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Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen

The ability of Au catalysts to effect the challenging task of utilizing molecular oxygen for the selective epoxidation of cyclooctene is fascinating. Although supported nanometre-size Au particles are poorly active, here we show that solubilized atomic Au clusters, present in ng ml(−1) concentration...

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Autores principales: Qian, Linping, Wang, Zhen, Beletskiy, Evgeny V., Liu, Jingyue, dos Santos, Haroldo J., Li, Tiehu, Rangel, Maria do C., Kung, Mayfair C., Kung, Harold H.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group 2017
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5379066/
https://www.ncbi.nlm.nih.gov/pubmed/28348389
http://dx.doi.org/10.1038/ncomms14881
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author Qian, Linping
Wang, Zhen
Beletskiy, Evgeny V.
Liu, Jingyue
dos Santos, Haroldo J.
Li, Tiehu
Rangel, Maria do C.
Kung, Mayfair C.
Kung, Harold H.
author_facet Qian, Linping
Wang, Zhen
Beletskiy, Evgeny V.
Liu, Jingyue
dos Santos, Haroldo J.
Li, Tiehu
Rangel, Maria do C.
Kung, Mayfair C.
Kung, Harold H.
author_sort Qian, Linping
collection PubMed
description The ability of Au catalysts to effect the challenging task of utilizing molecular oxygen for the selective epoxidation of cyclooctene is fascinating. Although supported nanometre-size Au particles are poorly active, here we show that solubilized atomic Au clusters, present in ng ml(−1) concentrations and stabilized by ligands derived from the oxidized hydrocarbon products, are active. They can be formed from various Au sources. They generate initiators and propagators to trigger the onset of the auto-oxidation reaction with an apparent turnover frequency of 440 s(−1), and continue to generate additional initiators throughout the auto-oxidation cycle without direct participation in the cycle. Spectroscopic characterization suggests that 7–8 atom clusters are effective catalytically. Extension of work based on these understandings leads to the demonstration that these Au clusters are also effective in selective oxidation of cyclohexene, and that solubilized Pt clusters are also capable of generating initiators for cyclooctene epoxidation.
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spelling pubmed-53790662017-04-11 Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen Qian, Linping Wang, Zhen Beletskiy, Evgeny V. Liu, Jingyue dos Santos, Haroldo J. Li, Tiehu Rangel, Maria do C. Kung, Mayfair C. Kung, Harold H. Nat Commun Article The ability of Au catalysts to effect the challenging task of utilizing molecular oxygen for the selective epoxidation of cyclooctene is fascinating. Although supported nanometre-size Au particles are poorly active, here we show that solubilized atomic Au clusters, present in ng ml(−1) concentrations and stabilized by ligands derived from the oxidized hydrocarbon products, are active. They can be formed from various Au sources. They generate initiators and propagators to trigger the onset of the auto-oxidation reaction with an apparent turnover frequency of 440 s(−1), and continue to generate additional initiators throughout the auto-oxidation cycle without direct participation in the cycle. Spectroscopic characterization suggests that 7–8 atom clusters are effective catalytically. Extension of work based on these understandings leads to the demonstration that these Au clusters are also effective in selective oxidation of cyclohexene, and that solubilized Pt clusters are also capable of generating initiators for cyclooctene epoxidation. Nature Publishing Group 2017-03-28 /pmc/articles/PMC5379066/ /pubmed/28348389 http://dx.doi.org/10.1038/ncomms14881 Text en Copyright © 2017, The Author(s) http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
spellingShingle Article
Qian, Linping
Wang, Zhen
Beletskiy, Evgeny V.
Liu, Jingyue
dos Santos, Haroldo J.
Li, Tiehu
Rangel, Maria do C.
Kung, Mayfair C.
Kung, Harold H.
Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen
title Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen
title_full Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen
title_fullStr Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen
title_full_unstemmed Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen
title_short Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen
title_sort stable and solubilized active au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5379066/
https://www.ncbi.nlm.nih.gov/pubmed/28348389
http://dx.doi.org/10.1038/ncomms14881
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