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Adsorption of CO2 on a micro-/mesoporous polyimine modified with tris(2-aminoethyl)amine
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Number of Authors: 3
2015 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, Vol. 3, no 31, 16229-16234 p.Article in journal (Refereed) Published
Abstract [en]

Amine-modified sorbents are relevant to the capturing of dilute carbon dioxide from gas mixtures, and micro-/mesoporous polymers are promising substrates due to their rich chemistry. Here, we prepared an aldehyde-rich polyimine with micro- and mesoporesby a Schiff-base condensation of 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarboxaldehyde using an excess of aldehyde. The micropores were crucial to the physisorption of CO2, while the mesopores provided space for the post-modification with tris(2-aminoethyl) amine (tren) that induced the chemisorption of CO2. The amine modified polymer showed a high uptake of CO2 at low pressures (1.13 mmol g(-1) at 0.05 bar and 273 K) and a high estimated CO2-over-N-2 selectivity (1.04 x 10(3) at 273 K for 5 v%/95 v% CO2/N-2 mixture). CO2 both physisorbed and chemisorbed on the amine-modified polyimine, which we confirmed by studying the CO2-amine chemistry using in situ FTIR spectroscopy and solid state C-13 NMR spectroscopy. Carbamic acid formed during the chemisorption of CO2, as the CO2 reacted with the amine groups. Due to the formation of carbamic acid, the isosteric heat of adsorption was high, with values up to 80 kJ mol(-1) at a low coverage of CO2. It appears that amine-modified porous polymers could be relevant to the removal of CO2 from gas streams with low concentrations.

Place, publisher, year, edition, pages
2015. Vol. 3, no 31, 16229-16234 p.
National Category
Chemical Sciences Environmental Engineering Materials Engineering
Research subject
Materials Chemistry
Identifiers
URN: urn:nbn:se:su:diva-120485DOI: 10.1039/c5ta01321fISI: 000358722200053OAI: oai:DiVA.org:su-120485DiVA: diva2:853208
Available from: 2015-09-11 Created: 2015-09-10 Last updated: 2017-12-04Bibliographically approved
In thesis
1. Imine/azo-linked microporous organic polymers: Design, synthesis and applications
Open this publication in new window or tab >>Imine/azo-linked microporous organic polymers: Design, synthesis and applications
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Microporous organic polymers (MOPs) are porous materials. Owing to their high surface area, tunable pore sizes and high physicochemical stability, they are studied for applications including gas capture and separation and heterogeneous catalysis. In this thesis, a series of imine/azo-linked MOPs were synthesized. The MOPs were examined as potential CO2 sorbents and as supports for heterogeneous catalysis.

The MOPs were synthesized by Schiff base polycondensations and oxidative couplings. The porosities of the imine-linked MOPs were tunable and affected by a range of factors, such as the synthesis conditions, monomer lengths, monomer ratios. All the MOPs had ultramicropores and displayed relatively high CO2 uptakes and CO2-over-N2 selectivities at the CO2 concentrations relevant for post-combustion capture of CO2. Moreover, the ketimine-linked MOPs were moderately hydrophobic, which might increase their efficiency for CO2 capture and separation.

The diverse synthesis routes and rich functionalities of MOPs allowed further post-modification to improve their performance in CO2 capture. A micro-/mesoporous polymer PP1-2, rich in aldehyde end groups, was post-synthetically modified by the alkyl amine tris(2-aminoethyl)amine (tren). The tethered amine moieties induced chemisorption of CO2 on the polymer, which was confirmed by the study of in situ infrared (IR) and solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. As a result, the modified polymer PP1-2-tren had a large CO2 capacity and very high CO2-over-N2 selectivity at low partial pressures of CO2.

Pd(II) species were incorporated in the selected MOPs by means of complexation or chemical bonding with the imine or azo groups. The Pd(II)-rich MOPs were tested as heterogeneous catalysts for various organic reactions. The porous Pd(II)-polyimine (Pd2+/PP-1) was an excellent co-catalyst in combination with chiral amine for cooperatively catalyzed and enantioselective cascade reactions. In addition, the cyclopalladated azo-linked MOP (Pd(II)/PP-2) catalyzed Suzuki and Heck coupling reactions highly efficiently.

Place, publisher, year, edition, pages
Stockholm: Stockholm University, 2015. 83 p.
Keyword
Microporous organic polymers, CO2 capture and separation, post-modification, chemisorption, heterogeneous catalysis
National Category
Materials Chemistry
Research subject
Materials Chemistry
Identifiers
urn:nbn:se:su:diva-121209 (URN)978-91-7649-274-1 (ISBN)
Public defence
2015-11-13, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Accepted. Paper 7: Manuscript.

Available from: 2015-10-22 Created: 2015-09-28 Last updated: 2015-10-21Bibliographically approved

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