Propene epoxidation with H-2/O-2 is a typical structure-sensitive reaction. For a given support containing tetra-coordinated Ti species such as TS-1, the catalytic activity is greatly influenced by supported Au nanoparticle size. The identification of size-dependent activity of Au catalyst was achieved over a series of Au nanoparticles (2.6-5.1 nm) deposited on the exterior surface of TS-1 by employing uncalcined TS-1. Through this approach, we could obtain very stable Au catalysts with distinguishable and uniform-sized Au particles, which are critical for structure-sensitivity analysis. The PO formation rate (mol(po) s(-1) mol(Au)(-1)) over these catalysts was found to vary with average Au diameter (d) as d(-2.7 +/- 0.3). Moreover, typical Au nanoparticles on uncalcined TS-1 appeared as truncated cuboctahedron with top facet of (1 1 1). Model calculations derived from the representative Au particle shape and the above size-dependent activity were then performed to show that corner sites of Au nanoparticles are dominant Au active sites for propene epoxidation. (C) 2014 Elsevier Inc. All rights reserved.