IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v16y2025i1d10.1038_s41467-025-61189-z.html
   My bibliography  Save this article

In situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1-x shield

Author

Listed:
  • Fanxing Zhang

    (Zhejiang University)

  • Ning Cao

    (Zhejiang University)

  • Chentao Wang

    (Zhejiang University
    Institute of Zhejiang University-Quzhou)

  • Shengxiang Wang

    (Spallation Neutron Source Science Center)

  • Yi He

    (Zhejiang University)

  • Yao Shi

    (Zhejiang University)

  • Mi Yan

    (Zhejiang University)

  • Ying Bao

    (Western Washington University)

  • Zhenglong Li

    (Institute of Zhejiang University-Quzhou
    Zhejiang University)

  • Pengfei Xie

    (Zhejiang University
    Institute of Zhejiang University-Quzhou)

Abstract

Electrochemical CO2-to-ethanol conversion is challenged by sluggish C-C coupling kinetics and wide products distribution. Although Cu+ has been demonstrated to enhance multi-carbon (C2+) formation, the stabilization of Cu+ under reduction conditions is difficult. Here, we report a hydrogen-ethanol pretreatment strategy to obtain Cu nanoparticles covered by highly dispersed and disordered ZnO1-x clusters. Ethanol-induced ZnO1-x redispersion gives rise to abundant Cu+ on the subsurface. The optimal catalyst delivers a 73.0% ethanol Faradaic efficiency (FE) and 86.0% total C2+ FE at −0.9 V, with a 2.3 mmol cm−2 h−1 ethanol formation rate and single-pass ethanol yield of 18.0%. The catalyst also exhibits stability beyond 500 h, attributed to the stabilization of Cu+ by the ZnO1-x shield that requires a high energy barrier for lattice oxygen removal. In situ X-ray spectroscopy and calculations reveal a volcano relationship between Cu+ ratio in Cu species and ethanol FE. Optimal Cu+ density not only facilitates *OC-COH coupling but also optimizes the adsorption energy of *CH2CH2O on catalyst for ethanol electrosynthesis.

Suggested Citation

  • Fanxing Zhang & Ning Cao & Chentao Wang & Shengxiang Wang & Yi He & Yao Shi & Mi Yan & Ying Bao & Zhenglong Li & Pengfei Xie, 2025. "In situ stabilization of Cu+ for CO2 Electroreduction via Environmental-molecules-induced ZnO1-x shield," Nature Communications, Nature, vol. 16(1), pages 1-14, December.
  • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-61189-z
    DOI: 10.1038/s41467-025-61189-z
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-025-61189-z
    File Function: Abstract
    Download Restriction: no

