| Autor: |
Haley A. Petersen, Abdulaziz W. Alherz, Taylor A. Stinson, Chloe G. Huntzinger, Charles B. Musgrave, Oana R. Luca |
| Jazyk: |
angličtina |
| Rok vydání: |
2022 |
| Předmět: |
|
| Zdroj: |
iScience, Vol 25, Iss 4, Pp 103997- (2022) |
| Druh dokumentu: |
article |
| ISSN: |
2589-0042 |
| DOI: |
10.1016/j.isci.2022.103997 |
| Popis: |
Summary: This work maps the thermodynamics of electrochemically generated C-nucleophiles for reactive capture of CO2. We identify a linear relationship between the pKa, the reduction potential of a protonated nucleophile (Ered), and the nucleophile’s free energy of CO2 binding (ΔGbind). Through synergistic experiments and computations, this study establishes a three-parameter correlation described by the equation ΔGbind=−0.78pKa+4.28Ered+20.95 for a series of twelve imidazol(in)ium/N-heterocyclic carbene pairs with an R2 of 0.92. The correlation allows us to predict the ΔGbind of C-nucleophiles to CO2 using reduction potentials or pKas of imidazol(in)ium cations. The carbenes in this study were found to exhibit a wide range CO2 binding strengths, from strongly CO2 binding to nonspontaneous. This observation suggests that the ΔGbind of imidazol(in)ium-based carbenes is tunable to a desired strength by appropriate structural changes. This work sets the stage for systematic energetic tuning of electrochemically enabled reactive separations. |
| Databáze: |
Directory of Open Access Journals |
| Externí odkaz: |
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