PNNL

Abstract

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. We present a microkinetic model as well as experimental data for the low-temperature water gas shift (WGS) reaction catalyzed by Pt at temperatures from 523 to 573 K and for various gas compositions at a pressure of 1 atm. Thermodynamic and kinetic parameters for the model are derived from periodic, self-consistent density functional theory (DFT-GGA) calculations on Pt(111). The destabilizing effect of high CO surface coverage on the binding energies of surface species is quantified through DFT calculations and accounted for in the microkinetic model. Deviations of specific fitted model parameters from DFT calculated parameters on Pt(111) point to the possible role of steps/defects in this reaction. Our model predicts reaction rates and reaction orders in good agreement with our experiments. The calculated and experimental apparent activation energies are 67.8 kJ/mol and 71.4 kJ/mol, respectively. The model shows that the most significant reaction channel proceeds via a carboxyl (COOH) intermediate. Formate (HCOO), which has been experimentally observed and thought to be the key WGS intermediate in the literature, is shown to act only as a spectator species.