IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v16y2025i1d10.1038_s41467-025-56271-5.html
   My bibliography  Save this article

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
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-025-56271-5
    File Function: Abstract
    Download Restriction: no
    File URL: https://libkey.io/10.1038/s41467-025-56271-5?utm_source=ideas
    LibKey link: if access is restricted and if your library uses this service, LibKey will redirect you to where you can use your library subscription to access this item
    ---><---

    References listed on IDEAS

    as
    1. 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.
    2. 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.
    3. 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.
    4. 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.
    5. 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.
    6. 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.
    Full references (including those not matched with items on IDEAS)

    Most related items

    These are the items that most often cite the same works as this one and are cited by the same works as this one.
    1. Lili Zhang & Ning Zhang & Huishan Shang & Zhiyi Sun & Zihao Wei & Jingtao Wang & Yuanting Lei & Xiaochen Wang & Dan Wang & Yafei Zhao & Zhongti Sun & Fang Zhang & Xu Xiang & Bing Zhang & Wenxing Chen, 2024. "High-density asymmetric iron dual-atom sites for efficient and stable electrochemical water oxidation," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    2. Hongqiang Jin & Peipei Li & Peixin Cui & Jinan Shi & Wu Zhou & Xiaohu Yu & Weiguo Song & Changyan Cao, 2022. "Unprecedentedly high activity and selectivity for hydrogenation of nitroarenes with single atomic Co1-N3P1 sites," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    3. Meihuan Liu & Jing Zhang & Hui Su & Yaling Jiang & Wanlin Zhou & Chenyu Yang & Shuowen Bo & Jun Pan & Qinghua Liu, 2024. "In situ modulating coordination fields of single-atom cobalt catalyst for enhanced oxygen reduction reaction," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    4. Yunxiang Lin & Bo Geng & Ruyun Zheng & Wei Chen & Jiahui Zhao & Hengjie Liu & Zeming Qi & Zhipeng Yu & Kun Xu & Xue Liu & Li Yang & Lei Shan & Li Song, 2025. "Optimizing surface active sites via burying single atom into subsurface lattice for boosted methanol electrooxidation," Nature Communications, Nature, vol. 16(1), pages 1-13, December.
    5. Sam, Daniel Kobina & Cao, Yan, 2024. "Electrocatalytic activities of iron-supported N-doped porous carbon towards the oxygen/hydrogen evolution reaction," Renewable Energy, Elsevier, vol. 237(PC).
    6. Yanzhe Shi & Bingcheng Luo & Rui Sang & Dandan Cui & Ye Sun & Runqi Liu & Zili Zhang & Yifei Sun & Henrik Junge & Matthias Beller & Xiang Li, 2024. "Combination of nanoparticles with single-metal sites synergistically boosts co-catalyzed formic acid dehydrogenation," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    7. Yangyang Liu & Can Li & Chunhui Tan & Zengxia Pei & Tao Yang & Shuzhen Zhang & Qianwei Huang & Yihan Wang & Zheng Zhou & Xiaozhou Liao & Juncai Dong & Hao Tan & Wensheng Yan & Huajie Yin & Zhao-Qing L, 2023. "Electrosynthesis of chlorine from seawater-like solution through single-atom catalysts," Nature Communications, Nature, vol. 14(1), pages 1-13, December.
    8. Sicheng Li & Tong Liu & Wei Zhang & Mingzhen Wang & Huijuan Zhang & Chunlan Qin & Lingling Zhang & Yudan Chen & Shuaiwei Jiang & Dong Liu & Xiaokang Liu & Huijuan Wang & Qiquan Luo & Tao Ding & Tao Ya, 2024. "Highly efficient anion exchange membrane water electrolyzers via chromium-doped amorphous electrocatalysts," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    9. Shuo Zhang & Jianghua Wu & Mengting Zheng & Xin Jin & Zihan Shen & Zhonghua Li & Yanjun Wang & Quan Wang & Xuebin Wang & Hui Wei & Jiangwei Zhang & Peng Wang & Shanqing Zhang & Liyan Yu & Lifeng Dong , 2023. "Fe/Cu diatomic catalysts for electrochemical nitrate reduction to ammonia," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    10. Tianyu Zhang & Jing Jin & Junmei Chen & Yingyan Fang & Xu Han & Jiayi Chen & Yaping Li & Yu Wang & Junfeng Liu & Lei Wang, 2022. "Pinpointing the axial ligand effect on platinum single-atom-catalyst towards efficient alkaline hydrogen evolution reaction," Nature Communications, Nature, vol. 13(1), pages 1-14, December.
