title: Investigating the mechanism of the selective hydrogenation reaction of cinnamaldehyde catalyzed by Ptn clusters.
abstract: Cinnamaldehyde (CAL) belongs to the group of aromatic α,β-unsaturated aldehydes; the selective hydrogenation of CAL plays an important role in the fine chemical and pharmaceutical industries. Using Ptn clusters as catalytic models, we studied the selective hydrogenation reaction mechanism for CAL catalyzed by Ptn (n = 6, 10, 14, 18) clusters by means of B3LYP in density functional theory at the 6-31+ G(d) level (the LanL2DZ extra basis set was used for the Pt atom). The rationality of the transition state was proved by vibration frequency analysis and intrinsic reaction coordinate computation. Moreover, atoms in molecules theory and nature bond orbital theory were applied to discuss the interaction among orbitals and the bonding characteristics. The results indicate that three kinds of products, namely 3-phenylpropyl aldehyde, 3-phenyl allyl alcohol and cinnamyl alcohol, are produced in the selective hydrogenation reaction catalyzed by Ptn clusters; each pathway possesses two reaction channels. Ptn clusters are more likely to catalyze the activation and hydrogenation of the C = O bond in CAL molecules, eventually producing cinnamic alcohol, which proves that Ptn clusters have a strong reaction selectivity to catalyze CAL. The reaction selectivity of the catalyzer cluster is closely related to the size of the Ptn cluster, with Pt14 clusters having the greatest reaction selectivity. Graphical Abstract The reaction mechanism for the selective hydrogenation reaction ofcinnamaldehyde catalyzed by Ptn clusters was studied by densityfunctional theory. The reactionselectivity of cluster catalyzer was concluded to be closely related to the size of Ptn clusters, with Pt14 clusters having the greatest reaction selectivity.
authors.affiliation: College of Chemistry and Material Science, Sichuan Normal University, Chengdu, 610066, People's Republic of China. lilcmail@163.com.
authors.forename: Laicai
authors.initials: L
authors.lastname: Li
authors.affiliation: College of Chemistry and Material Science, Sichuan Normal University, Chengdu, 610066, People's Republic of China.
authors.forename: Wei
authors.initials: W
authors.lastname: Wang
authors.affiliation: College of Chemistry and Material Science, Sichuan Normal University, Chengdu, 610066, People's Republic of China.
authors.forename: Xiaolan
authors.initials: X
authors.lastname: Wang
authors.affiliation: College of Chemistry and Material Science, Sichuan Normal University, Chengdu, 610066, People's Republic of China.
authors.forename: Lin
authors.initials: L
authors.lastname: Zhang
keywords: Cinnamaldehyde; Density functional theory; Reaction mechanism; Selective hydrogenation