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 CuOx–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 CuOx 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 CuOx–Au interface shifted from the CuOx monolayer bound to Au single-atoms to Au@CuOx 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 CuOx monolayer contributed to the much higher activity, whereas the fcc-AuCu/Au particle weakened its interaction with the thicker CuOx layer and thus decreased the activity.