    File URL: https://libkey.io/10.1038/s41467-025-61189-z?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. Haiping Xu & Dominic Rebollar & Haiying He & Lina Chong & Yuzi Liu & Cong Liu & Cheng-Jun Sun & Tao Li & John V. Muntean & Randall E. Winans & Di-Jia Liu & Tao Xu, 2020. "Highly selective electrocatalytic CO2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper," Nature Energy, Nature, vol. 5(8), pages 623-632, August.
    2. Miao Zhong & Kevin Tran & Yimeng Min & Chuanhao Wang & Ziyun Wang & Cao-Thang Dinh & Phil De Luna & Zongqian Yu & Armin Sedighian Rasouli & Peter Brodersen & Song Sun & Oleksandr Voznyy & Chih-Shan Ta, 2020. "Accelerated discovery of CO2 electrocatalysts using active machine learning," Nature, Nature, vol. 581(7807), pages 178-183, May.
    3. Antonia Herzog & Mauricio Lopez Luna & Hyo Sang Jeon & Clara Rettenmaier & Philipp Grosse & Arno Bergmann & Beatriz Roldan Cuenya, 2024. "Operando Raman spectroscopy uncovers hydroxide and CO species enhance ethanol selectivity during pulsed CO2 electroreduction," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    4. Pengtang Wang & Hao Yang & Cheng Tang & Yu Wu & Yao Zheng & Tao Cheng & Kenneth Davey & Xiaoqing Huang & Shi-Zhang Qiao, 2022. "Boosting electrocatalytic CO2–to–ethanol production via asymmetric C–C coupling," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    5. Hao Meng & Yusen Yang & Tianyao Shen & Zhiming Yin & Lei Wang & Wei Liu & Pan Yin & Zhen Ren & Lirong Zheng & Jian Zhang & Feng-Shou Xiao & Min Wei, 2023. "Designing Cu0−Cu+ dual sites for improved C−H bond fracture towards methanol steam reforming," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    6. Cheng Du & Joel P. Mills & Asfaw G. Yohannes & Wei Wei & Lei Wang & Siyan Lu & Jian-Xiang Lian & Maoyu Wang & Tao Guo & Xiyang Wang & Hua Zhou & Cheng-Jun Sun & John Z. Wen & Brian Kendall & Martin Co, 2023. "Cascade electrocatalysis via AgCu single-atom alloy and Ag nanoparticles in CO2 electroreduction toward multicarbon products," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    7. Jie Ding & Hong Yang & Xue-Lu Ma & Song Liu & Wei Liu & Qing Mao & Yanqiang Huang & Jun Li & Tao Zhang & Bin Liu, 2023. "A tin-based tandem electrocatalyst for CO2 reduction to ethanol with 80% selectivity," Nature Energy, Nature, vol. 8(12), pages 1386-1394, December.
    8. Xiao Chen & Shuaiqiang Jia & Jianxin Zhai & Jiapeng Jiao & Mengke Dong & Cheng Xue & Ting Deng & Hailian Cheng & Zhanghui Xia & Chunjun Chen & Xueqing Xing & Jianrong Zeng & Haihong Wu & Mingyuan He &, 2024. "Multivalent Cu sites synergistically adjust carbonaceous intermediates adsorption for electrocatalytic ethanol production," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    9. Kaiyuan Liu & Hao Shen & Zhiyi Sun & Qiang Zhou & Guoqiang Liu & Zhongti Sun & Wenxing Chen & Xin Gao & Pengwan Chen, 2025. "Transient pulsed discharge preparation of graphene aerogel supports asymmetric Cu cluster catalysts promote CO2 electroreduction," Nature Communications, Nature, vol. 16(1), pages 1-13, December.
    10. Kaihang Yue & Yanyang Qin & Honghao Huang & Zhuoran Lv & Mingzhi Cai & Yaqiong Su & Fuqiang Huang & Ya Yan, 2024. "Stabilized Cu0 -Cu1+ dual sites in a cyanamide framework for selective CO2 electroreduction to ethylene," Nature Communications, Nature, vol. 15(1), pages 1-12, 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. Shifu Wang & Fuhua Li & Jian Zhao & Yaqiong Zeng & Yifan Li & Zih-Yi Lin & Tsung-Ju Lee & Shuhui Liu & Xinyi Ren & Weijue Wang & Yusen Chen & Sung-Fu Hung & Ying-Rui Lu & Yi Cui & Xiaofeng Yang & Xuni, 2024. "Manipulating C-C coupling pathway in electrochemical CO2 reduction for selective ethylene and ethanol production over single-atom alloy catalyst," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    2. Kaiyuan Liu & Hao Shen & Zhiyi Sun & Qiang Zhou & Guoqiang Liu & Zhongti Sun & Wenxing Chen & Xin Gao & Pengwan Chen, 2025. "Transient pulsed discharge preparation of graphene aerogel supports asymmetric Cu cluster catalysts promote CO2 electroreduction," Nature Communications, Nature, vol. 16(1), pages 1-13, December.
    3. Jian Cheng & Ling Chen & Yanzhi Zhang & Min Wang & Zhangyi Zheng & Lin Jiang & Zhao Deng & Zhihe Wei & Mutian Ma & Likun Xiong & Wei Hua & Daqi Song & Wenxuan Huo & Yuebin Lian & Wenjun Yang & Fenglei, 2025. "Metal-organic double layer to stabilize selective multi-carbon electrosynthesis," Nature Communications, Nature, vol. 16(1), pages 1-15, December.
    4. Xiaodong Li & Li Li & Xiaohui Liu & Jiaqi Xu & Xingyuan Chu & Guangbo Chen & Dongqi Li & Mingchao Wang & Xia Wang & Chandrasekhar Naisa & Jing Gao & Yongfu Sun & Michael Grätzel & Xinliang Feng, 2025. "Designing multi-metal-site nanosheet catalysts for CO2 photoreduction to ethylene," Nature Communications, Nature, vol. 16(1), pages 1-11, December.
