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Polymers of Intrinsic Microporosity for Heterogeneous Base Catalysis / Tash Hawkins

Swansea University Author: Tash Hawkins

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DOI (Published version): 10.23889/SUthesis.62769

Abstract

The climate crisis is the greatest challenge facing this generation, and in order to meet ambitious targets set by global leaders, great advancements in sustainable technologies are needed. This thesis work aimed to develop a new series of polymers of intrinsic microporosity (PIMs) for catalytic app...

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Published: Swansea 2023
Institution: Swansea University
Degree level: Doctoral
Degree name: Ph.D
Supervisor: Carta, Mariolino
URI: https://cronfa.swan.ac.uk/Record/cronfa62769
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first_indexed 2023-02-28T12:20:06Z
last_indexed 2023-03-01T04:18:41Z
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spelling 2023-02-28T12:30:33.2004069 v2 62769 2023-02-28 Polymers of Intrinsic Microporosity for Heterogeneous Base Catalysis 504b1b0b26830fee1373ecc50801f01a Tash Hawkins Tash Hawkins true false 2023-02-28 CHEM The climate crisis is the greatest challenge facing this generation, and in order to meet ambitious targets set by global leaders, great advancements in sustainable technologies are needed. This thesis work aimed to develop a new series of polymers of intrinsic microporosity (PIMs) for catalytic applications. PIMs have been of great interest within materials chemistry since their development in the early 2000s, they are purely organic materials that have a lower environmental impact than competing materials and can be synthesised under relatively mild conditions. More specifically, Tröger’s’ base (TB) PIMs are materials that, along with the typical high porosity of PIMs, possess two bridgehead nitrogens that can be used to tune the polarity of the final material. In this work, we have synthesised a series of novel TB-PIMs which can act as basic catalysts because of the basicity of the bridgehead nitrogens. We have demonstrated that by increasing the degree of flexibility in the polymers, we can induce a “swelling” effect that facilitates the accessibility of the catalytic sites and allows the use of larger substrates, thus increasing the catalytic performance. We have also shown that new functionalities can very easily be incorporated into PIM structures, meaning that these materials can be tailor made for specific applications. We have demonstrated that by increasing the number of basic nitrogen sites in a repeated unit, we can further increase the rate of a reaction. Finally, we have shown that post-functionalised PIMs can successfully catalyse a range of environmentally important reactions. For instance, quaternised TB polymers were successfully used to catalyse the cycloaddition of CO2 into epoxides, to form cyclic carbonates that can be employed as sustainable solvents, and sulfonated PIMs have been successful in the transesterification of oils for biodiesel synthesis. We believe that this work lays a foundation for future research into PIM catalysts, as they are a versatile, facile, robust, and efficient catalytic technology. E-Thesis Swansea Polymers, Porous Materials, Catalysis, PIMs 22 2 2023 2023-02-22 10.23889/SUthesis.62769 ORCiD identifier: https://orcid.org/0000-0003-4784-2902 COLLEGE NANME Chemistry COLLEGE CODE CHEM Swansea University Carta, Mariolino Doctoral Ph.D EPSRC 2023-02-28T12:30:33.2004069 2023-02-28T12:17:44.6713242 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Tash Hawkins 1 62769__26697__6745606b17624a518f350f149bc1f52e.pdf Hawkins_Natasha_PhD_Thesis_Final_Redacted_Signature.pdf 2023-02-28T12:23:22.2776416 Output 5254875 application/pdf E-Thesis – open access true Copyright: The author, Natasha Hawkins, 2023. true eng
title Polymers of Intrinsic Microporosity for Heterogeneous Base Catalysis
spellingShingle Polymers of Intrinsic Microporosity for Heterogeneous Base Catalysis
Tash Hawkins
title_short Polymers of Intrinsic Microporosity for Heterogeneous Base Catalysis
title_full Polymers of Intrinsic Microporosity for Heterogeneous Base Catalysis
title_fullStr Polymers of Intrinsic Microporosity for Heterogeneous Base Catalysis
title_full_unstemmed Polymers of Intrinsic Microporosity for Heterogeneous Base Catalysis
title_sort Polymers of Intrinsic Microporosity for Heterogeneous Base Catalysis
author_id_str_mv 504b1b0b26830fee1373ecc50801f01a
author_id_fullname_str_mv 504b1b0b26830fee1373ecc50801f01a_***_Tash Hawkins
author Tash Hawkins
author2 Tash Hawkins
format E-Thesis
publishDate 2023
institution Swansea University
doi_str_mv 10.23889/SUthesis.62769
college_str Faculty of Science and Engineering
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hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemistry{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemistry
document_store_str 1
active_str 0
description The climate crisis is the greatest challenge facing this generation, and in order to meet ambitious targets set by global leaders, great advancements in sustainable technologies are needed. This thesis work aimed to develop a new series of polymers of intrinsic microporosity (PIMs) for catalytic applications. PIMs have been of great interest within materials chemistry since their development in the early 2000s, they are purely organic materials that have a lower environmental impact than competing materials and can be synthesised under relatively mild conditions. More specifically, Tröger’s’ base (TB) PIMs are materials that, along with the typical high porosity of PIMs, possess two bridgehead nitrogens that can be used to tune the polarity of the final material. In this work, we have synthesised a series of novel TB-PIMs which can act as basic catalysts because of the basicity of the bridgehead nitrogens. We have demonstrated that by increasing the degree of flexibility in the polymers, we can induce a “swelling” effect that facilitates the accessibility of the catalytic sites and allows the use of larger substrates, thus increasing the catalytic performance. We have also shown that new functionalities can very easily be incorporated into PIM structures, meaning that these materials can be tailor made for specific applications. We have demonstrated that by increasing the number of basic nitrogen sites in a repeated unit, we can further increase the rate of a reaction. Finally, we have shown that post-functionalised PIMs can successfully catalyse a range of environmentally important reactions. For instance, quaternised TB polymers were successfully used to catalyse the cycloaddition of CO2 into epoxides, to form cyclic carbonates that can be employed as sustainable solvents, and sulfonated PIMs have been successful in the transesterification of oils for biodiesel synthesis. We believe that this work lays a foundation for future research into PIM catalysts, as they are a versatile, facile, robust, and efficient catalytic technology.
published_date 2023-02-22T04:23:07Z
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score 10.99342