua Chen

    (Xi’an Jiaotong University)

Abstract

Breaking the geometric symmetry of traditional metal-N4 sites and further boosting catalytic activity are significant but challenging. Herein, planar chlorination engineering is proposed for successfully converting the traditional Zn-N4 site with low activity and selectivity for CO2 reduction reaction (CO2RR) into highly active Zn-N3 site with broken symmetry. The optimal catalyst Zn-SA/CNCl-1000 displays a highest faradaic efficiency for CO (FECO) around 97 ± 3% and good stability during 50 h test at high current density of 200 mA/cm2 in zero-gap membrane electrode assembly (MEA) electrolyzer, with promising application in industrial catalysis. At -0.93 V vs. RHE, the partial current density of CO (JCO) and the turnover frequency (TOF) value catalyzed by Zn-SA/CNCl-1000 are 271.7 ± 1.4 mA/cm2 and 29325 ± 151 h-1, as high as 29 times and 83 times those of Zn-SA/CN-1000 without planar chlorination engineering. The in-situ extended X-ray absorption fine structure (EXAFS) measurements and density functional theory (DFT) calculation reveal the adjacent C-Cl bond induces the self-reconstruction of Zn-N4 site into the highly active Zn-N3 sites with broken symmetry, strengthening the adsorption of *COOH intermediate, and thus remarkably improving CO2RR activity.

Suggested Citation

  • Shengjie Wei & Jiexin Zhu & Xingbao Chen & Rongyan Yang & Kailong Gu & Lei Li & Ching-Yu Chiang & Liqiang Mai & Shenghua Chen, 2025. "Planar chlorination engineering induced symmetry-broken single-atom site catalyst for enhanced CO2 electroreduction," Nature Communications, Nature, vol. 16(1), pages 1-12, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-56271-5
    DOI: 10.1038/s41467-025-56271-5
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    References listed on IDEAS

    as
    1. Shengjie Wei & Wenjie Ma & Minmin Sun & Pan Xiang & Ziqi Tian & Lanqun Mao & Lizeng Gao & Yadong Li, 2024. "Atom-pair engineering of single-atom nanozyme for boosting peroxidase-like activity," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    2. Huishan Shang & Xiangyi Zhou & Juncai Dong & Ang Li & Xu Zhao & Qinghua Liu & Yue Lin & Jiajing Pei & Zhi Li & Zhuoli Jiang & Danni Zhou & Lirong Zheng & Yu Wang & Jing Zhou & Zhengkun Yang & Rui Cao , 2020. "Engineering unsymmetrically coordinated Cu-S1N3 single atom sites with enhanced oxygen reduction activity," Nature Communications, Nature, vol. 11(1), pages 1-11, December.
    3. Juncai Dong & Yangyang Liu & Jiajing Pei & Haijing Li & Shufang Ji & Lei Shi & Yaning Zhang & Can Li & Cheng Tang & Jiangwen Liao & Shiqing Xu & Huabin Zhang & Qi Li & Shenlong Zhao, 2023. "Continuous electroproduction of formate via CO2 reduction on local symmetry-broken single-atom catalysts," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    4. Junjie Li & Ya-fei Jiang & Qi Wang & Cong-Qiao Xu & Duojie Wu & Mohammad Norouzi Banis & Keegan R. Adair & Kieran Doyle-Davis & Debora Motta Meira & Y. Zou Finfrock & Weihan Li & Lei Zhang & Tsun-Kong, 2021. "A general strategy for preparing pyrrolic-N4 type single-atom catalysts via pre-located isolated atoms," Nature Communications, Nature, vol. 12(1), pages 1-11, December.
    5. Jiexin Zhu & Jiantao Li & Ruihu Lu & Ruohan Yu & Shiyong Zhao & Chengbo Li & Lei Lv & Lixue Xia & Xingbao Chen & Wenwei Cai & Jiashen Meng & Wei Zhang & Xuelei Pan & Xufeng Hong & Yuhang Dai & Yu Mao , 2023. "Surface passivation for highly active, selective, stable, and scalable CO2 electroreduction," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    6. Kyu Min Lee & Jun Ho Jang & Mani Balamurugan & Jeong Eun Kim & Young In Jo & Ki Tae Nam, 2021. "Redox-neutral electrochemical conversion of CO2 to dimethyl carbonate," Nature Energy, Nature, vol. 6(7), pages 733-741, July.
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