Tailoring of the photocatalytic activity of CeO ₂ nanoparticles by the presence of plasmonic Ag nanoparticles

The present study investigates basic features of a photoelectrochemical system based on CeO₂ nanoparticles fixed on gold electrodes. Since photocurrent generation is limited to the absorption range of the CeO₂ in the UV range, the combination with metal nanoparticles has been studied. It can be shown that the combination of silver nanoparticles with the CeO₂ can shift the excitation range into the visible light wavelength range. Here a close contact between both components has been found to be essential and thus, hybrid CeO₂@Ag nanoparticles have been prepared and analyzed. We have collected arguments that electron transfer occurs between both compositional elements of the hybrid nanoparticles.The photocurrent generation can be rationalized on the basis of an energy diagram underlying the necessity of surface plasmon excitation in the metal nanoparticles, which is also supported by wavelength-dependent photocurrent measurements. However, electrochemical reactions seem to occur at the CeO₂ surface and consequently, the catalytic properties of this material can be exploited as exemplified with the photoelectrochemical reduction of hydrogen peroxide. It can be further demonstrated that the layer-by layer technique can be exploited to create a multilayer system on top of a gold electrode which allows the adjustment of the sensitivity of the photoelectrochemical system. Thus, with a 5-layer electrode with hybrid CeO₂@Ag nanoparticles submicromolar hydrogen peroxide concentrations can be detected.