Surface Reactivity at “Chiral” Platinum Surfaces

The electro-oxidation of d - and l -glucose has been investigated using the chiral electrode Pt{643} R and its enantiomorph Pt{643} S . Both electrodes are demonstrated to be enantioselective. We ascribe this behavior to the inherent (left or right) “handedness” of kink sites present at the surface. In contrast, no difference in d - and l -glucose oxidation could be detected using stepped Pt{211} and Pt{332} electrodes. Stepped surfaces are achiral, since they lack the prerequisite necessary for the observation of chirality, namely kink sites. For Pt{531}, a surface which contains only kink sites, a diastereomeric product excess of ∼80% is estimated for d - and l -glucose oxidation. This compares with a value of ∼60% for Pt{643}. Hence, the chiral discrimination appears to scale with the surface density of kink sites. These findings constitute the first experimental proof that chiral discrimination is an intrinsic property of kinked single-crystal surfaces.