Time-resolved photoluminescence of anatase/rutile TiO_2 phase junction revealing charge separation dynamics

Junctions are an important structure that allows charge separation in solar cells and photocatalysts. Here, we studied the charge transfer at an anatase/rutile TiO2 phase junction using time-resolved photoluminescence spectroscopy. Visible （-S00 nm） and near-infrared （NIR, -830 nm） emissions were monitored to give insight into the photoinduced charges of anatase and rutile in the junction, respectively, New fast photoluminescence decay components appeared in the visible emission of futile-phase dominated TiO2 and in the NIR emission of many mixed phase TiO2samples. The fast decays confirmed that the charge separation occurred at the phase junction. The visible emission intensity from the mixed phase TiO2 increased, revealing that charge transfer from rutile to anatase was the main pathway. The charge separation slowed the microsecond time scale photolumines- cence decay rate for charge carriers in both anatase and rutile. However, the millisecond decay of the charge carriers in anatase TiO2 was accelerated, while there was almost no change in the charge carrier dynamics of rutile TiO2. Thus, charge separation at the anatase/rutile phase junction caused an increase in the charge carrier concentration on a microsecond time scale, because of slower electron-hole recombination. The enhanced photocatalytic activity previously observed at ana- tase/rutile phase junctions is likely caused by the improved charge carrier dynamics we report here. These findings may contribute to the development of improved photocatalytic materials.

Phase-junction Ag/TiO_(2)nanocomposite as photocathode for H_(2)generation

Developing anatase/rutile phase-junction in Ti O_(2)to construct Z-scheme system is quite effective to improve its photoelectrochemical activity.In this work,the anatase/rutile phase-junction Ag/Ti O_(2)nanocomposites are developed as photocathodes for hydrogen production.The optimized Ag/Ti O_(2)nanocomposite achieves a high current density of 1.28 m A cm-2,an incident photon-to-current conversion efficiency(IPCE)of 10.8%,an applied bias photon-to-current efficiency(ABPE)of 0.32 at 390 nm and a charge carriers’lifetime up to 2000 s.Such enhancement on photoelectrochemical activity can be attributed to:(ⅰ)the generated Z-scheme system in the anatase/rutile phase-junction Ag/Ti O_(2)photocathode enhances the separation,diffusion and transformation of electron/hole pairs inside the structure,(ⅱ)Ag nanodots modification in the anatase/rutile phases leading to the tuned band gap with enhanced light absorption and(ⅲ)the formed Schottky barrier after Ag nanodots surface modification provides enough electron traps to avoid the recombination of photogenerated electrons and holes.Our results here suggest that developing phase-junction nanocomposite as photocathode will provide a new vision for their enhanced photoelectrochemical generation of hydrogen.

Photodegradation of benzene by TiO_2 nanoparticles prepared by flame CVD process

Photodegradation of benzene at ppb levels by mixed-phase TiO2 nanoparticles, synthesized by the oxidation of TiCl4 in propane/air turbulent flame chemical vapor deposition （CVD） process, is investigated experimentally by using a tubular photoreactor with thin TiO2 films coated on the reactor wall by sedimentation. Effects of inlet benzene concentration from 10 to 300μg/m3, rutile mass fraction from about 20 to 50% and photoluminescence （PL） intensity of TiO2 nanoparticles on degradation degree are examined under the conditions of 70% relative humidity, 38 μg/cm2 catalyst loading, 24mW/cm2 UV irradiation of 254 nm and 5.7 s residence time in the reactor. Based on experimental results, separation of photoinduced electron （e-） and hole （h＋） pairs by rutile phase is discussed as photo-induced electron （e-） in anatase phase will migrate to rutile surface due to that the potential of conductive band of rutile is lower than that of anatase, leading to more holes ready on anatase surface for oxidation reactions.

Relationship between Crystal Structure of Inclusions and Formation of Acicular Ferrites

The formation mechanism of intragranular ferrites with acicular morphology was discussed.The ferrites were characterized by scanning electron microscopy.The results showed that the ferrites had an acicular structure with radial,symmetrical,and acicular laths,and that the inclusions were the nucleation sites of the intragranular acicular ferrites.Transmission electron microscopy（TEM）was used to characterize the inclusions.The results of TEM with energy dispersive spectroscopy and TEM-selected area electron diffraction indicated that the complex inclusions consisted of Ti-Al complex oxides and MnS.The jagged edges of the complex inclusions can be ascribed to the effects of the crystal structure.The stabilization energy U of the coordination polyhedron growth units varies with the type of connection according to the calculation results.A larger Ucorresponds to more stable growth units,which induces the preferentially oriented growth of inclusions,at which point acicular ferrites are formed.