Compressive surface strained atomic-layer Cu₂O on Cu@Ag nanoparticles

Control of surface structure at the atomic level can effectively tune catalytic properties of nanomaterials. Tuning surface strain is an effective strategy for enhancing catalytic activity; however, the correlation studies between the surface strain with catalytic performance are scant because such mechanistic studies require the precise control of surface strain on catalysts. In this work, a simple strategy of precisely tuning compressive surface strain of atomic-layer Cu₂O on Cu@Ag (AL-Cu₂O/Cu@Ag) nanoparticles (NPs) is demonstrated. The AL-Cu2O is synthesized by structure evolution of Cu@Ag core-shell nanoparticles, and the precise thickness-control of AL-Cu₂O is achieved by tuning the molar ratio of Cu/Ag of the starting material. Aberration-corrected high-resolution transmission electron microscopy (AC-HRTEM) and EELS elemental mapping characterization showed that the compressive surface strain of AL-Cu₂O along the [111] and [200] directions can be precisely tuned from 6.5% to 1.6% and 6.6% to 4.7%, respectively, by changing the number of AL-Cu₂O layer from 3 to 6. The as-prepared AL-Cu₂O/Cu@Ag NPs exhibited excellent catalytic property in the synthesis of azobenzene from aniline, in which the strained 4-layers Cu₂O (4.5% along the [111] direction, 6.1% along the [200] direction) exhibits the best catalytic performance. This work may be beneficial for the design and surface engineering of catalysts toward specific applications.[Figure not available: see fulltext.].