Photoluminescence spectral change in layered titanate oxide intercalated with hydrated Eu3+.

A number of interesting photoluminescence properties of titanate layered oxide intercalated with hydrated Eu3+ have been demonstrated. Photoluminescence intensity of Eu3+ decreased rapidly with time during irradiation by UV light having energy higher than the band gap energy of the host TiO (Ti(1.81)O4) layer. This is presumably due to the decrease in energy transfer from the host TiO layer to Eu3+ as a result of the change in the hydration state of water molecules surrounding Eu3+, which is caused by the hole produced in the TiO valence band. When irradiation was discontinued, the emission intensity gradually recovered. The recovery time increased when the water in the interlayer is removed by heat treatment. This indicates that the state of interlayer water changes during irradiation and returns to its initial state after discontinuation of irradiation. The excitation spectra changed drastically at any given wavelength upon irradiation with UV light. A comparison of the excitation spectra before and after irradiation reveals that only the excitation peak at around the irradiation wavelength decreased upon irradiation, as in the case of spectral hole burning. The hydration state of water molecules surrounding Eu3+ presumably changes depending on the irradiation wavelength, leading to the above spectral change because the Eu/TiO film has a superlattice structure producing holes with different energies.

Photoelectrochemical oxidation of methanol on oxide nanosheets.

Photoelectrochemical oxidation of alcohol on various nanosheet electrodes such as Nb6O17, Ca2Nb3O10, Ti(0.91)O2, Ti4O9, and MnO2 system host layers were measured to evaluate the photocatalysis of water photolysis with alcohol as a sacrificial agent. The nanosheet electrodes were prepared by the layer-by-layer (LBL) method, using electrostatic principles. The highest photooxidation current density was observed in methanol solution for Nb6O17 and Ca2Nb3O10 nanosheets, while the density was lower for Ti(0.91)O2, Ti4O9, and MnO2 nanosheets in decreasing order. The rank in the photocurrent density was in agreement with that in the photocatalytic activity, which means that the degree of photooxidation of the alcohol determines the activity of the alcohol in the water photolysis process. The photocurrent was independent of the number of nanosheet layers on the electrode, indicating that only the mono-nanosheet layer attached directly on a substrate acts as a photoelectrocatalyst and that the interlayer space is not important. Consequently, higher photooxidation current on the Nb6O17 mono-nanosheet layer means that the charge separation of electron and hole under illumination is very large and that the hole-capturing process by CH3OH is very quick compared with the surface recombination on the Nb6O17 nanosheet. The adsorption of a transition metal cation on the nanosheet acted as the surface recombination center, because the photocurrent decreased after the adsorption. The photocatalytic mechanism has been discussed in detail in terms of various photoelectrochemical behaviors.

Photoluminescence properties of multilayer oxide films intercalated with rare earth ions by the layer-by-layer technique.

Multilayer oxide films consisting of a TiO-Eu3+-TiO-Tb3+-NbO-Tb3+-NbO-Eu3+ unit which was prepared by the layer-by-layer technique, showed photoluminescence with a high intensity containing both red and green lights.