Atomic-Scale Engineering of CuO_x-Au Interfaces over AuCu Single-Nanoparticles

A face-centered tetragonal (fct) AuCu particle with a size of 7.1 nm and an Au/Cu molar ratio of 1/1 was coated by a silica shell of 6 nm thickness. Segregation of Cu atoms from the metal particle under an oxidative atmosphere precisely mediated the CuO_x-Au interfacial structure by simply varying the temperature. As raising the temperature from 473 to 773 K, more Cu atoms emigrated from the AuCu particle and were oxidized into CuO_x layers that grew up to 0.8 nm in thickness. Simultaneously, the size of the Au-rich particle lowered moderately while the crystalline structure transformed from the fct phase into the face-centered cubic (fcc) phase. The CuO_x-Au interface shifted from the CuO_x monolayer bound to Au single-atoms to Au@CuO_x core-shell geometry, while the catalytic activity for CO oxidation at 433 K decreased dramatically. Moreover, a sharp loss in activity was observed as the crystal-phase transition occurred. This change in catalytic performance was ascribed to the geometrical configuration at the interfacial sites: the synergetic effect between the fct-AuCu particle and CuO_x monolayer contributed to the much higher activity, whereas the fcc-AuCu/Au particle weakened its interaction with the thicker CuO_x layer and thus decreased the activity.