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H(2) activation by hydrogenase-inspired NiFe catalyst using frustrated Lewis pair: effect of buffer and halide ion in the heterolytic H–H bond cleavage

Hydrogen is a clean fuel alternative to fossil fuels, and it is vital to develop catalysts for its efficient activation and production. We investigate the reaction mechanism of H(2) activation in an aqueous solution by the recently developed NiFe complex (Ogo et al. Sci. Adv. 2020, 6, eaaz8181) usin...

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Autores principales: Isegawa, Miho, Matsumoto, Takahiro, Ogo, Seiji
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9038005/
https://www.ncbi.nlm.nih.gov/pubmed/35480737
http://dx.doi.org/10.1039/d1ra05928a
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author Isegawa, Miho
Matsumoto, Takahiro
Ogo, Seiji
author_facet Isegawa, Miho
Matsumoto, Takahiro
Ogo, Seiji
author_sort Isegawa, Miho
collection PubMed
description Hydrogen is a clean fuel alternative to fossil fuels, and it is vital to develop catalysts for its efficient activation and production. We investigate the reaction mechanism of H(2) activation in an aqueous solution by the recently developed NiFe complex (Ogo et al. Sci. Adv. 2020, 6, eaaz8181) using density functional theory (DFT) calculation. Our computational results showed that H(2) is activated using frustrated Lewis pair. That is, H(2) binds to the Fe site of the NiFe complex, acting as a Lewis acid, while the added buffer, acting as Lewis base, abstracts protons to form a hydride complex. Furthermore, the higher basicity in the proton abstraction reaction characterises reaction more exergonic and lowers the reaction barrier. In addition, in the proton abstraction by the water molecule, the reaction barrier was lowered when anion such as Cl(−) is in the vicinity of the water. Understanding the chemical species that contribute to the catalytic process in cooperation with the metal catalyst at the atomic level should help to maximise the function of the catalyst.
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spelling pubmed-90380052022-04-26 H(2) activation by hydrogenase-inspired NiFe catalyst using frustrated Lewis pair: effect of buffer and halide ion in the heterolytic H–H bond cleavage Isegawa, Miho Matsumoto, Takahiro Ogo, Seiji RSC Adv Chemistry Hydrogen is a clean fuel alternative to fossil fuels, and it is vital to develop catalysts for its efficient activation and production. We investigate the reaction mechanism of H(2) activation in an aqueous solution by the recently developed NiFe complex (Ogo et al. Sci. Adv. 2020, 6, eaaz8181) using density functional theory (DFT) calculation. Our computational results showed that H(2) is activated using frustrated Lewis pair. That is, H(2) binds to the Fe site of the NiFe complex, acting as a Lewis acid, while the added buffer, acting as Lewis base, abstracts protons to form a hydride complex. Furthermore, the higher basicity in the proton abstraction reaction characterises reaction more exergonic and lowers the reaction barrier. In addition, in the proton abstraction by the water molecule, the reaction barrier was lowered when anion such as Cl(−) is in the vicinity of the water. Understanding the chemical species that contribute to the catalytic process in cooperation with the metal catalyst at the atomic level should help to maximise the function of the catalyst. The Royal Society of Chemistry 2021-08-23 /pmc/articles/PMC9038005/ /pubmed/35480737 http://dx.doi.org/10.1039/d1ra05928a Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
Isegawa, Miho
Matsumoto, Takahiro
Ogo, Seiji
H(2) activation by hydrogenase-inspired NiFe catalyst using frustrated Lewis pair: effect of buffer and halide ion in the heterolytic H–H bond cleavage
title H(2) activation by hydrogenase-inspired NiFe catalyst using frustrated Lewis pair: effect of buffer and halide ion in the heterolytic H–H bond cleavage
title_full H(2) activation by hydrogenase-inspired NiFe catalyst using frustrated Lewis pair: effect of buffer and halide ion in the heterolytic H–H bond cleavage
title_fullStr H(2) activation by hydrogenase-inspired NiFe catalyst using frustrated Lewis pair: effect of buffer and halide ion in the heterolytic H–H bond cleavage
title_full_unstemmed H(2) activation by hydrogenase-inspired NiFe catalyst using frustrated Lewis pair: effect of buffer and halide ion in the heterolytic H–H bond cleavage
title_short H(2) activation by hydrogenase-inspired NiFe catalyst using frustrated Lewis pair: effect of buffer and halide ion in the heterolytic H–H bond cleavage
title_sort h(2) activation by hydrogenase-inspired nife catalyst using frustrated lewis pair: effect of buffer and halide ion in the heterolytic h–h bond cleavage
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9038005/
https://www.ncbi.nlm.nih.gov/pubmed/35480737
http://dx.doi.org/10.1039/d1ra05928a
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