Enhanced Antibacterial Activity at Ag–Cu Nanojunctions: Unveiling the Mechanism with Simple Surfaces of CuNPs-on-Ag Films

[Image: see text] Deposition of CuNPs on silver film gives rise to the formation of active Ag–Cu interfaces leading to dramatic enhancements in antibacterial activity against Escherichia coli. Transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDAX) analyses reveal that CuNPs are covered in a thin Cu(2)O shell, while X-ray photoelectron spectroscopy measurements (XPS) reveal that the Ag film samples contain significant amounts of Ag(2)O. XPS analyses show that the deposition of CuNPs on Ag films leads to the formation of a photoactive Ag(2)O–Cu(2)O heterostructure. Following a Z-scheme mechanism, electrons from the conduction band of Ag(2)O recombine with photogenerated holes from the valence band of Cu(2)O. Consequently, electrons at Cu(2)O’s conduction band render Cu reduced and cause reductive activation of surface oxygen species on Cu forming reactive oxygen species (ROS). Interaction between metallic Cu and ROS species leads to the formation of a Cu(OH)(2) phase. Both ROS and Cu(OH)(2) species have previously been reported to lead to enhanced antibacterial properties. Holes on Ag(2)O produce a highly oxidized AgO phase, a phase reported to exhibit excellent antibacterial properties. Quantitative analysis of Cu and Ag high-resolution X-ray photoelectron spectroscopy (HR-XPS) spectra directly reveals several-fold increases in these active phases in full agreement with the observed increase in antibacterial activities. This study provides insight and surface design parameters by elucidating the important roles of Ag and Cu’s bifunctionality as active antibacterial materials.