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Influence of Pore Structure and Metal‐Node Geometry on the Polymerization of Ethylene over Cr‐Based Metal–Organic Frameworks
Metal–organic frameworks (MOFs) have received increasing interest as solid single‐site catalysts, owing to their tunable pore architecture and metal node geometry. The ability to exploit these modulators makes them prominent candidates for producing polyethylene (PE) materials with narrow dispersity...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8049024/ https://www.ncbi.nlm.nih.gov/pubmed/33512729 http://dx.doi.org/10.1002/chem.202005308 |
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author | Jongkind, Maarten K. Rivera‐Torrente, Miguel Nikolopoulos, Nikolaos Weckhuysen, Bert M. |
author_facet | Jongkind, Maarten K. Rivera‐Torrente, Miguel Nikolopoulos, Nikolaos Weckhuysen, Bert M. |
author_sort | Jongkind, Maarten K. |
collection | PubMed |
description | Metal–organic frameworks (MOFs) have received increasing interest as solid single‐site catalysts, owing to their tunable pore architecture and metal node geometry. The ability to exploit these modulators makes them prominent candidates for producing polyethylene (PE) materials with narrow dispersity index (Ð) values. Here a study is presented in which the ethylene polymerization properties, with Et(2)AlCl as activator, of three renowned Cr‐based MOFs, MIL‐101(Cr)‐NDC (NDC=2,6‐dicarboxynapthalene), MIL‐53(Cr) and HKUST‐1(Cr), are systematically investigated. Ethylene polymerization reactions revealed varying catalytic activities, with MIL‐101(Cr)‐NDC and MIL‐53(Cr) being significantly more active than HKUST‐1(Cr). Analysis of the PE products revealed large Ð values, demonstrating that polymerization occurs over a multitude of active Cr centers rather than a singular type of Cr site. Spectroscopic experiments, in the form of powder X‐ray diffraction (pXRD), UV/Vis‐NIR diffuse reflectance spectroscopy (DRS) and CO probe molecule Fourier transform infrared (FTIR) spectroscopy corroborated these findings, indicating that indeed for each MOF unique active sites are generated, however without alteration of the original oxidation state. Furthermore, the pXRD experiments indicated that one major prerequisite for catalytic activity was the degree of MOF activation by the Et(2)AlCl co‐catalyst, with the more active materials portraying a larger degree of activation. |
format | Online Article Text |
id | pubmed-8049024 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-80490242021-04-20 Influence of Pore Structure and Metal‐Node Geometry on the Polymerization of Ethylene over Cr‐Based Metal–Organic Frameworks Jongkind, Maarten K. Rivera‐Torrente, Miguel Nikolopoulos, Nikolaos Weckhuysen, Bert M. Chemistry Full Papers Metal–organic frameworks (MOFs) have received increasing interest as solid single‐site catalysts, owing to their tunable pore architecture and metal node geometry. The ability to exploit these modulators makes them prominent candidates for producing polyethylene (PE) materials with narrow dispersity index (Ð) values. Here a study is presented in which the ethylene polymerization properties, with Et(2)AlCl as activator, of three renowned Cr‐based MOFs, MIL‐101(Cr)‐NDC (NDC=2,6‐dicarboxynapthalene), MIL‐53(Cr) and HKUST‐1(Cr), are systematically investigated. Ethylene polymerization reactions revealed varying catalytic activities, with MIL‐101(Cr)‐NDC and MIL‐53(Cr) being significantly more active than HKUST‐1(Cr). Analysis of the PE products revealed large Ð values, demonstrating that polymerization occurs over a multitude of active Cr centers rather than a singular type of Cr site. Spectroscopic experiments, in the form of powder X‐ray diffraction (pXRD), UV/Vis‐NIR diffuse reflectance spectroscopy (DRS) and CO probe molecule Fourier transform infrared (FTIR) spectroscopy corroborated these findings, indicating that indeed for each MOF unique active sites are generated, however without alteration of the original oxidation state. Furthermore, the pXRD experiments indicated that one major prerequisite for catalytic activity was the degree of MOF activation by the Et(2)AlCl co‐catalyst, with the more active materials portraying a larger degree of activation. John Wiley and Sons Inc. 2021-03-01 2021-03-26 /pmc/articles/PMC8049024/ /pubmed/33512729 http://dx.doi.org/10.1002/chem.202005308 Text en © 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Full Papers Jongkind, Maarten K. Rivera‐Torrente, Miguel Nikolopoulos, Nikolaos Weckhuysen, Bert M. Influence of Pore Structure and Metal‐Node Geometry on the Polymerization of Ethylene over Cr‐Based Metal–Organic Frameworks |
title | Influence of Pore Structure and Metal‐Node Geometry on the Polymerization of Ethylene over Cr‐Based Metal–Organic Frameworks |
title_full | Influence of Pore Structure and Metal‐Node Geometry on the Polymerization of Ethylene over Cr‐Based Metal–Organic Frameworks |
title_fullStr | Influence of Pore Structure and Metal‐Node Geometry on the Polymerization of Ethylene over Cr‐Based Metal–Organic Frameworks |
title_full_unstemmed | Influence of Pore Structure and Metal‐Node Geometry on the Polymerization of Ethylene over Cr‐Based Metal–Organic Frameworks |
title_short | Influence of Pore Structure and Metal‐Node Geometry on the Polymerization of Ethylene over Cr‐Based Metal–Organic Frameworks |
title_sort | influence of pore structure and metal‐node geometry on the polymerization of ethylene over cr‐based metal–organic frameworks |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8049024/ https://www.ncbi.nlm.nih.gov/pubmed/33512729 http://dx.doi.org/10.1002/chem.202005308 |
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