Abstract
Carbon dioxide capture, corresponding to the recombination process of decarboxylation reactions of organic acids, is typically barrierless in the gas phase and has a relatively low barrier in aprotic solvents. However, these processes often encounter significant solvent-reorganization-induced barriers in aqueous solution if the decarboxylation product is not immediately protonated. Both the intrinsic stereoelectronic effects and solute-solvent interactions play critical roles in determining the overall decarboxylation equilibrium and free energy barrier. An understanding of the interplay of these factors is important for designing novel materials applied to greenhouse gas capture and storage as well as for unraveling the catalytic mechanisms of a range of carboxy lyases in biological CO2production. A range of decarboxylation reactions of organic acids with rates spanning nearly 30 orders of magnitude have been examined through dual-level combined quantum mechanical and molecular mechanical simulations to help elucidate the origin of solvation-induced free energy barriers for decarboxylation and the reverse carboxylation reactions in water.
Original language | English (US) |
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Pages (from-to) | 233-244 |
Number of pages | 12 |
Journal | JACS Au |
Volume | 1 |
Issue number | 2 |
DOIs | |
State | Published - Feb 22 2021 |
Bibliographical note
Funding Information:This work was supported in part by the Shenzhen Municipal Science and Technology Innovation Commission (Grant KQTD2017-0330155106581) and the National Natural Science Foundation of China (Grant 21533003).
Publisher Copyright:
© 2021 American Chemical Society. All rights reserved.
Keywords
- Bell-Evans-Polanyi relationship
- carbon dioxide capture
- combined QM/MM
- decarboxylation reaction
- dual-level method
- solvent effect