Environment-driven reactivity of H2 on PdRu surface alloys

Abstract

The dissociative adsorption of molecular hydrogen on Pd_xRu_1−x/Ru(0001) (0 ≤ x ≤ 1) has been investigated by means of He atom scattering, Density Functional Theory and quasi-classical trajectory calculations. Regardless of their surroundings, Pd atoms in the alloy are always less reactive than Ru ones. However, the reactivity of Ru atoms is enhanced by the presence of nearest neighbor Pd atoms. This environment-dependent reactivity of the Ru atoms in the alloy provides a sound explanation for the striking step-like dependence of the initial reactive sticking probability as a function of the Pd concentration observed in experiments. Moreover, we show that these environment-dependent effects on the reactivity of H₂ on single atoms allow one to get around the usual constraint imposed by the Brønsted–Evans–Polanyi relationship between the reaction barrier and chemisorption energy.