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Tröger’s Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis

Ariana Antonangelo, Tash Hawkins, Elena Tocci Orcid Logo, Chiara Muzzi, Alessio Fuoco Orcid Logo, Mariolino Carta Orcid Logo

Journal of the American Chemical Society, Volume: 144, Issue: 34, Pages: 15581 - 15594

Swansea University Authors: Ariana Antonangelo, Tash Hawkins, Mariolino Carta Orcid Logo

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DOI (Published version): 10.1021/jacs.2c04739

Abstract

Heterogeneous catalysis plays a pivotal role in the preparation of value-added chemicals, and it works more efficiently when combined with porous materials and supports. Because of that, a detailed assessment of porosity and pore size is essential when evaluating the performance of new heterogeneous...

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Published in: Journal of the American Chemical Society
ISSN: 0002-7863 1520-5126
Published: American Chemical Society (ACS) 2022
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URI: https://cronfa.swan.ac.uk/Record/cronfa60736
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spelling 2022-09-02T10:52:33.7839657 v2 60736 2022-08-05 Tröger’s Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis 4565af0854d884b5f995af8f5dc652fc Ariana Antonangelo Ariana Antonangelo true false 504b1b0b26830fee1373ecc50801f01a Tash Hawkins Tash Hawkins true false 56aebf2bba457f395149bbecbfa6d3eb 0000-0003-0718-6971 Mariolino Carta Mariolino Carta true false 2022-08-05 EAAS Heterogeneous catalysis plays a pivotal role in the preparation of value-added chemicals, and it works more efficiently when combined with porous materials and supports. Because of that, a detailed assessment of porosity and pore size is essential when evaluating the performance of new heterogeneous catalysts. Herein, we report the synthesis and characterization of a series of novel microporous Tröger’s base polymers and copolymers (TB-PIMs) with tunable pore size. The basicity of TB sites is exploited to catalyze the Knoevenagel condensation of benzaldehydes and malononitrile, and the dimension of the pores can be systematically adjusted with an appropriate selection of monomers and comonomers. The tunability of the pore size provides the enhanced accessibility of the catalytic sites for substrates, which leads to a great improvement in conversions, with the best results achieving completion in only 20 min. In addition, it enables the use of large benzaldehydes, which is prevented when using polymers with very small pores, typical of conventional PIMs. The catalytic reaction is more efficient than the corresponding homogeneous counterpart and is ultimately optimized with the addition of a small amount of a solvent, which facilitates the swelling of the pores and leads to a further improvement in the performance and to a better carbon economy. Molecular dynamic modeling of the copolymers’ structures is employed to describe the swellability of flexible chains, helping the understanding of the improved performance and demonstrating the great potential of these novel materials. Journal Article Journal of the American Chemical Society 144 34 15581 15594 American Chemical Society (ACS) 0002-7863 1520-5126 Catalysts, Copolymers, Materials, Polymers, Solvents 31 8 2022 2022-08-31 10.1021/jacs.2c04739 COLLEGE NANME Engineering and Applied Sciences School COLLEGE CODE EAAS Swansea University SU Library paid the OA fee (TA Institutional Deal) M.C., A.R.A., and N.H. gratefully acknowledge funding from the Engineering and Physical Sciences Research Council (EPSRC), Grant number: EP/T007362/1 “Novel polymers of intrinsic microporosity for heterogeneous base-catalyzed reactions (HBC-PIMs)” and Swansea University. 2022-09-02T10:52:33.7839657 2022-08-05T11:15:56.2495550 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Ariana Antonangelo 1 Tash Hawkins 2 Elena Tocci 0000-0001-8731-2063 3 Chiara Muzzi 4 Alessio Fuoco 0000-0002-8355-0141 5 Mariolino Carta 0000-0003-0718-6971 6 60736__24985__8b9ddb95fa694607907d27eeab0fe0a8.pdf 60736_VoR.pdf 2022-08-22T11:42:35.0458231 Output 7601629 application/pdf Version of Record true © 2022 The Authors. Released under the terms of a Creative Commons Attribution 4.0 International (CC BY 4.0) License. true eng https://creativecommons.org/licenses/by/4.0/
title Tröger’s Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis
spellingShingle Tröger’s Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis
Ariana Antonangelo
Tash Hawkins
Mariolino Carta
title_short Tröger’s Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis
title_full Tröger’s Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis
title_fullStr Tröger’s Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis
title_full_unstemmed Tröger’s Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis
title_sort Tröger’s Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis
author_id_str_mv 4565af0854d884b5f995af8f5dc652fc
504b1b0b26830fee1373ecc50801f01a
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author_id_fullname_str_mv 4565af0854d884b5f995af8f5dc652fc_***_Ariana Antonangelo
504b1b0b26830fee1373ecc50801f01a_***_Tash Hawkins
56aebf2bba457f395149bbecbfa6d3eb_***_Mariolino Carta
author Ariana Antonangelo
Tash Hawkins
Mariolino Carta
author2 Ariana Antonangelo
Tash Hawkins
Elena Tocci
Chiara Muzzi
Alessio Fuoco
Mariolino Carta
format Journal article
container_title Journal of the American Chemical Society
container_volume 144
container_issue 34
container_start_page 15581
publishDate 2022
institution Swansea University
issn 0002-7863
1520-5126
doi_str_mv 10.1021/jacs.2c04739
publisher American Chemical Society (ACS)
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
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description Heterogeneous catalysis plays a pivotal role in the preparation of value-added chemicals, and it works more efficiently when combined with porous materials and supports. Because of that, a detailed assessment of porosity and pore size is essential when evaluating the performance of new heterogeneous catalysts. Herein, we report the synthesis and characterization of a series of novel microporous Tröger’s base polymers and copolymers (TB-PIMs) with tunable pore size. The basicity of TB sites is exploited to catalyze the Knoevenagel condensation of benzaldehydes and malononitrile, and the dimension of the pores can be systematically adjusted with an appropriate selection of monomers and comonomers. The tunability of the pore size provides the enhanced accessibility of the catalytic sites for substrates, which leads to a great improvement in conversions, with the best results achieving completion in only 20 min. In addition, it enables the use of large benzaldehydes, which is prevented when using polymers with very small pores, typical of conventional PIMs. The catalytic reaction is more efficient than the corresponding homogeneous counterpart and is ultimately optimized with the addition of a small amount of a solvent, which facilitates the swelling of the pores and leads to a further improvement in the performance and to a better carbon economy. Molecular dynamic modeling of the copolymers’ structures is employed to describe the swellability of flexible chains, helping the understanding of the improved performance and demonstrating the great potential of these novel materials.
published_date 2022-08-31T08:08:53Z
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score 11.047306

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