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Synopsis Ag/ZnO heterostructure nanocatalysts with excellent photocatalytic performance were successfully prepared through a simple solvothermal method. The correlation between the structure and photocatalytic property was investigated in detail. It was found that the addition of Ag + resulted in the formation of zerovalent metallic Ag deposits on the surface of ZnO nanocrystals, and the photocatalytic activity of Ag/ZnO nanocatalysts is dependent on their structure, especially the heterostructure. The presence of Ag nanoparticles and oxygen vacancy on the surface of ZnO nanorods promotes the separation of photogenerated electron−hole pairs and thus enhances the photocatalytic activity.

A high yield of the dimer-type heterostructure of Ag/ZnO nanocrystals with different Ag contents is successfully prepared through a simple solvothermal method in the absence of surfactants. The samples are characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, UV−vis spectroscopy, and IR spectroscopy. The results show that all samples are composed of metallic Ag and ZnO; Ag nanoparticles locate on the surface of ZnO nanorods; the binding energy of Ag 3d 5/2 for the Ag/ZnO sample with a Ag content of 5.0 atom% shifts remarkably to the lower binding energy compared with the corresponding value of pure metallic Ag because of the interaction between Ag and ZnO nanocrystals; the concentration of oxygen vacancy for the as-synthesized samples varies with the increasing Ag content, and the Ag/ZnO sample with a Ag content of 5.0 atom% has the largest density of oxygen vacancy. In addition, the relationship between their structure and photocatalytic property is investigated in detail. It is found that the photocatalytic property is closely related to its structure, such as heterostructure, oxygen defect, and crystallinity. The presence of metallic Ag nanoparticles and oxygen vacancy on the surface of ZnO nanorods promotes the separation of photogenerated electron−hole pairs and thus enhances the photocatalytic activity.