Role of Steps inN2Activation on Ru(0001)

Using adsorption experiments and density functional calculations we show that ${\mathrm{N}}_2$ dissociation on the Ru(0001) surface is totally dominated by steps. The measured adsorption rate at the steps is at least 9 orders of magnitude higher than on the terraces at 500 K, and the corresponding calculated difference in activation energy is 1.5 eV. The low barrier at the step is shown to be due to a combination of electronic and geometrical effects. The consequences for Ru as a catalyst for ammonia synthesis are discussed.