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Proton Donors Induce a Differential Transport Effect for Selectivity toward Ammonia in Lithium-Mediated Nitrogen Reduction

Cite this: ACS Catal. 2022, 12, 9, 5197–5208
Publication Date (Web):April 15, 2022
https://doi.org/10.1021/acscatal.2c00389
Copyright © 2022 American Chemical Society

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    Abstract

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    Alternative approaches for producing ammonia are necessary to reduce the environmental impact of its production. The lithium-mediated electrochemical nitrogen reduction reaction (LM-NRR) is one attractive alternative method for producing ammonia at small scales in a distributed process. This process requires a proton donor in the electrolyte to produce ammonia from nitrogen, but the role of the proton donor in selective ammonia production is not well understood. In this work, we experimentally tested several classes of proton donors for the ability to promote LM-NRR. We found that a wide array of alcohols can promote nitrogen reduction and that n-butanol leads to the highest ammonia Faradaic efficiencies. Among the tested proton donors, even slight changes in the proton donor structure can significantly affect the yield of ammonia. In addition, most active proton donors exhibit a thresholding behavior as a function of their concentration, where the selectivity toward ammonia increases dramatically above a certain concentration of the proton donor. We found evidence to imply that these effects could be due to the proton-donor-induced changes in the properties of the solid electrolyte interphase (SEI), which lead to changes in the diffusion of relevant species through the SEI to the reactive electrode. By selectively allowing for diffusion of nitrogen over the proton donor to the electrode, the SEI can promote selective nitrogen reduction to ammonia. A coupled kinetic transport model of the process was proposed to explain the observed trends and to predict ammonia production as a function of operating conditions.

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    This article is cited by 17 publications.

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    2. Eric J. McShane, Valerie A. Niemann, Peter Benedek, Xianbiao Fu, Adam C. Nielander, Ib Chorkendorff, Thomas F. Jaramillo, Matteo Cargnello. Quantifying Influence of the Solid-Electrolyte Interphase in Ammonia Electrosynthesis. ACS Energy Letters 2023, Article ASAP.
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    14. Yuxian Fan, Xiang Xue, Lingyue Zhu, Yuwei Qin, Dandan Yuan, Di Gu, Baohui Wang. The state-of-the-art in the electroreduction of NO x for the production of ammonia in aqueous and nonaqueous media at ambient conditions: a review. New Journal of Chemistry 2023, 11 https://doi.org/10.1039/D2NJ06362J
    15. O. Westhead, M. Spry, A. Bagger, Z. Shen, H. Yadegari, S. Favero, R. Tort, M. Titirici, M. P. Ryan, R. Jervis, Y. Katayama, A. Aguadero, A. Regoutz, A. Grimaud, I. E. L. Stephens. The role of ion solvation in lithium mediated nitrogen reduction. Journal of Materials Chemistry A 2023, 408 https://doi.org/10.1039/D2TA07686A
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    17. Xianbiao Fu, Jiahao Zhang, Yijin Kang. Recent advances and challenges of electrochemical ammonia synthesis. Chem Catalysis 2022, 2 (10) , 2590-2613. https://doi.org/10.1016/j.checat.2022.09.001

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