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Wide-pH-range adaptable ammonia electrosynthesis from nitrate on Cu-Pd interfaces

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Abstract

Ammonia production via electrochemical nitrate reduction is essential for environmental protection and the emerging hydrogen economy. Complex nitrate wastewater with a wide pH range calls for flexible catalysts with high selectivity. A high Faradaic efficiency (FE) of NH3 cannot be obtained under strong acid or alkaline conditions due to the uncontrollable adsorption energy and coverage of hydrogen species (H*) on active sites. This article describes the design and fabrication of a copper-palladium (Cu-Pd) alloy nanocrystal catalyst that inhibits H2 and nitrite generation in electrolytes with different nitrate concentrations and varied pH. The interfacial sites of Cu-Pd alloys could enhance the adsorption energy and coverage of H* while increasing the reaction rate constant of NO2*-to-NO*, which achieves a rapid conversion of NO2* along with a decreased FE of NO2−. Under ambient conditions, optimal FE(NH3) is close to 100% at a wide pH range, with the solar-to-chemical conversion efficiency approaching 4.29%. The combination of thermodynamics and kinetics investigations would offer new insights into the reduction mechanism of NO2* for further development of nitrate reduction.

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Acknowledgements

This work was supported by the National Key R&D Program of China (2021YFA1500804), the National Natural Science Foundation of China (22121004, 51861125104), the Natural Science Foundation of Tianjin City (18JCJQJC47500), Haihe Laboratory of Sustainable Chemical Transformations, the Program of Introducing Talents of Discipline to Universities (BP0618007) and the Xplorer Prize.

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Author notes

  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin, 300072, China

    Yongtao Wang, Peng Zhang, Xiaoyun Lin, Gong Zhang, Hui Gao, Qingzhen Wang, Zhi-Jian Zhao, Tuo Wang & Jinlong Gong

  2. Collaborative Innovation Center of Chemical Science and Engineering, Tianjin, 300072, China

    Yongtao Wang, Peng Zhang, Xiaoyun Lin, Gong Zhang, Hui Gao, Qingzhen Wang, Zhi-Jian Zhao, Tuo Wang & Jinlong Gong

  3. Haihe Laboratory of Sustainable Chemical Transformations, Tianjin, 300192, China

    Yongtao Wang, Peng Zhang, Xiaoyun Lin, Gong Zhang, Hui Gao, Qingzhen Wang, Zhi-Jian Zhao, Tuo Wang & Jinlong Gong

  4. International Campus of Tianjin University, Joint School of National University of Singapore and Tianjin University, Binhai New City, Fuzhou, 350207, China

    Tuo Wang

Authors
  1. Yongtao Wang
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  2. Peng Zhang
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Correspondence to Tuo Wang.

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Supporting information The supporting information is available online at https://chem.scichina.com and https://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Wang, Y., Zhang, P., Lin, X. et al. Wide-pH-range adaptable ammonia electrosynthesis from nitrate on Cu-Pd interfaces. Sci. China Chem. 66, 913–922 (2023). https://doi.org/10.1007/s11426-022-1411-0

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  • DOI: https://doi.org/10.1007/s11426-022-1411-0

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