Accurate coverage-dependence incorporated into first-principles kinetic models: Catalytic NO oxidation on Pt(111)
Title of Paper:
Accurate coverage-dependence incorporated into first-principles kinetic models: Catalytic NO oxidation on Pt(111)
Summary:
本文提出并实现了基于第一原理的预测表面催化反应动力学的方法，能够定量准确地预测反应动力学相关的性质。
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 Brønsted–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 O2 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.
Co-author:
吴超，D.J. Schmidt, C. Wolverton, W.F. Schneider
Page Number:
doi:10.1016/j.jcat.2011.10.020
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