Cargando…
Understanding catalytic synergy in dinuclear polymerization catalysts for sustainable polymers
Understanding the chemistry underpinning intermetallic synergy and the discovery of generally applicable structure-performances relationships are major challenges in catalysis. Additionally, high-performance catalysts using earth-abundant, non-toxic and inexpensive elements must be prioritised. Here...
Autores principales: | , , , , , |
---|---|
Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2023
|
Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10409799/ https://www.ncbi.nlm.nih.gov/pubmed/37553344 http://dx.doi.org/10.1038/s41467-023-40284-z |
_version_ | 1785086324236091392 |
---|---|
author | Fiorentini, Francesca Diment, Wilfred T. Deacy, Arron C. Kerr, Ryan W. F. Faulkner, Stephen Williams, Charlotte K. |
author_facet | Fiorentini, Francesca Diment, Wilfred T. Deacy, Arron C. Kerr, Ryan W. F. Faulkner, Stephen Williams, Charlotte K. |
author_sort | Fiorentini, Francesca |
collection | PubMed |
description | Understanding the chemistry underpinning intermetallic synergy and the discovery of generally applicable structure-performances relationships are major challenges in catalysis. Additionally, high-performance catalysts using earth-abundant, non-toxic and inexpensive elements must be prioritised. Here, a series of heterodinuclear catalysts of the form Co(III)M(I/II), where M(I/II) = Na(I), K(I), Ca(II), Sr(II), Ba(II) are evaluated for three different polymerizations, by assessment of rate constants, turn over frequencies, polymer selectivity and control. This allows for comparisons of performances both within and between catalysts containing Group I and II metals for CO(2)/propene oxide ring-opening copolymerization (ROCOP), propene oxide/phthalic anhydride ROCOP and lactide ring-opening polymerization (ROP). The data reveal new structure-performance correlations that apply across all the different polymerizations: catalysts featuring s-block metals of lower Lewis acidity show higher rates and selectivity. The epoxide/heterocumulene ROCOPs both show exponential activity increases (vs. Lewis acidity, measured by the pK(a) of [M(OH(2))(m)](n+)), whilst the lactide ROP activity and CO(2)/epoxide selectivity show linear increases. Such clear structure-activity/selectivity correlations are very unusual, yet are fully rationalised by the polymerization mechanisms and the chemistry of the catalytic intermediates. The general applicability across three different polymerizations is significant for future exploitation of catalytic synergy and provides a framework to improve other catalysts. |
format | Online Article Text |
id | pubmed-10409799 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-104097992023-08-10 Understanding catalytic synergy in dinuclear polymerization catalysts for sustainable polymers Fiorentini, Francesca Diment, Wilfred T. Deacy, Arron C. Kerr, Ryan W. F. Faulkner, Stephen Williams, Charlotte K. Nat Commun Article Understanding the chemistry underpinning intermetallic synergy and the discovery of generally applicable structure-performances relationships are major challenges in catalysis. Additionally, high-performance catalysts using earth-abundant, non-toxic and inexpensive elements must be prioritised. Here, a series of heterodinuclear catalysts of the form Co(III)M(I/II), where M(I/II) = Na(I), K(I), Ca(II), Sr(II), Ba(II) are evaluated for three different polymerizations, by assessment of rate constants, turn over frequencies, polymer selectivity and control. This allows for comparisons of performances both within and between catalysts containing Group I and II metals for CO(2)/propene oxide ring-opening copolymerization (ROCOP), propene oxide/phthalic anhydride ROCOP and lactide ring-opening polymerization (ROP). The data reveal new structure-performance correlations that apply across all the different polymerizations: catalysts featuring s-block metals of lower Lewis acidity show higher rates and selectivity. The epoxide/heterocumulene ROCOPs both show exponential activity increases (vs. Lewis acidity, measured by the pK(a) of [M(OH(2))(m)](n+)), whilst the lactide ROP activity and CO(2)/epoxide selectivity show linear increases. Such clear structure-activity/selectivity correlations are very unusual, yet are fully rationalised by the polymerization mechanisms and the chemistry of the catalytic intermediates. The general applicability across three different polymerizations is significant for future exploitation of catalytic synergy and provides a framework to improve other catalysts. Nature Publishing Group UK 2023-08-08 /pmc/articles/PMC10409799/ /pubmed/37553344 http://dx.doi.org/10.1038/s41467-023-40284-z Text en © The Author(s) 2023 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 licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence 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 licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Fiorentini, Francesca Diment, Wilfred T. Deacy, Arron C. Kerr, Ryan W. F. Faulkner, Stephen Williams, Charlotte K. Understanding catalytic synergy in dinuclear polymerization catalysts for sustainable polymers |
title | Understanding catalytic synergy in dinuclear polymerization catalysts for sustainable polymers |
title_full | Understanding catalytic synergy in dinuclear polymerization catalysts for sustainable polymers |
title_fullStr | Understanding catalytic synergy in dinuclear polymerization catalysts for sustainable polymers |
title_full_unstemmed | Understanding catalytic synergy in dinuclear polymerization catalysts for sustainable polymers |
title_short | Understanding catalytic synergy in dinuclear polymerization catalysts for sustainable polymers |
title_sort | understanding catalytic synergy in dinuclear polymerization catalysts for sustainable polymers |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10409799/ https://www.ncbi.nlm.nih.gov/pubmed/37553344 http://dx.doi.org/10.1038/s41467-023-40284-z |
work_keys_str_mv | AT fiorentinifrancesca understandingcatalyticsynergyindinuclearpolymerizationcatalystsforsustainablepolymers AT dimentwilfredt understandingcatalyticsynergyindinuclearpolymerizationcatalystsforsustainablepolymers AT deacyarronc understandingcatalyticsynergyindinuclearpolymerizationcatalystsforsustainablepolymers AT kerrryanwf understandingcatalyticsynergyindinuclearpolymerizationcatalystsforsustainablepolymers AT faulknerstephen understandingcatalyticsynergyindinuclearpolymerizationcatalystsforsustainablepolymers AT williamscharlottek understandingcatalyticsynergyindinuclearpolymerizationcatalystsforsustainablepolymers |