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Visible light-driven C−H activation and C–C coupling of methanol into ethylene glycol

The development of new methods for the direct transformation of methanol into two or multi-carbon compounds via controlled carbon–carbon coupling is a highly attractive but challenging goal. Here, we report the first visible-light-driven dehydrogenative coupling of methanol into ethylene glycol, an...

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Autores principales: Xie, Shunji, Shen, Zebin, Deng, Jiao, Guo, Pu, Zhang, Qinghong, Zhang, Haikun, Ma, Chao, Jiang, Zheng, Cheng, Jun, Deng, Dehui, Wang, Ye
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2018
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5862904/
https://www.ncbi.nlm.nih.gov/pubmed/29563511
http://dx.doi.org/10.1038/s41467-018-03543-y
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author Xie, Shunji
Shen, Zebin
Deng, Jiao
Guo, Pu
Zhang, Qinghong
Zhang, Haikun
Ma, Chao
Jiang, Zheng
Cheng, Jun
Deng, Dehui
Wang, Ye
author_facet Xie, Shunji
Shen, Zebin
Deng, Jiao
Guo, Pu
Zhang, Qinghong
Zhang, Haikun
Ma, Chao
Jiang, Zheng
Cheng, Jun
Deng, Dehui
Wang, Ye
author_sort Xie, Shunji
collection PubMed
description The development of new methods for the direct transformation of methanol into two or multi-carbon compounds via controlled carbon–carbon coupling is a highly attractive but challenging goal. Here, we report the first visible-light-driven dehydrogenative coupling of methanol into ethylene glycol, an important chemical currently produced from petroleum. Ethylene glycol is formed with 90% selectivity and high efficiency, together with hydrogen over a molybdenum disulfide nanofoam-modified cadmium sulfide nanorod catalyst. Mechanistic studies reveal a preferential activation of C−H bond instead of O−H bond in methanol by photoexcited holes on CdS via a concerted proton–electron transfer mechanism, forming a hydroxymethyl radical (⋅CH(2)OH) that can readily desorb from catalyst surfaces for subsequent coupling. This work not only offers an alternative nonpetroleum route for the synthesis of EG but also presents a unique visible-light-driven catalytic C−H activation with the hydroxyl group in the same molecule keeping intact.
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spelling pubmed-58629042018-03-23 Visible light-driven C−H activation and C–C coupling of methanol into ethylene glycol Xie, Shunji Shen, Zebin Deng, Jiao Guo, Pu Zhang, Qinghong Zhang, Haikun Ma, Chao Jiang, Zheng Cheng, Jun Deng, Dehui Wang, Ye Nat Commun Article The development of new methods for the direct transformation of methanol into two or multi-carbon compounds via controlled carbon–carbon coupling is a highly attractive but challenging goal. Here, we report the first visible-light-driven dehydrogenative coupling of methanol into ethylene glycol, an important chemical currently produced from petroleum. Ethylene glycol is formed with 90% selectivity and high efficiency, together with hydrogen over a molybdenum disulfide nanofoam-modified cadmium sulfide nanorod catalyst. Mechanistic studies reveal a preferential activation of C−H bond instead of O−H bond in methanol by photoexcited holes on CdS via a concerted proton–electron transfer mechanism, forming a hydroxymethyl radical (⋅CH(2)OH) that can readily desorb from catalyst surfaces for subsequent coupling. This work not only offers an alternative nonpetroleum route for the synthesis of EG but also presents a unique visible-light-driven catalytic C−H activation with the hydroxyl group in the same molecule keeping intact. Nature Publishing Group UK 2018-03-21 /pmc/articles/PMC5862904/ /pubmed/29563511 http://dx.doi.org/10.1038/s41467-018-03543-y Text en © The Author(s) 2018 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
spellingShingle Article
Xie, Shunji
Shen, Zebin
Deng, Jiao
Guo, Pu
Zhang, Qinghong
Zhang, Haikun
Ma, Chao
Jiang, Zheng
Cheng, Jun
Deng, Dehui
Wang, Ye
Visible light-driven C−H activation and C–C coupling of methanol into ethylene glycol
title Visible light-driven C−H activation and C–C coupling of methanol into ethylene glycol
title_full Visible light-driven C−H activation and C–C coupling of methanol into ethylene glycol
title_fullStr Visible light-driven C−H activation and C–C coupling of methanol into ethylene glycol
title_full_unstemmed Visible light-driven C−H activation and C–C coupling of methanol into ethylene glycol
title_short Visible light-driven C−H activation and C–C coupling of methanol into ethylene glycol
title_sort visible light-driven c−h activation and c–c coupling of methanol into ethylene glycol
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5862904/
https://www.ncbi.nlm.nih.gov/pubmed/29563511
http://dx.doi.org/10.1038/s41467-018-03543-y
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