Comparison of chemiluminescence from luminol solution and luminol-TiO2 suspension after illumination of a 355 nm pulse laser.

Chemiluminescence (CL) from luminol solution and luminol-TiO2 suspension after illumination of a 355 nm pulse laser is compared. Both the CL systems showed the CL spectra with maximum wavelength of 430 nm, suggesting that the emission was from the excite state of 3-aminophthalate ion. The TiO2 photocatalytically induced luminol CL could be separately detected either when the pulse laser power was smaller than 0.15 mJ/pulse or a slit was placed beyond -2-2 mm in the vertical direction of the laser beam. The TiO2 photocatalytically induced luminol CL intensity was linear to the laser power, while that of the 355 nm pulse laser-induced was nonlinear. A log-log plot between the 355 nm pulse laser-induced luminol CL intensity and laser power showed a near-linear regression fit with a slope of 2.11, suggesting that a two-photon absorption process of luminol was present in the 355 nm pulse laser-induced luminol CL. Adsorbed oxygen on the surface of TiO2 seemed to greatly contribute to the photocatalytically induced CL.

Chemiluminescence from luminol solution after illumination of a 355 nm pulse laser.

Chemiluminescence (CL) on the time scale of microseconds to milliseconds from luminol solution after illumination of a 355 nm pulse laser is reported. It was found that the CL is the emission from 3-aminophthalate ion (AP*). In CL decay after the pulse laser illumination, a peak was observed from about 200 to 30 micros depending on the laser power and the luminol concentration. It seemed that there was a fast and slow decay process; their kinetics were greatly dependent on the laser power and the luminol concentration. Dissolved oxygen was involved in the CL and played the same role on the whole time scale of microseconds to milliseconds. Involvement of reactive oxygen species such as H(2)O(2), (1)O(2), O(2) (*-) and OH in the CL was examined by adding their scavengers. Experimental results suggested that the possibility of involvement of H(2)O(2) and (1)O(2) in the CL was low. The CL in time periods less than 50 micros might be related to *OH. The (*)O(2) (*-)-induced CL increased with time after 50 micros and became dominant on the time scale of milliseconds. The CL was considered to be caused by both the photoionization and type I reaction mechanisms.

Time-resolved chemiluminescence study of the TiO2 photocatalytic reaction and its induced active oxygen species.

The time-resolved chemiluminescence (CL) method has been applied to study the TiO(2) photocatalytic reaction on a micros-ms timescale. The experimental set-up for time-resolved CL was improved for confirmation of the unique luminol CL induced by the photocatalytic reaction. The third harmonic light (355 nm) from an Nd:YAG laser was used for the light source of the TiO(2) photocatalytic reaction. Luminol CL induced by this reaction was detected by a photomultiplier tube (PMT) and a preamplifier was used for amplifying the CL signal. Experimental conditions affecting the photocatalytically induced CL were discussed in detail. The involvement of active oxygen species such as .OH, O(2) (.-) and H(2)O(2) in the CL was examined by adding their scavengers. It is concluded that .OH was greatly involved in the CL on a micros-ms timescale, especially in time periods <100 micros after illumination of the pulse laser. On the other hand, CL generated by O(2) (.-) began to increase after 100 micros and became dominant after 2.5 ms. A small part of the CL might be generated by H(2)O(2) on the whole micros-ms timescale. A CL reaction mechanism related with .OH and dissolved oxygen was proposed to explain the photocatalytically induced luminol CL on a micros-ms timescale, especially in periods <100 micros.