A DFT study on methanol decomposition over single atom Pt/CeO catalysts: the effect of the position of Pt.

Pt/CeO catalysts exhibit excellent catalytic performance for the methanol dehydrogenation (MD) reaction. In this work, MD reactions on three systems of Pt/CeO(110)), Pt/CeO(110), and Pt/CeO(110) are investigated density functional theory (DFT) calculations. The CHOH adsorption, electronic structure of the catalyst, and mechanism of methanol decomposition (MD) are systematically calculated. The results reveal that the d-band center of the Pt atom moves away from the Fermi level in the order of Pt/CeO(110) < Pt/CeO(110) < Pt/CeO(110), and the order of the activity of the MD reaction is Pt/CeO(110) < Pt/CeO(10) < Pt/CeO(110). The results of the microkinetic dynamics simulation verify that only Pt/CeO(110) is conducive to the decomposition of methanol at low temperatures (373 K), and the products CO and H are easily dissociated from the catalyst surface. This work uncovers that both the small size and the Ce vacancy substituted sites of Pt favor the performance of the Pt/CeO catalyst, and provides theoretical guidance for the construction and design of efficient metal-support catalysts for the MD reaction.