CO2 reduction using aluminum hydride Generation of in-situ frustrated Lewis pairs and small molecule activation therein

CO2 reduction using aluminum hydride : Generation of in-situ frustrated Lewis pairs and small molecule activation therein

© 2024 Wiley Periodicals LLC.

Bibliographische Detailangaben
Veröffentlicht in:Journal of computational chemistry. - 1984. - 45(2024), 14 vom: 30. Apr., Seite 1098-1111
1. Verfasser: Mondal, Himangshu (VerfasserIn)
Weitere Verfasser: Chattaraj, Pratim Kumar
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2024
Zugriff auf das übergeordnete Werk:Journal of computational chemistry
Schlagworte:Journal Article DFT FLP PIO and EDA‐NOCV activation strain model
Beschreibung
Zusammenfassung:© 2024 Wiley Periodicals LLC.
CO2 reduction is appealing for the long-term production of high-value fuels and chemicals. Herein, using density functional theory (DFT) based calculations, we study the CO2 reduction pathway to formic acid using aluminum hydride and phosphine derivatives. Our primary focus is on aluminum hydride derivatives, aimed at improving the efficiency of the CO2 reduction process. Substituents with σ-donating properties at the aluminum center are discovered to lower the activation barriers. We demonstrate how di-tert-butylphosphine oxide (LB-O)/di-tert-butylphosphine sulfide (LB-S)/di-tert-butylphosphanimine (LB-N) work together with aluminum hydride to facilitate CO2 reduction process and generate in-situ frustrated Lewis pairs (FLPs), such as FLP-O, FLP-S, and FLP-N. The activation strain model (ASM) analysis reveals the significance of strain energy in determining activation barriers. EDA-NOCV and PIO analyses elucidate the orbital interactions at the corresponding transition states. Furthermore, the study delves into the activation of various small molecules, such as dihydrogen, acetylene, ethylene, carbon dioxide, nitrous oxide, and acetonitrile, using those in-situ generated FLPs. The study highlights the low activation barriers and emphasizes the potential for small molecule activation in this context
Beschreibung:Date Revised 12.04.2024
published: Print-Electronic
Citation Status PubMed-not-MEDLINE
ISSN:1096-987X
DOI:10.1002/jcc.27285