An Efficient Photocatalyst Structure: TiO2(B) Nanofibers with a Shell of Anatase Nanocrystals

Abstract

A new efficient photocatalyst structure, a shell of anatase nanocrystals on the fibril core of a single TiO2(B) crystal, was obtained via two consecutive partial phase transition processes. In the first stage of the process, titanate nanofibers reacted with dilute acid solution under moderate hydrothermal conditions, yielding the anatase nanocrystals on the fiber. In the subsequent heating process, the fibril core of titanate was converted into a TiO2(B) single crystal while the anatase crystals in the shell remained unchanged. The anatase nanocrystals do not attach to the TiO2(B) core randomly but coherently with a close crystallographic registry to the core to form a stable phase interface. For instance, (001) planes in anatase and (100) planes of TiO2(B) join together to form a stable interface. Such a unique structure has several features that enhance the photocatalytic activity of these fibers. First, the differences in the band edges of the two phases promote migration of the photogenerated holes from anatase shell to the TiO2(B) core. Second, the well-matched phase interfaces allow photogenerated electrons and holes to readily migrate across the interfaces because the holes migrate much faster than excited electrons, more holes than electrons migrate to TiO2(B) and this reduces the recombination of the photogenerated charges in anatase shell. Third, the surface of the anatase shell has both a strong ability to regenerate surface hydroxyl groups and adsorb O2, the oxidant of the reaction, to yield reactive hydroxyl radicals (OH·) through reaction between photogenerated holes and surface hydroxyl groups. The adsorbed O2 molecules can capture the excited electrons on the surface, forming reactive O2− species. The more reactive species generated on the external surface, the higher the photocatalytic activity will be, and generation of the reactive species also contributes to reducing recombination of the photogenerated charges. Indeed, the mixed-phase nanofibers exhibited superior photocatalytic activity for degradation of sulforhodamine B under UV light to the nanofibers of either pure phase alone or mechanical mixtures of the pure phase nanofibers with a similar phase composition. Finally, the nanofibril morphology has an additional advantage that they can be separated readily after reaction for reuse by sedimentation. This is very important because the high cost for separating the catalyst nanocrystals has seriously impeded the applications of TiO2 photocatalysts on an industrial scale.