Scaling Platinum-Catalyzed Hydrogen Dissociation on Corrugated Surfaces.

We determine absolute reactivities for dissociation at low coordinated Pt sites. Two curved Pt(111) single-crystal surfaces allow us to probe either straight or highly kinked step edges with molecules impinging at a low impact energy. A model extracts the average reactivity of inner and outer kink atoms, which is compared to the reactivity of straight A- and B-type steps. Local surface coordination numbers do not adequately capture reactivity trends for H dissociation. We utilize the increase of reactivity with step density to determine the area over which a step causes increased dissociation. This step-type specific reactive area extends beyond the step edge onto the (111) terrace. It defines the reaction cross-section for H dissociation at the step, bypassing assumptions about contributions of individual types of surface atoms. Our results stress the non-local nature of H interaction with a surface and provide insight into reactivity differences for nearly identical step sites.