Hydrogenation of Carbon Dioxide into Formic Acid by Aluminum Ligated NNN Pincer Fullerene Through Metal–Ligand H2O-Assisted Pathway: A Computational Study

Autor: Mansour Zahedi, Maryam Anafcheh
Rok vydání: 2021
Předmět:
Zdroj: Catalysis Letters. 152:1224-1232
ISSN: 1572-879X
1011-372X
DOI: 10.1007/s10562-021-03723-4
Popis: The AlH2-catalyzed hydrogenation of carbon dioxide into formic acid by a novel catalyst of aluminum ligated NNN pincerfullerene, AlH2-bis(imino)pyrollidinofullerene, was investigated through metal–ligand cooperative (out of metal–ligand cooperative) pathway with/without presence of water molecule. In view of the density functional calculations, among the four different pathways, the first hydrogenation of CO2, in which the hydrogen transfer process occurs from NH2 of ligand through the metal–ligand cooperative pathway, was preferred. Based on the natural bond orbital (NBO) method and atoms-in-molecules (AIM) analysis, the appropriate charge distribution of intermediates, which is accompanied with the O⋯H–O inter-residue hydrogen bonding in seven-membered cyclic structures, led to a better kinetically and thermodynamically performance of the H2O-assisted pathway. Finally, the rotational isomerization and the second hydrogenation catalytic cycle through hydrogen molecule insertion to NO bond in metal–ligand H2O-assisted pathway led to dissociation of H2CO2 and Al–H2 complex.
Databáze: OpenAIRE
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