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Polyphenylene-Based Solid Acid as an Efficient Catalyst for Activation and Hydration of Alkynes
[Image: see text] Porous polymer catalysts possess the potential to combine the advantages of heterogeneous and homogeneous catalysis, namely, easy postreaction recycling and high dispersion of active sites. Here, we designed a −SO(3)H functionalized polyphenylene (PPhen) framework with purely sp(2)...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2020
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7304856/ https://www.ncbi.nlm.nih.gov/pubmed/32581424 http://dx.doi.org/10.1021/acs.chemmater.0c01763 |
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author | Liu, Yiyun Wang, Bolun Kang, Liqun Stamatopoulos, Apostolos Gu, Hao Wang, Feng Ryan |
author_facet | Liu, Yiyun Wang, Bolun Kang, Liqun Stamatopoulos, Apostolos Gu, Hao Wang, Feng Ryan |
author_sort | Liu, Yiyun |
collection | PubMed |
description | [Image: see text] Porous polymer catalysts possess the potential to combine the advantages of heterogeneous and homogeneous catalysis, namely, easy postreaction recycling and high dispersion of active sites. Here, we designed a −SO(3)H functionalized polyphenylene (PPhen) framework with purely sp(2)-hybridized carbons, which exhibited high activity in the hydration of alkynes including challenging aliphatic substrates such as 1-octyne. The superiority of the structure lies in its covalent crosslink in the xy-plane with a π–π stacking interaction between the planes, enabling simultaneously high swellability and porosity (653 m(2)·g(–1)). High acidic site density (2.12 mmol·g(–1)) was achieved under a mild sulfonation condition. Similar turnover frequencies (0.015 ± 0.001 min(–1)) were obtained regardless of acidic density and crosslink content, suggesting high accessibility for all active sites over PPhen. In addition, the substituted benzene groups can activate alkynes through a T-shape CH/π interaction, as indicated by the 8 and 16 cm(–1) red shift of the alkyne C–H stretching peak for phenylacetylene and 1-octyne, respectively, in the infrared (IR) spectra. These advantages render PPhen-SO(3)H a promising candidate as a solid catalyst replacing the highly toxic liquid phase acids such as the mercury salt. |
format | Online Article Text |
id | pubmed-7304856 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-73048562020-06-22 Polyphenylene-Based Solid Acid as an Efficient Catalyst for Activation and Hydration of Alkynes Liu, Yiyun Wang, Bolun Kang, Liqun Stamatopoulos, Apostolos Gu, Hao Wang, Feng Ryan Chem Mater [Image: see text] Porous polymer catalysts possess the potential to combine the advantages of heterogeneous and homogeneous catalysis, namely, easy postreaction recycling and high dispersion of active sites. Here, we designed a −SO(3)H functionalized polyphenylene (PPhen) framework with purely sp(2)-hybridized carbons, which exhibited high activity in the hydration of alkynes including challenging aliphatic substrates such as 1-octyne. The superiority of the structure lies in its covalent crosslink in the xy-plane with a π–π stacking interaction between the planes, enabling simultaneously high swellability and porosity (653 m(2)·g(–1)). High acidic site density (2.12 mmol·g(–1)) was achieved under a mild sulfonation condition. Similar turnover frequencies (0.015 ± 0.001 min(–1)) were obtained regardless of acidic density and crosslink content, suggesting high accessibility for all active sites over PPhen. In addition, the substituted benzene groups can activate alkynes through a T-shape CH/π interaction, as indicated by the 8 and 16 cm(–1) red shift of the alkyne C–H stretching peak for phenylacetylene and 1-octyne, respectively, in the infrared (IR) spectra. These advantages render PPhen-SO(3)H a promising candidate as a solid catalyst replacing the highly toxic liquid phase acids such as the mercury salt. American Chemical Society 2020-05-01 2020-05-26 /pmc/articles/PMC7304856/ /pubmed/32581424 http://dx.doi.org/10.1021/acs.chemmater.0c01763 Text en Copyright © 2020 American Chemical Society This is an open access article published under a Creative Commons Attribution (CC-BY) License (http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html) , which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
spellingShingle | Liu, Yiyun Wang, Bolun Kang, Liqun Stamatopoulos, Apostolos Gu, Hao Wang, Feng Ryan Polyphenylene-Based Solid Acid as an Efficient Catalyst for Activation and Hydration of Alkynes |
title | Polyphenylene-Based Solid Acid as an Efficient Catalyst
for Activation and Hydration of Alkynes |
title_full | Polyphenylene-Based Solid Acid as an Efficient Catalyst
for Activation and Hydration of Alkynes |
title_fullStr | Polyphenylene-Based Solid Acid as an Efficient Catalyst
for Activation and Hydration of Alkynes |
title_full_unstemmed | Polyphenylene-Based Solid Acid as an Efficient Catalyst
for Activation and Hydration of Alkynes |
title_short | Polyphenylene-Based Solid Acid as an Efficient Catalyst
for Activation and Hydration of Alkynes |
title_sort | polyphenylene-based solid acid as an efficient catalyst
for activation and hydration of alkynes |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7304856/ https://www.ncbi.nlm.nih.gov/pubmed/32581424 http://dx.doi.org/10.1021/acs.chemmater.0c01763 |
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