IDEAS home Printed from https://ideas.repec.org/a/nat/natcom/v16y2025i1d10.1038_s41467-025-58628-2.html
   My bibliography  Save this article

Internal hydrogen-bond enhanced two-electron oxygen reduction reaction for π-d conjugated metal-organic framework to H2O2 synthesis

Author

Listed:
  • Zhiyuan Sang

    (Tianjin University)

  • Yuqian Qiao

    (Peking University)

  • Rui Chen

    (Tianjin University)

  • Lichang Yin

    (Chinese Academy of Science)

  • Feng Hou

    (Tianjin University)

  • Ji Liang

    (Tianjin University)

Abstract

Tailoring the electronic structure of electrocatalysts for oxygen reduction reaction (ORR) has been widely adopted to optimize their performance. However, the steric effect originating from the layered or crystal structure of a catalyst is often neglected. Herein, we demonstrate the importance of such steric effect in a one-dimensional π-d conjugated metal-organic framework with Ni-(NH)4 nodes (Ni-BTA) for optimizing its electrocatalytic performance, where the activity and selectivity towards two-electron ORR for H2O2 production are largely enhanced. Theoretical simulation and in-situ characterization demonstrate the formation of inter-layer H-bonds between *OOH intermediates and -N-H groups in the adjacent top layers of the Ni-sites, enhancing the *OOH binding energy to an optimum value. Thus, the as-prepared Ni-BTA catalyst exhibits an outstanding electrocatalytic 2e−-ORR performances under neutral and alkaline conditions (e.g., >85% H2O2 selectivity from −0.1-0.4 V vs. RHE and >13.5 mol g−1 h−1 H2O2 yield in neutral electrolytes), also showing great potential on water treatment and disinfection. Here, we highlight the alternative avenues for utilizing the non-coordinated structure to regulate the catalytic performance, thus providing opportunities for the design of catalysts and beyond.

Suggested Citation

  • Zhiyuan Sang & Yuqian Qiao & Rui Chen & Lichang Yin & Feng Hou & Ji Liang, 2025. "Internal hydrogen-bond enhanced two-electron oxygen reduction reaction for π-d conjugated metal-organic framework to H2O2 synthesis," Nature Communications, Nature, vol. 16(1), pages 1-12, December.
  • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-58628-2
    DOI: 10.1038/s41467-025-58628-2
    as

    Download full text from publisher

    File URL: https://www.nature.com/articles/s41467-025-58628-2
    File Function: Abstract
    Download Restriction: no

