Probing the Kinetic Origin of Varying Oxidative Stability of Ethyl- vs. Propyl-spaced Amines for Direct Air Capture.

Autor: Li S; Materials Science Division, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA Email Address., Cerón MR; Materials Science Division, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA Email Address., Eshelman HV; Materials Science Division, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA Email Address., Varni AJ; Materials Science Division, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA Email Address., Maiti A; Materials Science Division, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA Email Address., Akhade S; Materials Science Division, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA Email Address., Pang SH; Materials Science Division, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA Email Address.
Jazyk: angličtina
Zdroj: ChemSusChem [ChemSusChem] 2023 Mar 08; Vol. 16 (5), pp. e202201908. Date of Electronic Publication: 2023 Jan 09.
DOI: 10.1002/cssc.202201908
Abstrakt: Amine-based adsorbents are promising for direct air capture of CO 2 , yet oxidative degradation remains a key unmitigated risk hindering wide-scale deployment. Borrowing wisdom from the basic auto-oxidation scheme, insights are gained into the underlying degradation mechanisms of polyamines by quantum chemical, advanced sampling simulations, adsorbent synthesis, and accelerated degradation experiments. The reaction kinetics of polyamines are contrasted with that of typical aliphatic polymers and they elucidate for the first time the critical role of aminoalkyl hydroperoxide decomposition in the oxidative degradation of amino-oligomers. The experimentally observed variation in oxidative stability of polyamines with different backbone structures is explained by the relationship between the local chemical structure and the free energy barrier of aminoalkyl hydroperoxide decomposition, suggesting that its energetics can be used as a descriptor to screen and design new polyamines with improved stability. The developed computational capability sheds light on radical-induced degradation chemistry of other organic functional materials.
(© 2022 Wiley-VCH GmbH.)
Databáze: MEDLINE
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