Understanding Trends in Catalytic Activity: The Effect of Adsorbate-Adsorbate Interactions for CO Oxidation Over Transition Metals

Using high temperature CO oxidation as the example, trends in the reactivity of transition metals are discussed on the basis of density functional theory (DFT) calculations. Volcano type relations between the catalytic rate and adsorption energies of important intermediates are introduced and the effect of adsorbate–adsorbate interac- tion on the trends is discussed. We find that adsorbate– adsorbate interactions significantly increase the activity of strong binding metals (left side of the volcano) but the interactions do not change the relative activity of different metals and have a very small influence on the position of the top of the volcano, that is, on which metal is the best catalyst.