    11. Fangqing Wang & Peichao Zou & Yangyang Zhang & Wenli Pan & Ying Li & Limin Liang & Cong Chen & Hui Liu & Shijian Zheng, 2023. "Activating lattice oxygen in high-entropy LDH for robust and durable water oxidation," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    12. Li Zhang & Xiaoju Yang & Qing Yuan & Zhiming Wei & Jie Ding & Tianshu Chu & Chao Rong & Qiao Zhang & Zhenkun Ye & Fu-Zhen Xuan & Yueming Zhai & Bowei Zhang & Xuan Yang, 2023. "Elucidating the structure-stability relationship of Cu single-atom catalysts using operando surface-enhanced infrared absorption spectroscopy," Nature Communications, Nature, vol. 14(1), pages 1-9, December.
    13. Xin Zhao & Ruiqi Fang & Fengliang Wang & Xiangpeng Kong & Yingwei Li, 2022. "Atomic design of dual-metal hetero-single-atoms for high-efficiency synthesis of natural flavones," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    14. Xiubei Yang & Qizheng An & Xuewen Li & Yubin Fu & Shuai Yang & Minghao Liu & Qing Xu & Gaofeng Zeng, 2024. "Charging modulation of the pyridine nitrogen of covalent organic frameworks for promoting oxygen reduction reaction," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    15. Yurui Fan & Haomiao Xu & Guanqun Gao & Mingming Wang & Wenjun Huang & Lei Ma & Yancai Yao & Zan Qu & Pengfei Xie & Bin Dai & Naiqiang Yan, 2024. "Asymmetric Ru-In atomic pairs promote highly active and stable acetylene hydrochlorination," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    16. Xingbao Chen & Ruihu Lu & Chengbo Li & Wen Luo & Ruohan Yu & Jiexin Zhu & Lei Lv & Yuhang Dai & Shanhe Gong & Yazhou Zhou & Weiwei Xiong & Jiahao Wu & Hongwei Cai & Xinfei Wu & Zhaohui Deng & Boyu Xin, 2025. "Activating inert non-defect sites in Bi catalysts using tensile strain engineering for highly active CO2 electroreduction," Nature Communications, Nature, vol. 16(1), pages 1-13, December.
    17. Hongnan Jia & Na Yao & Yiming Jin & Liqing Wu & Juan Zhu & Wei Luo, 2024. "Stabilizing atomic Ru species in conjugated sp2 carbon-linked covalent organic framework for acidic water oxidation," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    18. Zhimeng Tang & Lei Xu & Cheng Xie & Lirong Guo & Libo Zhang & Shenghui Guo & Jinhui Peng, 2023. "Synthesis of CuCo2S4@Expanded Graphite with crystal/amorphous heterointerface and defects for electromagnetic wave absorption," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    19. Pengcheng Ye & Keqing Fang & Haiyan Wang & Yahao Wang & Hao Huang & Chenbin Mo & Jiqiang Ning & Yong Hu, 2024. "Lattice oxygen activation and local electric field enhancement by co-doping Fe and F in CoO nanoneedle arrays for industrial electrocatalytic water oxidation," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    20. Kejun Bu & Qingyang Hu & Xiaohuan Qi & Dong Wang & Songhao Guo & Hui Luo & Tianquan Lin & Xiaofeng Guo & Qiaoshi Zeng & Yang Ding & Fuqiang Huang & Wenge Yang & Ho-Kwang Mao & Xujie Lü, 2022. "Nested order-disorder framework containing a crystalline matrix with self-filled amorphous-like innards," Nature Communications, Nature, vol. 13(1), pages 1-9, December.

    More about this item

    Statistics

    Access and download statistics

    Corrections

    All material on this site has been provided by the respective publishers and authors. You can help correct errors and omissions. When requesting a correction, please mention this item's handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-56271-5. See general information about how to correct material in RePEc.

    If you have authored this item and are not yet registered with RePEc, we encourage you to do it here. This allows to link your profile to this item. It also allows you to accept potential citations to this item that we are uncertain about.

    If CitEc recognized a bibliographic reference but did not link an item in RePEc to it, you can help with this form .

    If you know of missing items citing this one, you can help us creating those links by adding the relevant references in the same way as above, for each refering item. If you are a registered author of this item, you may also want to check the "citations" tab in your RePEc Author Service profile, as there may be some citations waiting for confirmation.

    For technical questions regarding this item, or to correct its authors, title, abstract, bibliographic or download information, contact: Sonal Shukla or Springer Nature Abstracting and Indexing (email available below). General contact details of provider: http://www.nature.com .

    Please note that corrections may take a couple of weeks to filter through the various RePEc services.

    IDEAS is a RePEc service. RePEc uses bibliographic data supplied by the respective publishers.