    File URL: https://libkey.io/10.1038/s41467-025-58628-2?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. Wei Peng & Jiaxin Liu & Xiaoqing Liu & Liqun Wang & Lichang Yin & Haotian Tan & Feng Hou & Ji Liang, 2023. "Facilitating two-electron oxygen reduction with pyrrolic nitrogen sites for electrochemical hydrogen peroxide production," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    2. Qiang Sun & Nicholas J. Oliveira & Soonho Kwon & Sergiy Tyukhtenko & Jason J. Guo & Nathalie Myrthil & Steven A. Lopez & Ian Kendrick & Sanjeev Mukerjee & Lu Ma & Steven N. Ehrlich & Jingkun Li & Will, 2023. "Understanding hydrogen electrocatalysis by probing the hydrogen-bond network of water at the electrified Pt–solution interface," Nature Energy, Nature, vol. 8(8), pages 859-869, August.
    3. Shiming Yu & Xing Cheng & Yueshuai Wang & Bo Xiao & Yiran Xing & Jun Ren & Yue Lu & Hongyi Li & Chunqiang Zhuang & Ge Chen, 2022. "High activity and selectivity of single palladium atom for oxygen hydrogenation to H2O2," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    4. Peike Cao & Xie Quan & Xiaowa Nie & Kun Zhao & Yanming Liu & Shuo Chen & Hongtao Yu & Jingguang G. Chen, 2023. "Metal single-site catalyst design for electrocatalytic production of hydrogen peroxide at industrial-relevant currents," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    5. Jiannan Du & Guokang Han & Wei Zhang & Lingfeng Li & Yuqi Yan & Yaoxuan Shi & Xue Zhang & Lin Geng & Zhijiang Wang & Yueping Xiong & Geping Yin & Chunyu Du, 2023. "CoIn dual-atom catalyst for hydrogen peroxide production via oxygen reduction reaction in acid," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    6. Kun Jiang & Seoin Back & Austin J. Akey & Chuan Xia & Yongfeng Hu & Wentao Liang & Diane Schaak & Eli Stavitski & Jens K. Nørskov & Samira Siahrostami & Haotian Wang, 2019. "Highly selective oxygen reduction to hydrogen peroxide on transition metal single atom coordination," Nature Communications, Nature, vol. 10(1), pages 1-11, December.
    7. Hsiang-Ting Lien & Sun-Tang Chang & Po-Tuan Chen & Deniz P. Wong & Yu-Chung Chang & Ying-Rei Lu & Chung-Li Dong & Chen-Hao Wang & Kuei-Hsien Chen & Li-Chyong Chen, 2020. "Probing the active site in single-atom oxygen reduction catalysts via operando X-ray and electrochemical spectroscopy," Nature Communications, Nature, vol. 11(1), pages 1-8, December.
    8. Yang Xia & Xunhua Zhao & Chuan Xia & Zhen-Yu Wu & Peng Zhu & Jung Yoon (Timothy) Kim & Xiaowan Bai & Guanhui Gao & Yongfeng Hu & Jun Zhong & Yuanyue Liu & Haotian Wang, 2021. "Highly active and selective oxygen reduction to H2O2 on boron-doped carbon for high production rates," Nature Communications, Nature, vol. 12(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. Xiaofeng Xiao & Zechao Zhuang & Shuhu Yin & Jiexin Zhu & Tao Gan & Ruohan Yu & Jinsong Wu & Xiaochun Tian & Yanxia Jiang & Dingsheng Wang & Feng Zhao, 2024. "Topological transformation of microbial proteins into iron single-atom sites for selective hydrogen peroxide electrosynthesis," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    2. Wei Peng & Jiaxin Liu & Xiaoqing Liu & Liqun Wang & Lichang Yin & Haotian Tan & Feng Hou & Ji Liang, 2023. "Facilitating two-electron oxygen reduction with pyrrolic nitrogen sites for electrochemical hydrogen peroxide production," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    3. Zhirong Zhang & Chen Feng & Dongdi Wang & Shiming Zhou & Ruyang Wang & Sunpei Hu & Hongliang Li & Ming Zuo & Yuan Kong & Jun Bao & Jie Zeng, 2022. "Selectively anchoring single atoms on specific sites of supports for improved oxygen evolution," Nature Communications, Nature, vol. 13(1), pages 1-10, December.
    4. Jun Qi & Yadong Du & Qi Yang & Na Jiang & Jiachun Li & Yi Ma & Yangjun Ma & Xin Zhao & Jieshan Qiu, 2023. "Energy-saving and product-oriented hydrogen peroxide electrosynthesis enabled by electrochemistry pairing and product engineering," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    5. Qianjun Zhi & Rong Jiang & Xiya Yang & Yucheng Jin & Dongdong Qi & Kang Wang & Yunpeng Liu & Jianzhuang Jiang, 2024. "Dithiine-linked metalphthalocyanine framework with undulated layers for highly efficient and stable H2O2 electroproduction," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
    6. Xiao Zhou & Yuan Min & Changming Zhao & Cai Chen & Ming-Kun Ke & Shi-Lin Xu & Jie-Jie Chen & Yuen Wu & Han-Qing Yu, 2024. "Constructing sulfur and oxygen super-coordinated main-group electrocatalysts for selective and cumulative H2O2 production," Nature Communications, Nature, vol. 15(1), pages 1-13, December.
