title: Effects of correlated parameters and uncertainty in electronic-structure-based chemical kinetic modelling.
abstract: Kinetic models based on first principles are becoming common place in heterogeneous catalysis because of their ability to interpret experimental data, identify the rate-controlling step, guide experiments and predict novel materials. To overcome the tremendous computational cost of estimating parameters of complex networks on metal catalysts, approximate quantum mechanical calculations are employed that render models potentially inaccurate. Here, by introducing correlative global sensitivity analysis and uncertainty quantification, we show that neglecting correlations in the energies of species and reactions can lead to an incorrect identification of influential parameters and key reaction intermediates and reactions. We rationalize why models often underpredict reaction rates and show that, despite the uncertainty being large, the method can, in conjunction with experimental data, identify influential missing reaction pathways and provide insights into the catalyst active site and the kinetic reliability of a model. The method is demonstrated in ethanol steam reforming for hydrogen production for fuel cells.
authors.affiliation: Catalysis Center for Energy Innovation and Center for Catalytic Science and Technology, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, USA.
authors.forename: Jonathan E
authors.initials: JE
authors.lastname: Sutton
authors.affiliation: Catalysis Center for Energy Innovation and Center for Catalytic Science and Technology, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, USA.|Beijing Institute of Technology, School of Physics, Beijing 100081, China.
authors.forename: Wei
authors.initials: W
authors.lastname: Guo
authors.affiliation: Department of Mathematics and Statistics, University of Massachusetts at Amherst, Amherst, Massachusetts 01003, USA.
authors.forename: Markos A
authors.initials: MA
authors.lastname: Katsoulakis
authors.affiliation: Catalysis Center for Energy Innovation and Center for Catalytic Science and Technology, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, Delaware 19716, USA.
authors.forename: Dionisios G
authors.initials: DG
authors.lastname: Vlachos