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Specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media

The electrolysis of nitrate reduction to ammonia (NRA) is promising for obtaining value-added chemicals and mitigating environmental concerns. Recently, catalysts with high-performance ammonia synthesis from nitrate has been achieved under alkaline or acidic conditions. However, NRA in neutral solut...

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Autores principales: Liu, Chunlei, Zhang, Gong, Zhang, Wei, Gu, Zhenao, Zhu, Guibing
Formato: Online Artículo Texto
Lenguaje:English
Publicado: National Academy of Sciences 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9934295/
https://www.ncbi.nlm.nih.gov/pubmed/36626554
http://dx.doi.org/10.1073/pnas.2209979120
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author Liu, Chunlei
Zhang, Gong
Zhang, Wei
Gu, Zhenao
Zhu, Guibing
author_facet Liu, Chunlei
Zhang, Gong
Zhang, Wei
Gu, Zhenao
Zhu, Guibing
author_sort Liu, Chunlei
collection PubMed
description The electrolysis of nitrate reduction to ammonia (NRA) is promising for obtaining value-added chemicals and mitigating environmental concerns. Recently, catalysts with high-performance ammonia synthesis from nitrate has been achieved under alkaline or acidic conditions. However, NRA in neutral solution still suffers from the low yield rate and selectivity of ammonia due to the low binding affinity and nucleophilicity of NO(3)(−). Here, we confirmed that the in-situ-generated Fe(II) ions existed as specifically adsorbed cations in the inner Helmholtz plane (IHP) with a low redox potential. Inspired by this, a strategy (Fe-IHP strategy) was proposed to enhance NRA activity by tuning the affinity of the electrode–electrolyte interface. The specifically adsorbed Fe(II) ions [SA-Fe(II)] greatly alleviated the electrostatic repulsion around the interfaceresulting in a 10-fold lower in the adsorption-free energy of NO(3)(−) when compared to the case without SA-Fe(II). Meanwhile, the modulated interface accelerated the kinetic mass transfer process by 25 folds compared to the control. Under neutral conditions, a Faraday efficiency of 99.6%, a selectivity of 99%, and an extremely high NH(3) yield rate of 485.8 mmol h(−1) g(−1) (FeOOH) were achieved. Theoretical calculations and in-situ Raman spectroscopy confirmed the electron-rich state of the SA-Fe(II) donated to p orbitals of N atom and favored the hydrogenation of *NO to *NOH for promoting the formation of high-selectivity ammonia. In sum, these findings complement the textbook on the specific adsorption of cations and provide insights into the design of low-cost NRA catalysts with efficient ammonia synthesis.
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spelling pubmed-99342952023-07-10 Specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media Liu, Chunlei Zhang, Gong Zhang, Wei Gu, Zhenao Zhu, Guibing Proc Natl Acad Sci U S A Physical Sciences The electrolysis of nitrate reduction to ammonia (NRA) is promising for obtaining value-added chemicals and mitigating environmental concerns. Recently, catalysts with high-performance ammonia synthesis from nitrate has been achieved under alkaline or acidic conditions. However, NRA in neutral solution still suffers from the low yield rate and selectivity of ammonia due to the low binding affinity and nucleophilicity of NO(3)(−). Here, we confirmed that the in-situ-generated Fe(II) ions existed as specifically adsorbed cations in the inner Helmholtz plane (IHP) with a low redox potential. Inspired by this, a strategy (Fe-IHP strategy) was proposed to enhance NRA activity by tuning the affinity of the electrode–electrolyte interface. The specifically adsorbed Fe(II) ions [SA-Fe(II)] greatly alleviated the electrostatic repulsion around the interfaceresulting in a 10-fold lower in the adsorption-free energy of NO(3)(−) when compared to the case without SA-Fe(II). Meanwhile, the modulated interface accelerated the kinetic mass transfer process by 25 folds compared to the control. Under neutral conditions, a Faraday efficiency of 99.6%, a selectivity of 99%, and an extremely high NH(3) yield rate of 485.8 mmol h(−1) g(−1) (FeOOH) were achieved. Theoretical calculations and in-situ Raman spectroscopy confirmed the electron-rich state of the SA-Fe(II) donated to p orbitals of N atom and favored the hydrogenation of *NO to *NOH for promoting the formation of high-selectivity ammonia. In sum, these findings complement the textbook on the specific adsorption of cations and provide insights into the design of low-cost NRA catalysts with efficient ammonia synthesis. National Academy of Sciences 2023-01-10 2023-01-17 /pmc/articles/PMC9934295/ /pubmed/36626554 http://dx.doi.org/10.1073/pnas.2209979120 Text en Copyright © 2023 the Author(s). Published by PNAS. https://creativecommons.org/licenses/by-nc-nd/4.0/This article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND) (https://creativecommons.org/licenses/by-nc-nd/4.0/) .
spellingShingle Physical Sciences
Liu, Chunlei
Zhang, Gong
Zhang, Wei
Gu, Zhenao
Zhu, Guibing
Specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media
title Specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media
title_full Specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media
title_fullStr Specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media
title_full_unstemmed Specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media
title_short Specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media
title_sort specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media
topic Physical Sciences
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9934295/
https://www.ncbi.nlm.nih.gov/pubmed/36626554
http://dx.doi.org/10.1073/pnas.2209979120
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