RESUMO
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 Cu2O shell, while X-ray photoelectron spectroscopy measurements (XPS) reveal that the Ag film samples contain significant amounts of Ag2O. XPS analyses show that the deposition of CuNPs on Ag films leads to the formation of a photoactive Ag2O-Cu2O heterostructure. Following a Z-scheme mechanism, electrons from the conduction band of Ag2O recombine with photogenerated holes from the valence band of Cu2O. Consequently, electrons at Cu2O'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 Ag2O 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.
RESUMO
Ni based catalysts have been widely studied for H2 production due to the ability of Ni to break C-C and C-H bonds. In this work, we study inverse catalysts prepared by well-controlled sub-monolayer deposition of CeO2 nanocubes onto Ni thin films for ethanol steam reforming (ESR). Results show that controlling the coverage of CeO2 nanocubes on Ni enhances H2 production by more than an order of magnitude compared to pure Ni. Contrary to the idea that C deposits must be continuously oxidized for sustained H2 production, the surface of the most active catalysts show significant C deposition, yet no deactivation is observed. HAADF-STEM analysis reveals the formation of carbon filaments (CFILs), which propel Ni particles upward at the filament tips via a catalytic tip growth mechanism, resulting in a Ni@CFIL active phase for ESR. Near-ambient pressure XPS indicates that the Ni@CFIL active phase forms as a result of C gradients at the interface between regions of pure Ni metal and domains of closely packed CeO2 nanocubes. These results show that the mesoscale morphology of deposited CeO2 nanocubes is responsible for templating the formation of a Ni@CFIL catalyst, which resists deactivation leading to highly active and stable H2 production from ethanol.
