title: Evidence to challenge the universality of the Horiuti-Polanyi mechanism for hydrogenation in heterogeneous catalysis: origin and trend of the preference of a non-Horiuti-Polanyi mechanism.
abstract: The Horiuti-Polanyi mechanism has been considered to be universal for explaining the mechanisms of hydrogenation reactions in heterogeneous catalysis for several decades. In this work, we examine this mechanism for the hydrogenation of acrolein, the simplest α,β-unsaturated aldehyde, in gold-based systems as well as some other metals using extensive first-principles calculations. It is found that a non-Horiuti-Polanyi mechanism is favored in some cases. Furthermore, the physical origin and trend of this mechanism are revealed and discussed regarding the geometrical and electronic effects, which will have a significant influence on current understandings on heterogeneous catalytic hydrogenation reactions and the future catalyst design for these reactions.
authors.affiliation: State Key Laboratory of Chemical Engineering, Center for Computational Chemistry and Research Institute of Industrial Catalysis, East China University of Science & Technology , Shanghai 200237, P.R. China.
authors.forename: Bo
authors.initials: B
authors.lastname: Yang
authors.forename: Xue-Qing
authors.initials: XQ
authors.lastname: Gong
authors.forename: Hai-Feng
authors.initials: HF
authors.lastname: Wang
authors.forename: Xiao-Ming
authors.initials: XM
authors.lastname: Cao
authors.forename: John J
authors.initials: JJ
authors.lastname: Rooney
authors.forename: P
authors.initials: P
authors.lastname: Hu