Theoretical investigation of 1,3-butanediol adsorption on an oxygen-defected CeO2(111) surface

The adsorption of 1,3-butanediol on an oxygen-defect site of a CeO2 (111) surface was investigated with density functional theory (DFT) and paired interacting orbital (PIO) calculations in connection with the investigation of a CeO2 (111) stoichiometric surface. At the oxygen-defect site, two adsorption structures were obtained by DFT calculations. In the structures, the two oxygen atoms of the OH groups interact with exposed Ce cations at the oxygen-defect site. The adsorption structures at the oxygen-defect site are more stable than that on the stoichiometric surface. In the most stable adsorption structure, one hydrogen atom of the 2-position methylene group interacts with the third Ce cation at the oxygen-defect site of the CeO 2 (111) surface. We confirmed the elongation of two C[single bond]O bonds and one C[single bond]H bond of the 2-position methylene group in the most stable adsorption structure. We also executed PIO calculations of 1,3-butanediol-CeO2 (111) systems to analyze interacting orbitals. In-phase interaction between the two oxygen atoms in 1,3-butanediol and Ce cations was observed, indicating that the 1,3-butanediol molecule is anchored by two O[single bond]Ce bonds. Out-of-phase interactions between O and C atoms at 1-position and between H and C atoms at 2-position were confirmed.