    7. Peike Cao & Xie Quan & Xiaowa Nie & Kun Zhao & Yanming Liu & Shuo Chen & Hongtao Yu & Jingguang G. Chen, 2023. "Metal single-site catalyst design for electrocatalytic production of hydrogen peroxide at industrial-relevant currents," Nature Communications, Nature, vol. 14(1), pages 1-12, December.
    8. Ping Liu & Teng Liang & Yutong Li & Ziqing Zhang & Zhuo Li & Ji Bian & Liqiang Jing, 2024. "Photocatalytic H2O2 production over boron-doped g-C3N4 containing coordinatively unsaturated FeOOH sites and CoOx clusters," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    9. Che Lah, Nurul Akmal, 2021. "Late transition metal nanocomplexes: Applications for renewable energy conversion and storage," Renewable and Sustainable Energy Reviews, Elsevier, vol. 145(C).
    10. Zhen Zhang & Zhenyu Xing & Xianglin Luo & Chong Cheng & Xikui Liu, 2025. "Densely populated macrocyclic dicobalt sites in ladder polymers for low-overpotential oxygen reduction catalysis," Nature Communications, Nature, vol. 16(1), pages 1-12, December.
    11. Jiannan Du & Guokang Han & Wei Zhang & Lingfeng Li & Yuqi Yan & Yaoxuan Shi & Xue Zhang & Lin Geng & Zhijiang Wang & Yueping Xiong & Geping Yin & Chunyu Du, 2023. "CoIn dual-atom catalyst for hydrogen peroxide production via oxygen reduction reaction in acid," Nature Communications, Nature, vol. 14(1), pages 1-10, December.
    12. Longxiang Liu & Liqun Kang & Jianrui Feng & David G. Hopkinson & Christopher S. Allen & Yeshu Tan & Hao Gu & Iuliia Mikulska & Veronica Celorrio & Diego Gianolio & Tianlei Wang & Liquan Zhang & Kaiqi , 2024. "Atomically dispersed asymmetric cobalt electrocatalyst for efficient hydrogen peroxide production in neutral media," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    13. Ruilin Wang & Hao Luo & Chengyu Duan & Huimin Liu & Mengdi Sun & Quan Zhou & Zheshun Ou & Yinglong Lu & Guanghui Luo & Jimmy C. Yu & Zhuofeng Hu, 2024. "Crystal OH mediating pathway for hydrogen peroxide production via two-electron water oxidation in non-carbonate electrolytes," Nature Communications, Nature, vol. 15(1), pages 1-12, December.
    14. Qilong Wu & Haiyuan Zou & Xin Mao & Jinghan He & Yanmei Shi & Shuangming Chen & Xuecheng Yan & Liyun Wu & Chengguang Lang & Bin Zhang & Li Song & Xin Wang & Aijun Du & Qin Li & Yi Jia & Jun Chen & Xia, 2023. "Unveiling the dynamic active site of defective carbon-based electrocatalysts for hydrogen peroxide production," Nature Communications, Nature, vol. 14(1), pages 1-11, December.
    15. Jinxing Chen & Qian Ma & Xiliang Zheng & Youxing Fang & Jin Wang & Shaojun Dong, 2022. "Kinetically restrained oxygen reduction to hydrogen peroxide with nearly 100% selectivity," Nature Communications, Nature, vol. 13(1), pages 1-9, December.
    16. Yuchen Hao & Liwei Chen & Haodong Liu & Wenfeng Nie & Xiangjie Ge & Jiani Li & Hui-Zi Huang & Chao Sun & Cuncai Lv & Shangbo Ning & Linjie Gao & Yaguang Li & Shufang Wang & An-Xiang Yin & Bo Wang & Ji, 2025. "Continuous photo-oxidation of methane to methanol at an atomically tailored reticular gas-solid interface," Nature Communications, Nature, vol. 16(1), pages 1-13, December.
    17. Liangbo Xie & Pengfei Wang & Yi Li & Dongpeng Zhang & Denghui Shang & Wenwen Zheng & Yuguo Xia & Sihui Zhan & Wenping Hu, 2022. "Pauling-type adsorption of O2 induced electrocatalytic singlet oxygen production on N–CuO for organic pollutants degradation," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    18. Arthur G. Fink & Roxanna S. Delima & Alexandra R. Rousseau & Camden Hunt & Natalie E. LeSage & Aoxue Huang & Monika Stolar & Curtis P. Berlinguette, 2024. "Indirect H2O2 synthesis without H2," Nature Communications, Nature, vol. 15(1), pages 1-9, December.
    19. Xiao Zhang & Xunhua Zhao & Peng Zhu & Zachary Adler & Zhen-Yu Wu & Yuanyue Liu & Haotian Wang, 2022. "Electrochemical oxygen reduction to hydrogen peroxide at practical rates in strong acidic media," Nature Communications, Nature, vol. 13(1), pages 1-11, December.
    20. Yuhan Wu & Yuying Zhao & Qixin Yuan & Hao Sun & Ao Wang & Kang Sun & Geoffrey I. N. Waterhouse & Ziyun Wang & Jingjie Wu & Jianchun Jiang & Mengmeng Fan, 2024. "Electrochemically synthesized H2O2 at industrial-level current densities enabled by in situ fabricated few-layer boron nanosheets," Nature Communications, Nature, vol. 15(1), pages 1-13, 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_s41467-025-58628-2. 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.