open access

https://hdl.handle.net/2115/82235

Frontier Molecular Orbital Based Analysis of Solid-Adsorbate Interactions over Group 13 Metal Oxide Surfaces

英語

2020-07-16

American Chemical Society

Journal of physical chemistry c

124(28)

15355-15365

Adsorption is an essential process that takes place in heterogeneous catalysis. In the current study, solid-adsorbate interactions occurring between a variety of small molecules and surfaces of group beta metal oxides, including beta-Ga2O3(100), beta-Ga2O3(001), theta-Al2O3 (100), theta-Al2O3 (001), theta-Al2O3 (010), In2O3(110), and In2O3(111), were investigated using density functional theory calculations and a machine learning (ML)-based statistical method. The adsorbates utilized for this purpose include CO, CO2, ND NH3, H2O, acetonitrile, acetone, acetamide, acetic acid, alkanes, alkenes, aromatic compounds, alcohols, and amines. The results show that the adsorption energies (E-ads) of each metal oxide surface correlate linearly with the highest occupied molecular orbital (HOMO) energies of the adsorbates and not with energies of the lowest unoccupied molecular orbital (LUMO) of the small molecules. Moreover, in these systems, contributions to molecular adsorption are dominated by interactions between the HOMOs of the adsorbates and the surface conduction band of the metal oxides. Furthermore, the surface energy was found to be an important parameter influencing E-ads values of different metal oxides. Finally, the results of statistical analysis using a ML approach confirmed that adsorbate HOMOs and surface energy of metal oxides are the most influential factors governing molecular adsorption, and also demonstrated that dipole moments of adsorbates contribute to controlling to adsorption.

学術雑誌論文

Accepted Manuscript

This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.jpcc.0c04480 .

1932-7447