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This contribution aims to provide a brief account of the remarkable recent findings and advances in heterogeneous catalyst design based on facet rich Pt(111) on carbon materials. Platinum(111) hexagonal nanocrystals are prepared using Tween 20 as a facet directing agent via a simple, efficient and scalable thermolytic reduction process in air. These highly dispersed Pt(111) nanocrystals on carbon act as single site catalytic systems and exhibit exceptional activity (yield and ee ∼99%) and recyclability for the asymmetric hydrogenation of α-ketoesters.