ACS Earth Space Chem. 2022 Aug 18;6(8):2009-2023. doi: 10.1021/acsearthspacechem.2c00084. Epub 2022 Jul 27.
Understanding how to catalytically break the C-H bond of aromatic molecules, such as polycyclic aromatic hydrocarbons (PAHs), is currently a big challenge and a subject of study in catalysis, astrochemistry, and planetary science. In the latter, the study of the breakdown reaction of PAHs on mineral surfaces is important to understand if PAHs are linked to prebiotic molecules in regions of star and planet formation. In this work, we employed a periodic density functional theory along with Grimme’s D4 (DFT-D4) approach for studying the adsorption of a sample of PAHs (naphthalene, anthracene, fluoranthene, pyrene, coronene, and benzocoronene) and fullerene on the  forsterite surface and its defective surfaces (Fe-doped and Ni-doped surfaces and a MgO-Schottky vacancy) for their implications in catalysis and astrochemistry. On the basis of structural and binding energy analysis, large PAHs and fullerene present stronger adsorption on the pristine, Fe-doped, and Ni-doped forsterite surfaces than small PAHs. On a MgO-Schottky vacancy, parallel adsorption of the PAH leads to the chemisorption process (C-Si and/or C-O bonds), whereas perpendicular orientation of the PAH leads to the catalytic breaking of the aromatic C-H bond via a barrierless reaction. Spin density and charge analysis show that C-H dissociation is promoted by electron donation from the vacancy to the PAH. As a result of the undercoordinated Si and O atoms, the vacancy acts as a Frustrated Lewis Pair (FLP) catalyst. Therefore, a MgO-Schottky vacancy  forsterite surface proved to have potential catalytic activity for the activation of C-H bond in aromatic molecules.