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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...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2021
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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. |
format | Online Article Text |
id | pubmed-9038005 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
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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