E-Thesis 391 views 176 downloads
Polymers of Intrinsic Microporosity for Heterogeneous Base Catalysis / Tash Hawkins
Swansea University Author: Tash Hawkins
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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Swansea
2023
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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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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 |
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Tash Hawkins |
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E-Thesis |
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2023 |
institution |
Swansea University |
doi_str_mv |
10.23889/SUthesis.62769 |
college_str |
Faculty of Science and Engineering |
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|
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facultyofscienceandengineering |
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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 |
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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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1763663924860813312 |
score |
11.030318 |