    5. Xinyang Gao & Yongjun Jiang & Jiyuan Liu & Guoshuai Shi & Chunlei Yang & Qinshang Xu & Yuanqing Yun & Yuluo Shen & Mingwei Chang & Chenyuan Zhu & Tingyu Lu & Yin Wang & Guanchen Du & Shuzhou Li & Shen, 2024. "Intermediate-regulated dynamic restructuring at Ag-Cu biphasic interface enables selective CO2 electroreduction to C2+ fuels," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    6. Kaihang Yue & Yanyang Qin & Honghao Huang & Zhuoran Lv & Mingzhi Cai & Yaqiong Su & Fuqiang Huang & Ya Yan, 2024. "Stabilized Cu0 -Cu1+ dual sites in a cyanamide framework for selective CO2 electroreduction to ethylene," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    7. Jiaqi Feng & Limin Wu & Xinning Song & Libing Zhang & Shunhan Jia & Xiaodong Ma & Xingxing Tan & Xinchen Kang & Qinggong Zhu & Xiaofu Sun & Buxing Han, 2024. "CO2 electrolysis to multi-carbon products in strong acid at ampere-current levels on La-Cu spheres with channels," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    8. Bo Peng & Hao She & Zihao Wei & Zhiyi Sun & Ziwei Deng & Zhongti Sun & Wenxing Chen, 2025. "Sulfur-doping tunes p-d orbital coupling over asymmetric Zn-Sn dual-atom for boosting CO2 electroreduction to formate," Nature Communications, Nature, vol. 16(1), pages 1-11, December.
    9. Weihua Guo & Siwei Zhang & Junjie Zhang & Haoran Wu & Yangbo Ma & Yun Song & Le Cheng & Liang Chang & Geng Li & Yong Liu & Guodan Wei & Lin Gan & Minghui Zhu & Shibo Xi & Xue Wang & Boris I. Yakobson , 2023. "Accelerating multielectron reduction at CuxO nanograins interfaces with controlled local electric field," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    10. Xin Yu Zhang & Zhen Xin Lou & Jiacheng Chen & Yuanwei Liu & Xuefeng Wu & Jia Yue Zhao & Hai Yang Yuan & Minghui Zhu & Sheng Dai & Hai Feng Wang & Chenghua Sun & Peng Fei Liu & Hua Gui Yang, 2023. "Direct OC-CHO coupling towards highly C2+ products selective electroreduction over stable Cu0/Cu2+ interface," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    11. Cheng Du & Joel P. Mills & Asfaw G. Yohannes & Wei Wei & Lei Wang & Siyan Lu & Jian-Xiang Lian & Maoyu Wang & Tao Guo & Xiyang Wang & Hua Zhou & Cheng-Jun Sun & John Z. Wen & Brian Kendall & Martin Co, 2023. "Cascade electrocatalysis via AgCu single-atom alloy and Ag nanoparticles in CO2 electroreduction toward multicarbon products," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    12. Yongxiang Liang & Jiankang Zhao & Yu Yang & Sung-Fu Hung & Jun Li & Shuzhen Zhang & Yong Zhao & An Zhang & Cheng Wang & Dominique Appadoo & Lei Zhang & Zhigang Geng & Fengwang Li & Jie Zeng, 2023. "Stabilizing copper sites in coordination polymers toward efficient electrochemical C-C coupling," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    13. Yaowei Huang & Da Xu & Shuai Deng & Meng Lin, 2024. "A hybrid electro-thermochemical device for methane production from the air," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    14. Xiaoyun Lin & Xiaowei Du & Shican Wu & Shiyu Zhen & Wei Liu & Chunlei Pei & Peng Zhang & Zhi-Jian Zhao & Jinlong Gong, 2024. "Machine learning-assisted dual-atom sites design with interpretable descriptors unifying electrocatalytic reactions," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    15. Jiaqi Feng & Libing Zhang & Shoujie Liu & Liang Xu & Xiaodong Ma & Xingxing Tan & Limin Wu & Qingli Qian & Tianbin Wu & Jianling Zhang & Xiaofu Sun & Buxing Han, 2023. "Modulating adsorbed hydrogen drives electrochemical CO2-to-C2 products," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    16. Qitao Chen & Baodong Mao & Yanhong Liu & Yunjie Zhou & Hui Huang & Song Wang & Longhua Li & Wei-Cheng Yan & Weidong Shi & Zhenhui Kang, 2024. "Designing 2D carbon dot nanoreactors for alcohol oxidation coupled with hydrogen evolution," Nature Communications, Nature, vol. 15(1), pages 1-14, December.
    17. Charles E. Creissen & Marc Fontecave, 2022. "Keeping sight of copper in single-atom catalysts for electrochemical carbon dioxide reduction," Nature Communications, Nature, vol. 13(1), pages 1-4, December.
    18. Zhiyuan Han & An Chen & Zejian Li & Mengtian Zhang & Zhilong Wang & Lixue Yang & Runhua Gao & Yeyang Jia & Guanjun Ji & Zhoujie Lao & Xiao Xiao & Kehao Tao & Jing Gao & Wei Lv & Tianshuai Wang & Jinji, 2024. "Machine learning-based design of electrocatalytic materials towards high-energy lithium||sulfur batteries development," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    19. SJ, Balaji & Babu, Suresh Chandra & Pal, Suresh, 2021. "Understanding Science and Policy Making in Agriculture: A Machine Learning Application for India," 2021 Conference, August 17-31, 2021, Virtual 315227, International Association of Agricultural Economists.
    20. Yong Zhang & Feifei Chen & Xinyi Yang & Yiran Guo & Xinghua Zhang & Hong Dong & Weihua Wang & Feng Lu & Zunming Lu & Hui Liu & Hui Liu & Yao Xiao & Yahui Cheng, 2025. "Electronic metal-support interaction modulates Cu electronic structures for CO2 electroreduction to desired products," Nature Communications, Nature, vol. 16(1), pages 1-12, 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_s41467-025-61189-z. 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.