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Single-zinc vacancy unlocks high-rate H2O2 electrosynthesis from mixed dioxygen beyond Le Chatelier principle

Author

Listed:
  • Qi Huang

    (Nanjing University of Science and Technology, Ministry of Education)

  • Baokai Xia

    (Nanjing University of Science and Technology, Ministry of Education)

  • Ming Li

    (Nanjing University of Science and Technology, Ministry of Education)

  • Hongxin Guan

    (Nanjing University of Science and Technology, Ministry of Education)

  • Markus Antonietti

    (Max Planck Institute of Colloids and Interfaces)

  • Sheng Chen

    (Nanjing University of Science and Technology, Ministry of Education
    Max Planck Institute of Colloids and Interfaces)

Abstract

Le Chatelier’s principle is a basic rule in textbook defining the correlations of reaction activities and specific system parameters (like concentrations), serving as the guideline for regulating chemical/catalytic systems. Here we report a model system breaking this constraint in O2 electroreduction in mixed dioxygen. We unravel the central role of creating single-zinc vacancies in a crystal structure that leads to enzyme-like binding of the catalyst with enhanced selectivity to O2, shifting the reaction pathway from Langmuir-Hinshelwood to an upgraded triple-phase Eley-Rideal mechanism. The model system shows minute activity alteration of H2O2 yields (25.89~24.99 mol gcat−1 h−1) and Faradaic efficiencies (92.5%~89.3%) in the O2 levels of 100%~21% at the current density of 50~300 mA cm−2, which apparently violate macroscopic Le Chatelier’s reaction kinetics. A standalone prototype device is built for high-rate H2O2 production from atmospheric air, achieving the highest Faradaic efficiencies of 87.8% at 320 mA cm−2, overtaking the state-of-the-art catalysts and approaching the theoretical limit for direct air electrolysis (~345.8 mA cm−2). Further techno-economics analyses display the use of atmospheric air feedstock affording 21.7% better economics as comparison to high-purity O2, achieving the lowest H2O2 capital cost of 0.3 $ Kg−1. Given the recent surge of demonstrations on tailoring chemical/catalytic systems based on the Le Chatelier’s principle, the present finding would have general implications, allowing for leveraging systems “beyond” this classical rule.

Suggested Citation

  • Qi Huang & Baokai Xia & Ming Li & Hongxin Guan & Markus Antonietti & Sheng Chen, 2024. "Single-zinc vacancy unlocks high-rate H2O2 electrosynthesis from mixed dioxygen beyond Le Chatelier principle," Nature Communications, Nature, vol. 15(1), pages 1-10, December.
  • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-024-48256-7
    DOI: 10.1038/s41467-024-48256-7
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    References listed on IDEAS

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    1. Zhi Wen Chen & Jian Li & Pengfei Ou & Jianan Erick Huang & Zi Wen & LiXin Chen & Xue Yao & GuangMing Cai & Chun Cheng Yang & Chandra Veer Singh & Qing Jiang, 2024. "Unusual Sabatier principle on high entropy alloy catalysts for hydrogen evolution reactions," Nature Communications, Nature, vol. 15(1), pages 1-11, December.
    2. 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.
    3. Haeun Shin & Kentaro U. Hansen & Feng Jiao, 2021. "Techno-economic assessment of low-temperature carbon dioxide electrolysis," Nature Sustainability, Nature, vol. 4(10), pages 911-919, October.
    4. Jinwei Xu & Xueli Zheng & Zhiping Feng & Zhiyi Lu & Zewen Zhang & William Huang & Yanbin Li & Djordje Vuckovic & Yuanqing Li & Sheng Dai & Guangxu Chen & Kecheng Wang & Hansen Wang & James K. Chen & W, 2021. "Organic wastewater treatment by a single-atom catalyst and electrolytically produced H2O2," Nature Sustainability, Nature, vol. 4(3), pages 233-241, March.
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