Prediction of Mode Specificity, Bond Selectivity, Normal Scaling, and Surface Lattice Effects in Water Dissociative Chemisorption on Several Metal Surfaces Using the Sudden Vector Projection Model

Abstract

Dissociative chemisorption of water is a key step in many heterogeneous catalytic processes such as water–gas shift and steam reformation. As a result, a better understanding of the mechanism and dynamics of these processes is important for developing a predictive model of catalysis. In this work, we use the recently proposed Sudden Vector Projection (SVP) model to predict mode specificity, bond selectivity, normal scaling behavior, and surface lattice effects in water dissociative chemisorption on Ni(111), Cu(111), Pt(111), and Pt(110)-(1 × 2), based on direct plane-wave density functional theory calculations. While mode specificity and bond selectivity are similar on these surfaces, the SVP model predicts significant differences in the reaction promoting effects of kinetic energies in the surface normal and along the surface plane, signifying the different characters of the transition state on these metal surfaces. Furthermore, the involvement of surface atoms is shown, which predicts significant surface temperature effects.