title: A DFT+U study of acetylene selective hydrogenation on oxygen defective anatase (101) and rutile (110) TiO2 supported Pd4 cluster.
abstract: The reaction mechanisms for selective acetylene hydrogenation on three different supports, Pd(4) cluster, oxygen defective anatase (101), and rutile (110) titania supported Pd(4), cluster are studied using the density functional theory calculations with a Hubbard U correction (DFT+U). The present calculations show that the defect anatase support binds Pd(4) cluster more strongly than that of rutile titania due to the existence of Ti(3+) in anatase titania. Consequently, the binding energies of adsorbed species such as acetylene and ethylene on Pd(4) cluster become weaker on anatase supported catalysts compared to the rutile supported Pd(4) cluster. Anatase catalyst has higher selectivity of acetylene hydrogenation than rutile catalyst. On the one hand, the activation energies of ethylene formation are similar on the two catalysts, while they vary a lot on ethyl formation. The rutile supported Pd catalyst with lower activation energy is preferable for further hydrogenation. On the other hand, the relatively weak adsorption energy of ethylene is gained on anatase surface, which means it is easier for ethylene desorption, hence getting higher selectivity. For further understanding, the energy decomposition method and micro-kinetic analysis are also introduced.
authors.affiliation: Department of Chemistry and the Tianjin Key Laboratory of Metal and Molecule-Based Material Chemistry, Nankai University, Tianjin 300071, People's Republic of China.
authors.forename: Jie
authors.initials: J
authors.lastname: Yang
authors.forename: Cun-Qin
authors.initials: CQ
authors.lastname: Lv
authors.forename: Yong
authors.initials: Y
authors.lastname: Guo
authors.forename: Gui-Chang
authors.initials: GC
authors.lastname: Wang