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Imidazole functionalized MIL-101(Cr), via metal coordination, as a highly active catalyst for carbon dioxide utilization

Imidazole functionalized MIL-101(Cr), via metal coordination, as a highly active catalyst for carbon dioxide utilization
Imidazole functionalized MIL-101(Cr), via metal coordination, as a highly active catalyst for carbon dioxide utilization
Metal organic frameworks (MOFs) are hugely flexible materials with a vast variety of applications. As catalysts, they show great promise owing to their highly porous nature, large surface area, thermal and chemical stability and ease of modification – metal node and linker are variable during and post synthesis. As
solids, MOFs are heterogeneous catalysts which can be more active and are more easily recycled, providing a more environmentally benign alternative to their homogenous analogues. The work presented shall display the effect of post synthetic modification (PSM) of MIL-101, a chromium based terephthalate MOF. Unmodified, MIL-101 shows moderate catalytic activity in CO utilization forming cyclic carbonates. A facile PSM technique, see Figure 1, to incorporate 1-methyl imidazole on the coordinatively unsaturated sites (CUS) of MIL-101 is shown to significantly improve the catalytic performance. Extensive characterisation (XRD, SEM, TGA, BET, and XPS), confirm the retention of the framework following
PSM, whilst FT-IR, UV-Vis and EPR affirm imidazole location on the CUS. Well dispersed, isolated sites for CO utilization are therefore created, without significant alteration of the framework properties. Cataltyic results for the reaction of butylene oxide with CO with MIL-101-Me give an 80 % yield, Figure 1, at a turnover frequency of 770 hr , which compared to the unmodified MIL-101, 30 %, is appreciably enhanced. Computational modelling provides explanation of the unprecedented activity whereby simulations show the
addition of the imidazole introduces additional CO binding sites, prompting the formation of CO -epoxide clusters which increase likelihood of reaction. Both recycle tests and post-catalysis characterisation have proven the MIL-101-Me maintains activity and structure over several cycles.
Potter, Matthew
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Stewart, Daniel
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Elliott, Stuart J
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Sazio, Pier-John
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Zhang, Liling
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Luo, He Kuan
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Zhang, Zhongxing
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Teng, Jing Hua
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Ivaldi, Chiara
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Miletto, Ivana
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Gianotti, Enrica
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Raja, Robert
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Webb, William
fb2b9d49-23f1-4645-aaf5-f92dd5f6bdad
Potter, Matthew
34dee7dc-2f62-4022-bb65-fc7b7fb526d2
Stewart, Daniel
03dcd3ae-9a52-402a-b8d6-ab2b99c878e6
Elliott, Stuart J
6cc724de-f75f-4c0f-a00a-e712b4e73b12
Sazio, Pier-John
0d6200b5-9947-469a-8e97-9147da8a7158
Zhang, Liling
d472c402-2324-485e-8c7b-e1f8e10fa10d
Luo, He Kuan
c46a124b-9eea-43de-88e8-67fbbeedc1dc
Zhang, Zhongxing
8967ca12-8399-4b1b-a66f-8cf0a59d07c2
Teng, Jing Hua
29e44c90-e078-4afc-ab30-1145c8c1d9b3
Ivaldi, Chiara
fe070b80-fa46-4380-a029-6e520c1ee9c9
Miletto, Ivana
ece4ff95-5f2f-42a3-8416-faf0806b32ee
Gianotti, Enrica
8951198a-24fa-4002-b3fe-2cebd6acdccc
Raja, Robert
74faf442-38a6-4ac1-84f9-b3c039cb392b
Webb, William
fb2b9d49-23f1-4645-aaf5-f92dd5f6bdad

Potter, Matthew, Stewart, Daniel, Elliott, Stuart J, Sazio, Pier-John, Zhang, Liling, Luo, He Kuan, Zhang, Zhongxing, Teng, Jing Hua, Ivaldi, Chiara, Miletto, Ivana, Gianotti, Enrica, Raja, Robert and Webb, William (2018) Imidazole functionalized MIL-101(Cr), via metal coordination, as a highly active catalyst for carbon dioxide utilization. American Chemical Society National Meeting & Exposition: Nanoscience, Nanotechnology & Beyond, , Boston, United States. 19 - 22 Aug 2018.

Record type: Conference or Workshop Item (Other)

Abstract

Metal organic frameworks (MOFs) are hugely flexible materials with a vast variety of applications. As catalysts, they show great promise owing to their highly porous nature, large surface area, thermal and chemical stability and ease of modification – metal node and linker are variable during and post synthesis. As
solids, MOFs are heterogeneous catalysts which can be more active and are more easily recycled, providing a more environmentally benign alternative to their homogenous analogues. The work presented shall display the effect of post synthetic modification (PSM) of MIL-101, a chromium based terephthalate MOF. Unmodified, MIL-101 shows moderate catalytic activity in CO utilization forming cyclic carbonates. A facile PSM technique, see Figure 1, to incorporate 1-methyl imidazole on the coordinatively unsaturated sites (CUS) of MIL-101 is shown to significantly improve the catalytic performance. Extensive characterisation (XRD, SEM, TGA, BET, and XPS), confirm the retention of the framework following
PSM, whilst FT-IR, UV-Vis and EPR affirm imidazole location on the CUS. Well dispersed, isolated sites for CO utilization are therefore created, without significant alteration of the framework properties. Cataltyic results for the reaction of butylene oxide with CO with MIL-101-Me give an 80 % yield, Figure 1, at a turnover frequency of 770 hr , which compared to the unmodified MIL-101, 30 %, is appreciably enhanced. Computational modelling provides explanation of the unprecedented activity whereby simulations show the
addition of the imidazole introduces additional CO binding sites, prompting the formation of CO -epoxide clusters which increase likelihood of reaction. Both recycle tests and post-catalysis characterisation have proven the MIL-101-Me maintains activity and structure over several cycles.

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Published date: 19 August 2018
Venue - Dates: American Chemical Society National Meeting & Exposition: Nanoscience, Nanotechnology & Beyond, , Boston, United States, 2018-08-19 - 2018-08-22

Identifiers

Local EPrints ID: 425737
URI: http://eprints.soton.ac.uk/id/eprint/425737
PURE UUID: d6c3119c-febd-47c0-aad9-e3340448cca3
ORCID for Matthew Potter: ORCID iD orcid.org/0000-0001-9849-3306
ORCID for Daniel Stewart: ORCID iD orcid.org/0000-0003-3409-6517
ORCID for Pier-John Sazio: ORCID iD orcid.org/0000-0002-6506-9266
ORCID for Robert Raja: ORCID iD orcid.org/0000-0002-4161-7053

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Date deposited: 02 Nov 2018 17:30
Last modified: 07 Oct 2021 02:02

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Contributors

Author: Matthew Potter ORCID iD
Author: Daniel Stewart ORCID iD
Author: Stuart J Elliott
Author: Pier-John Sazio ORCID iD
Author: Liling Zhang
Author: He Kuan Luo
Author: Zhongxing Zhang
Author: Jing Hua Teng
Author: Chiara Ivaldi
Author: Ivana Miletto
Author: Enrica Gianotti
Author: Robert Raja ORCID iD
Author: William Webb

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