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The origin of overpotential in lithium-mediated nitrogen reduction

The verification of the lithium-mediated nitrogen reduction system in 2019 has led to an explosion in the literature focussing on improving the metrics of faradaic efficiency, stability, and activity. However, while the literature acknowledges the vast intrinsic overpotential for nitrogen reduction...

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Autores principales: Westhead, O., Tort, R., Spry, M., Rietbrock, J., Jervis, R., Grimaud, A., Bagger, A., Stephens, I. E. L.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10354832/
https://www.ncbi.nlm.nih.gov/pubmed/37089070
http://dx.doi.org/10.1039/d2fd00156j
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author Westhead, O.
Tort, R.
Spry, M.
Rietbrock, J.
Jervis, R.
Grimaud, A.
Bagger, A.
Stephens, I. E. L.
author_facet Westhead, O.
Tort, R.
Spry, M.
Rietbrock, J.
Jervis, R.
Grimaud, A.
Bagger, A.
Stephens, I. E. L.
author_sort Westhead, O.
collection PubMed
description The verification of the lithium-mediated nitrogen reduction system in 2019 has led to an explosion in the literature focussing on improving the metrics of faradaic efficiency, stability, and activity. However, while the literature acknowledges the vast intrinsic overpotential for nitrogen reduction due to the reliance on in situ lithium plating, it has thus far been difficult to accurately quantify this overpotential and effectively analyse further voltage losses. In this work, we present a simple method for determining the Reversible Hydrogen Electrode (RHE) potential in the lithium-mediated nitrogen reduction system. This method allows for an investigation of the Nernst equation and reveals sources of potential losses. These are namely the solvation of the lithium ion in the electrolyte and resistive losses due to the formation of the solid electrolyte interphase. The minimum observed overpotential was achieved in a 0.6 M LiClO(4), 0.5 vol% ethanol in tetrahydrofuran electrolyte. This was −3.59 ± 0.07 V vs. RHE, with a measured faradaic efficiency of 6.5 ± 0.2%. Our method allows for easy comparison between the lithium-mediated system and other nitrogen reduction paradigms, including biological and homogeneous mechanisms.
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spelling pubmed-103548322023-07-20 The origin of overpotential in lithium-mediated nitrogen reduction Westhead, O. Tort, R. Spry, M. Rietbrock, J. Jervis, R. Grimaud, A. Bagger, A. Stephens, I. E. L. Faraday Discuss Chemistry The verification of the lithium-mediated nitrogen reduction system in 2019 has led to an explosion in the literature focussing on improving the metrics of faradaic efficiency, stability, and activity. However, while the literature acknowledges the vast intrinsic overpotential for nitrogen reduction due to the reliance on in situ lithium plating, it has thus far been difficult to accurately quantify this overpotential and effectively analyse further voltage losses. In this work, we present a simple method for determining the Reversible Hydrogen Electrode (RHE) potential in the lithium-mediated nitrogen reduction system. This method allows for an investigation of the Nernst equation and reveals sources of potential losses. These are namely the solvation of the lithium ion in the electrolyte and resistive losses due to the formation of the solid electrolyte interphase. The minimum observed overpotential was achieved in a 0.6 M LiClO(4), 0.5 vol% ethanol in tetrahydrofuran electrolyte. This was −3.59 ± 0.07 V vs. RHE, with a measured faradaic efficiency of 6.5 ± 0.2%. Our method allows for easy comparison between the lithium-mediated system and other nitrogen reduction paradigms, including biological and homogeneous mechanisms. The Royal Society of Chemistry 2022-11-29 /pmc/articles/PMC10354832/ /pubmed/37089070 http://dx.doi.org/10.1039/d2fd00156j Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Westhead, O.
Tort, R.
Spry, M.
Rietbrock, J.
Jervis, R.
Grimaud, A.
Bagger, A.
Stephens, I. E. L.
The origin of overpotential in lithium-mediated nitrogen reduction
title The origin of overpotential in lithium-mediated nitrogen reduction
title_full The origin of overpotential in lithium-mediated nitrogen reduction
title_fullStr The origin of overpotential in lithium-mediated nitrogen reduction
title_full_unstemmed The origin of overpotential in lithium-mediated nitrogen reduction
title_short The origin of overpotential in lithium-mediated nitrogen reduction
title_sort origin of overpotential in lithium-mediated nitrogen reduction
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10354832/
https://www.ncbi.nlm.nih.gov/pubmed/37089070
http://dx.doi.org/10.1039/d2fd00156j
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