The University of Southampton
University of Southampton Institutional Repository

Carbon capturing for sustainable polymer production: The first heterogeneous MOF catalyst for CO2 copolymerisation

Carbon capturing for sustainable polymer production: The first heterogeneous MOF catalyst for CO2 copolymerisation
Carbon capturing for sustainable polymer production: The first heterogeneous MOF catalyst for CO2 copolymerisation
As environmental concerns over greenhouse emissions increase, the fixation and utilisationof carbon dioxide (CO2) remains a pivotal area of research. A widely-reported method forCO2 utilisation is the catalytic copolymerisation with epoxides to form poly(alkylenecarbonates). Formation of poly(propylene carbonate) (PPC) from propylene oxide (PO) isprevalent in catalysis as the final polymer is biodegradable and CO2 can contribute up to43% of the polymer weight.1 Currently, sustainable alternatives are being investigated withhomogeneous catalysts, with chromium(III)- or cobalt(III)- salens2 and Zn-b-diiminatecomplexes3 among the most active, however, scarce few examples of recyclable, easilyseparated heterogeneous systems, with high polycarbonate selectivity and catalyticturnover, exist within the literature. Due to their synthetic versatility, porosity and innate CO2sorption capabilities, MOFs have significant potential for use as CO2 utilisation catalysts, yetthey have only been shown to form the thermodynamically favoured cyclic carbonateproduct, with no examples to date of copolymerisation occurring, to the best of ourknowledge.Through the determination of structure-activity correlations drawn from literature sources andour own work, a suitable MOF was identified, synthesised and successfully shown to provideexceptional catalytic activity for the copolymerisation reaction. Herein, we report the firstexample of a highly selective, co-catalyst free, metal-organic framework (MOF), capable ofcatalysing the copolymerisation between CO2 and propylene oxide. The MOF catalystfacilitates >90% conversion in dramatically reduced timescales compared to those requiredfor widely used zinc glutarate catalysts, under milder reaction conditions, to produce PPCwith high CO2 insertion into the polymer backbone with a catalytic turn-over frequency inexcess of 1000 hr-1. In-situ MAS-NMR, XAS and FT-IR characterisation, supported by DFTmodelling, have been used to bring insight to the observed polymer selectivity and thebinding interaction between the framework and the CO2/PO substrates.The discovery of this MOF for this copolymerisation demonstrates the versatility of MOFcatalysts and provides a promising development in the ever-essential field of carbon captureutilisation technology.
The project leading to these results has received funding from the European Union’s Horizon 2020 Research and Innovation Programme, under grant agreement N. 720783 - MULTI2HYCAT
Stewart, Daniel
03dcd3ae-9a52-402a-b8d6-ab2b99c878e6
Dwyer, Charlotte
2b69c5de-8c72-45ec-b4d6-43fe1f6a7e0f
Carravetta, Marina
1b12fa96-4a6a-4689-ab3b-ccc68f1d7691
Cossi, Maurizio
d1a3f2b8-6592-4268-a15d-a91e219c1afa
Miletto, Ivana
9a3fe0ee-6afd-4e72-abff-8e83a9114ae9
Gianotti, Enrica
2496d8d3-780f-4fe0-a43e-147e68331078
Potter, Matthew
34dee7dc-2f62-4022-bb65-fc7b7fb526d2
Raman, Sumesh
9e458e40-65a4-4a2b-9501-47b555ab43ba
Williams, Charlotte
f0d513e4-c54a-4d96-a9c8-fa024906b30f
Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b
Stewart, Daniel
03dcd3ae-9a52-402a-b8d6-ab2b99c878e6
Dwyer, Charlotte
2b69c5de-8c72-45ec-b4d6-43fe1f6a7e0f
Carravetta, Marina
1b12fa96-4a6a-4689-ab3b-ccc68f1d7691
Cossi, Maurizio
d1a3f2b8-6592-4268-a15d-a91e219c1afa
Miletto, Ivana
9a3fe0ee-6afd-4e72-abff-8e83a9114ae9
Gianotti, Enrica
2496d8d3-780f-4fe0-a43e-147e68331078
Potter, Matthew
34dee7dc-2f62-4022-bb65-fc7b7fb526d2
Raman, Sumesh
9e458e40-65a4-4a2b-9501-47b555ab43ba
Williams, Charlotte
f0d513e4-c54a-4d96-a9c8-fa024906b30f
Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b

Stewart, Daniel, Dwyer, Charlotte, Carravetta, Marina, Cossi, Maurizio, Miletto, Ivana, Gianotti, Enrica, Potter, Matthew, Raman, Sumesh, Williams, Charlotte and Raja, Robert (2018) Carbon capturing for sustainable polymer production: The first heterogeneous MOF catalyst for CO2 copolymerisation. International MOF Conference 2018, University of Auckland, New Zealand. 09 - 13 Dec 2018.

