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Mechanistic classification and benchmarking of polyolefin depolymerization over silica-alumina-based catalysts

Carbon-carbon bond cleavage mechanisms play a key role in the selective deconstruction of alkanes and polyolefins. Here, we show that the product distribution, which encompasses carbon range and formation of unsaturated and isomerization products, serves as a distinctive feature that allows the reac...

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Autores principales: Lee, Wei-Tse, van Muyden, Antoine, Bobbink, Felix D., Mensi, Mounir D., Carullo, Jed R., Dyson, Paul J.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9385622/
https://www.ncbi.nlm.nih.gov/pubmed/35977921
http://dx.doi.org/10.1038/s41467-022-32563-y
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author Lee, Wei-Tse
van Muyden, Antoine
Bobbink, Felix D.
Mensi, Mounir D.
Carullo, Jed R.
Dyson, Paul J.
author_facet Lee, Wei-Tse
van Muyden, Antoine
Bobbink, Felix D.
Mensi, Mounir D.
Carullo, Jed R.
Dyson, Paul J.
author_sort Lee, Wei-Tse
collection PubMed
description Carbon-carbon bond cleavage mechanisms play a key role in the selective deconstruction of alkanes and polyolefins. Here, we show that the product distribution, which encompasses carbon range and formation of unsaturated and isomerization products, serves as a distinctive feature that allows the reaction pathways of different catalysts to be classified. Co, Ni, or Ru nanoparticles immobilized on amorphous silica-alumina, Zeo-Y and ZSM-5, were evaluated as catalysts in the deconstruction of n-hexadecane model substrate with hydrogen to delineate between different mechanisms, i.e., monofunctional- (acid site dominated) or bifunctional-hydrocracking (acid site & metal site) versus hydrogenolysis (metal site dominated), established from the product distributions. The ZSM-5-based catalysts were further studied in the depolymerization of polyethylene. Based on these studies, the catalysts are plotted on an activity-mechanism map that functions as an expandable basis to benchmark catalytic activity and to identify optimal catalysts that afford specific product distributions. The systematic approach reported here should facilitate the acceleration of catalyst discovery for polyolefin depolymerization.
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spelling pubmed-93856222022-08-19 Mechanistic classification and benchmarking of polyolefin depolymerization over silica-alumina-based catalysts Lee, Wei-Tse van Muyden, Antoine Bobbink, Felix D. Mensi, Mounir D. Carullo, Jed R. Dyson, Paul J. Nat Commun Article Carbon-carbon bond cleavage mechanisms play a key role in the selective deconstruction of alkanes and polyolefins. Here, we show that the product distribution, which encompasses carbon range and formation of unsaturated and isomerization products, serves as a distinctive feature that allows the reaction pathways of different catalysts to be classified. Co, Ni, or Ru nanoparticles immobilized on amorphous silica-alumina, Zeo-Y and ZSM-5, were evaluated as catalysts in the deconstruction of n-hexadecane model substrate with hydrogen to delineate between different mechanisms, i.e., monofunctional- (acid site dominated) or bifunctional-hydrocracking (acid site & metal site) versus hydrogenolysis (metal site dominated), established from the product distributions. The ZSM-5-based catalysts were further studied in the depolymerization of polyethylene. Based on these studies, the catalysts are plotted on an activity-mechanism map that functions as an expandable basis to benchmark catalytic activity and to identify optimal catalysts that afford specific product distributions. The systematic approach reported here should facilitate the acceleration of catalyst discovery for polyolefin depolymerization. Nature Publishing Group UK 2022-08-17 /pmc/articles/PMC9385622/ /pubmed/35977921 http://dx.doi.org/10.1038/s41467-022-32563-y Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/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/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Article
Lee, Wei-Tse
van Muyden, Antoine
Bobbink, Felix D.
Mensi, Mounir D.
Carullo, Jed R.
Dyson, Paul J.
Mechanistic classification and benchmarking of polyolefin depolymerization over silica-alumina-based catalysts
title Mechanistic classification and benchmarking of polyolefin depolymerization over silica-alumina-based catalysts
title_full Mechanistic classification and benchmarking of polyolefin depolymerization over silica-alumina-based catalysts
title_fullStr Mechanistic classification and benchmarking of polyolefin depolymerization over silica-alumina-based catalysts
title_full_unstemmed Mechanistic classification and benchmarking of polyolefin depolymerization over silica-alumina-based catalysts
title_short Mechanistic classification and benchmarking of polyolefin depolymerization over silica-alumina-based catalysts
title_sort mechanistic classification and benchmarking of polyolefin depolymerization over silica-alumina-based catalysts
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9385622/
https://www.ncbi.nlm.nih.gov/pubmed/35977921
http://dx.doi.org/10.1038/s41467-022-32563-y
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