Full Catalytic Pathway of Methane Oxidation on PdO Determined from First Principles


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

Journal of the American Chemical Society (0002-7863). Vol. 137 (2015), 37, p. 12035-12044.

Maxime Van den Bossche and Henrik Grönbeck

In this paper the authors address the reaction pathways that occur in the catalytic combustion of methane over PdO catalysts. Although PdO(101) has previously been recognized as the most active PdO surface, and the interaction of various adsorbates with the surface has been studied, the question remained through which elementary reactions methane is converted all the way to carbon dioxide. 


In order to tackle this problem, the authors apply a first-principles microkinetics framework. The kinetic parameters for many different surface reactions are estimated via density functional and transition state theory calculations. Then, the interplay of the individual reactions is resolved by integrating the rate equations. The favourable comparison between the calculated and experimentally observed kinetic behaviour serves as a validation of the model. In this way, the probable conversion pathways are revealed, as well as the molecular origin of the measured activation energies and reaction orders.

Published: Wed 02 Dec 2015.