Record type: Conference or Workshop Item (Other)

Abstract

As environmental concerns over greenhouse emissions increase, the fixation and utilisationof carbon dioxide (CO2) remains a pivotal area of research. A widely-reported method forCO2 utilisation is the catalytic copolymerisation with epoxides to form poly(alkylenecarbonates). Formation of poly(propylene carbonate) (PPC) from propylene oxide (PO) isprevalent in catalysis as the final polymer is biodegradable and CO2 can contribute up to43% of the polymer weight.1 Currently, sustainable alternatives are being investigated withhomogeneous catalysts, with chromium(III)- or cobalt(III)- salens2 and Zn-b-diiminatecomplexes3 among the most active, however, scarce few examples of recyclable, easilyseparated heterogeneous systems, with high polycarbonate selectivity and catalyticturnover, exist within the literature. Due to their synthetic versatility, porosity and innate CO2sorption capabilities, MOFs have significant potential for use as CO2 utilisation catalysts, yetthey have only been shown to form the thermodynamically favoured cyclic carbonateproduct, with no examples to date of copolymerisation occurring, to the best of ourknowledge.Through the determination of structure-activity correlations drawn from literature sources andour own work, a suitable MOF was identified, synthesised and successfully shown to provideexceptional catalytic activity for the copolymerisation reaction. Herein, we report the firstexample of a highly selective, co-catalyst free, metal-organic framework (MOF), capable ofcatalysing the copolymerisation between CO2 and propylene oxide. The MOF catalystfacilitates >90% conversion in dramatically reduced timescales compared to those requiredfor widely used zinc glutarate catalysts, under milder reaction conditions, to produce PPCwith high CO2 insertion into the polymer backbone with a catalytic turn-over frequency inexcess of 1000 hr-1. In-situ MAS-NMR, XAS and FT-IR characterisation, supported by DFTmodelling, have been used to bring insight to the observed polymer selectivity and thebinding interaction between the framework and the CO2/PO substrates.The discovery of this MOF for this copolymerisation demonstrates the versatility of MOFcatalysts and provides a promising development in the ever-essential field of carbon captureutilisation technology.
The project leading to these results has received funding from the European Union’s Horizon 2020 Research and Innovation Programme, under grant agreement N. 720783 - MULTI2HYCAT

Text
MOF2018 Abstract DSTEWART - Author's Original
Restricted to Repository staff only
Request a copy

More information

In preparation date: 2018
Published date: 9 November 2018
Venue - Dates: International MOF Conference 2018, University of Auckland, New Zealand, 2018-12-09 - 2018-12-13

Identifiers

Local EPrints ID: 428209
URI: http://eprints.soton.ac.uk/id/eprint/428209
PURE UUID: 6b2331a5-eb71-49e7-8185-f281f7fd2835
ORCID for Daniel Stewart: ORCID iD orcid.org/0000-0003-3409-6517
ORCID for Marina Carravetta: ORCID iD orcid.org/0000-0002-6296-2104
ORCID for Matthew Potter: ORCID iD orcid.org/0000-0001-9849-3306
ORCID for Robert Raja: ORCID iD orcid.org/0000-0002-4161-7053

Catalogue record

Date deposited: 15 Feb 2019 17:30
Last modified: 18 Feb 2021 17:42

Export record

Contributors

Author: Daniel Stewart ORCID iD
Author: Charlotte Dwyer
Author: Maurizio Cossi
Author: Ivana Miletto
Author: Enrica Gianotti
Author: Matthew Potter ORCID iD
Author: Sumesh Raman
Author: Charlotte Williams
Author: Robert Raja ORCID iD

University divisions

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×