Methane Oxidation over PdO(101) Revealed by First-Principles Kinetic Modeling

The
catalytic oxidation of methane to carbon dioxide and water
over PdO(101) is investigated with first-principles based microkinetic
modeling. Extensive exploration of the reaction landscape allows for
determination of preferred pathways at different reaction conditions.
The predicted kinetic behavior is in good agreement with a range of
experimental findings including reaction orders in methane, water,
and oxygen as well as apparent activation energies. The results consolidate
the role of the PdO(101) surface in the activity of PdO catalysts
and offer starting points for computational design of materials with
improved catalytic activity. Moreover, the study demonstrates the
predictive power of first-principles based kinetic modeling for oxide
surfaces when hybrid functionals are applied in conjugation with kinetic
models that go beyond the mean-field approximation.