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New Insights into the Mechanism of Interaction Between CO2 and Polymers from Thermodynamic Parameters Obtained by in situ ATR-FTIR Spectroscopy Full article

Journal PCCP: Physical Chemistry Chemical Physics
ISSN: 1463-9076 , E-ISSN: 1463-9084
Output data Year: 2016, Volume: 18, Number: 9, Pages: 6465-6475 Pages count : 11 DOI: 10.1039/c5cp06431g
Tags SUPERCRITICAL CARBON-DIOXIDE; AB-INITIO; IR SPECTROSCOPY; IMPREGNATION; EXTRACTION; ACID; TEMPERATURE; PRESSURE; SORPTION; SOLVENT
Authors Gabrienko Anton A. 1,2 , Ewing Andrew V. 1 , Chibiryaev Andrey M. 2,3 , Agafontsev Alexander M. 3,4 , Dubkov Konstantin A. 2 , Kazarian Sergei G. 1
Affiliations
1 Department of Chemical Engineering, Imperial College London, South Kensington Campus, London, UK SW7 2AZ
2 Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk 630090, Russia
3 Faculty of Natural Sciences, Novosibirsk State University, Pirogov street 2, Novosibirsk 630090, Russia
4 Vorozhtsov Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 9, Novosibirsk 630090, Russia

Funding (2)

1 Federal Agency for Scientific Organizations V.44.1.15.
2 Skolkovo Foundation 3 от 25.12.2014

Abstract: This work reports new physical insights of the thermodynamic parameters and mechanisms of possible interactions occurring in polymers subjected to high-pressure CO2. ATR-FTIR spectroscopy has been used in situ to determine the thermodynamic parameters of the intermolecular interactions between CO2 and different functional groups of the polymers capable of specific interactions with sorbed CO2 molecules. Based on the measured ATR-FTIR spectra of the polymer samples subjected to high-pressure CO2 (30 bar) at different temperatures (300–340 K), it was possible to characterize polymer–polymer and CO2–polymer interactions. Particularly, the enthalpy and entropy of the formation of the specific noncovalent complexes between CO2 and the hydroxy (–OH), carbonyl (C=O) and hydroxyimino (=N–OH) functional groups of the polymer samples have been measured. Furthermore, the obtained spectroscopic results have provided an opportunity for the structure of these complexes to be proposed. An interesting phenomenon regarding the behavior of CO2/polymer systems has also been observed. It has been found that only for the polyketone, the value of enthalpy was negative indicating an exothermic process during the formation of the CO2–polymer non-covalent complexes. Conversely, for the polyoxime and polyalcohol samples there is a positive enthalpy determined. This is a result of the initial polymer–polymer interactions requiring more energy to break than is released during the formation of the CO2–polymer complex. The effect of increasing temperature to facilitate the breaking of the polymer–polymer interactions has also been observed. Hence, a mechanism for the formation of CO2–polymer complexes was suggested based on these results, which occurs via a two-step process: (1) the breaking of the existing polymer–polymer interactions followed by (2) the formation of new CO2–polymer noncovalent interactions.
Cite: Gabrienko A.A. , Ewing A.V. , Chibiryaev A.M. , Agafontsev A.M. , Dubkov K.A. , Kazarian S.G.
New Insights into the Mechanism of Interaction Between CO2 and Polymers from Thermodynamic Parameters Obtained by in situ ATR-FTIR Spectroscopy
PCCP: Physical Chemistry Chemical Physics. 2016. V.18. N9. P.6465-6475. DOI: 10.1039/c5cp06431g WOS Scopus РИНЦ ANCAN OpenAlex
Dates:
Submitted: Oct 22, 2015
Accepted: Jan 27, 2016
Published online: Feb 10, 2016
Published print: Mar 1, 2016
Identifiers:
Web of science: WOS:000371139400012
Scopus: 2-s2.0-84959147929
Elibrary: 26895206
Chemical Abstracts: 2016:227835
Chemical Abstracts (print): 164:303747
OpenAlex: W2255276307
Citing:
DB Citing
Web of science 43
Scopus 47
Elibrary 46
OpenAlex 45
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