title: Predicting Promoter-Induced Bond Activation on Solid Catalysts Using Elementary Bond Orders.
abstract: In this Letter, we examine bond activation induced by nonmetal surface promoters in the context of dehydrogenation reactions. We use C-H bond activation in methane dehydrogenation on transition metals as an example to understand the origin of the promoting or poisoning effect of nonmetals. The electronic structure of the surface and the bond order of the promoter are found to establish all trends in bond activation. On the basis of these results, we develop a predictive model that successfully describes the energetics of C-H, O-H, and N-H bond activation across a range of reactions. For a given reaction step, a single data point determines whether a nonmetal will promote bond activation or poison the surface and by how much. We show how our model leads to general insights that can be directly used to predict bond activation energetics on transition metal sulfides and oxides, which can be perceived as promoted surfaces. These results can then be directly used in studies on full catalytic pathways.
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University , 443 Via Ortega, Stanford, California 94305, United States.|SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States.
authors.forename: Charlie
authors.initials: C
authors.lastname: Tsai
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University , 443 Via Ortega, Stanford, California 94305, United States.|SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States.
authors.forename: Allegra A
authors.initials: AA
authors.lastname: Latimer
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University , 443 Via Ortega, Stanford, California 94305, United States.|SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States.
authors.forename: Jong Suk
authors.initials: JS
authors.lastname: Yoo
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University , 443 Via Ortega, Stanford, California 94305, United States.|SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States.
authors.forename: Felix
authors.initials: F
authors.lastname: Studt
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University , 443 Via Ortega, Stanford, California 94305, United States.|SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States.
authors.forename: Frank
authors.initials: F
authors.lastname: Abild-Pedersen
keywords: Bond activation; bond order; electronic structure; promoters; reactivity model; scaling relations