Atomic-Scale Assembly of a Heterogeneous Catalytic Site

The distance between surface Pd atoms has been shown to control the catalytic formation of vinyl acetate from ethylene and acetic acid by AuPd catalysts. Here, we use the bulk alloy's thermodynamic properties, as well as the surface lattice spacing of a AuPd(100) alloy single-crystal model catalyst to control and optimize the concentration of the active site (Pd atom pairs at a specific Pd−Pd distance with Au nearest-neighbors). Scanning tunneling microscopy reveals that sample annealing has a direct effect on the surface Pd arrangements: short-range order preferentially forms Pd pairs located in the c(2 × 2) sites, which are known to be optimal for vinyl acetate synthesis. This effect could be harnessed for future industrial catalyst design.