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Synthesis of microporous organic polymers with high CO2-over-N-2 selectivity and CO2 adsorption
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK).
2013 (English)In: Journal of Materials Chemistry A, ISSN 2050-7488, Vol. 1, no 10, 3406-3414 p.Article in journal (Refereed) Published
Abstract [en]

A series of microporous organic polymers (MOPs) were synthesized by Schiff base condensation of 1,3,5-tris(4-aminophenyl)benzene and a number of dialdehyde monomers. The polymers were structurally characterized by in situ infrared and ex situ solid state C-13{H-1} nuclear magnetic resonance (NMR) spectroscopy. Synthesis conditions were optimized to enhance CO2 uptake by the MOPs. Synthesis at low temperatures results in the MOPs being linked by imine groups. Heating of the MOPs reduces the number of imine groups and after heating to >300 degrees C nitrile groups were found to be present in the MOPs. The MOPs have specific surface areas up to 614 m(2) g(-1) and narrow pore size distributions of similar to 4 to 8 angstrom. The selectivity of CO2-over-N-2 at 273 K and 1 bar was 56-77, which requires either an influence of chemisorption on CO2 or a molecular sieving (or kinetic selection) of CO2-over-N-2. The materials had also heats of adsorption typical for physisorption of CO2.

Place, publisher, year, edition, pages
2013. Vol. 1, no 10, 3406-3414 p.
National Category
Physical Chemistry Materials Chemistry
Research subject
Materials Chemistry
Identifiers
URN: urn:nbn:se:su:diva-88756DOI: 10.1039/c3ta01160gISI: 000314784000027OAI: oai:DiVA.org:su-88756DiVA: diva2:613072
Funder
VINNOVASwedish Research Council
Note

AuthorCount:2;

Available from: 2013-03-26 Created: 2013-03-26 Last updated: 2015-10-02Bibliographically 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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