Accurate coverage-dependence incorporated into first-principles kinetic models: Catalytic NO oxidation on Pt (111)

作者：Wu C; Schmidt D J; Wolverton C; Schneider W F^*

来源：Journal of Catalysis, 2012, 286: 88-94.

DOI：10.1016/j.jcat.2011.10.020

• Adsorbate-adsorbate interactions
• DFT
• Cluster expansion
• Rate laws
• NO oxidation kinetics
• Pt (111)
• O-2 dissociation

The coverage, of surface adsorbates influences both the number and types of sites available for catalytic reactions at a heterogeneous surface, but accounting for adsorbate-adsorbate interactions and understanding their implications on observed rates remain challenges for simulation. Here, we demonstrate the use of a density functional theory (DFT)-parameterized cluster expansion (CE) to incorporate accurate adsorbate-adsorbate interactions into a surface kinetic model. The distributions of adsorbates and reaction sites at a metal surface as a function of reaction conditions are obtained through Grand Canonical Monte Carlo simulations on the CE Hamiltonian. Reaction rates at those sites are obtained from the CE through a DFT-parameterized Bronsted-Evans-Polyani (BEP) relationship. The approach provides ready access both to steady-state rates and rate derivatives and further provides insight into the microscopic factors that influence observed rate behavior. We demonstrate the approach for steady-state O-2 dissociation at an O-covered Pt (1 1 1) surface a model for catalytic NO oxidation at this surface and recover apparent activation energies and rate orders consistent with experiment.

• 出版日期2012-2
• 单位西北大学