title: Understanding trends in C-H bond activation in heterogeneous catalysis.
abstract: While the search for catalysts capable of directly converting methane to higher value commodity chemicals and liquid fuels has been active for over a century, a viable industrial process for selective methane activation has yet to be developed. Electronic structure calculations are playing an increasingly relevant role in this search, but large-scale materials screening efforts are hindered by computationally expensive transition state barrier calculations. The purpose of the present letter is twofold. First, we show that, for the wide range of catalysts that proceed via a radical intermediate, a unifying framework for predicting C-H activation barriers using a single universal descriptor can be established. Second, we combine this scaling approach with a thermodynamic analysis of active site formation to provide a map of methane activation rates. Our model successfully rationalizes the available empirical data and lays the foundation for future catalyst design strategies that transcend different catalyst classes.
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 450 Serra Mall Stanford, California 94305, USA.
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, 450 Serra Mall Stanford, California 94305, USA.
authors.forename: Ambarish R
authors.initials: AR
authors.lastname: Kulkarni
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 450 Serra Mall Stanford, California 94305, USA.
authors.forename: Hassan
authors.initials: H
authors.lastname: Aljama
authors.affiliation: Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, California 94720, USA.
authors.forename: Joseph H
authors.initials: JH
authors.lastname: Montoya
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 450 Serra Mall Stanford, California 94305, USA.
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, 450 Serra Mall Stanford, California 94305, USA.
authors.forename: Charlie
authors.identifier: 0000-0002-3294-2807
authors.initials: C
authors.lastname: Tsai
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 450 Serra Mall Stanford, California 94305, USA.|SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, USA.
authors.forename: Frank
authors.initials: F
authors.lastname: Abild-Pedersen
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 450 Serra Mall Stanford, California 94305, USA.|SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, USA.
authors.forename: Felix
authors.initials: F
authors.lastname: Studt
authors.affiliation: SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, 450 Serra Mall Stanford, California 94305, USA.|SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, USA.
authors.forename: Jens K
authors.initials: JK
authors.lastname: Nørskov