Accurate coverage-dependence incorporated into first-principles kinetic models: Catalytic NO oxidation on Pt (1 1 1)

C. Wu, D. J. Schmidt, C. Wolverton, W. F. Schneider*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

158 Scopus citations

Abstract

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 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.

Original languageEnglish (US)
Pages (from-to)88-94
Number of pages7
JournalJournal of Catalysis
Volume286
DOIs
StatePublished - Feb 2012

Funding

We thank Dr. Rachel Getman, Dr. Andrew Smeltz, Prof. Fabio Ribeiro, Prof. Nick Delgass, Dr. Jean-Sabin McEwen, Dr. Zhengzheng Chen, and Mr. Jason Bray for helpful discussions. We also acknowledge computational resources provided by the Center for Research Computing at the University of Notre Dame and the Center for Nanoscale Materials at Argonne National Laboratory. Financial support for this work was provided the US Department of Energy under Grant DE-FG02–06ER15839 and by the National Science Foundation under Contract Nos. CBET-0731020 and CBET-0730841.

Keywords

  • Adsorbate-adsorbate interactions
  • Cluster expansion
  • DFT
  • NO oxidation kinetics
  • O dissociation
  • Pt (1 1 1)
  • Rate laws

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

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