Low temperature synthesis of polyaniline–crystalline TiO2–halloysite composite nanotubes with enhanced visible light photocatalytic activity

Abstract

A series of one-dimensional polyaniline–crystalline TiO2–halloysite composite nanotubes with different mass ratio of polyaniline to TiO2 are facilely prepared by employing the low-temperature synthesis of crystalline TiO2 on halloysite nanotubes. The halloysite nanotubes can adsorb TiO2/polyaniline precursors and induce TiO2 nanocrystals/polyaniline to grow on the support in situ simultaneously. By simply adjusting the acidity of reaction system, PANI-crystalline TiO2–HA composite nanotubes composed of anatase, a mixed phase TiO2 and different PANI redox state are obtained. The XRD and UV–vis results show that the surface polyaniline sensitization has no effect on the crystalline structure of halloysite and TiO2 and the light response of TiO2 is extended to visible-light regions. Photocatalysis test results reveal the photocatalytic activity will be affected by the pH value and the volume ratio of ANI to TTIP. The highest photocatalytic activity is achieved with the composite photocatalysts prepared at pH 0.5 and 1% volume ratio of ANI and TTIP owing to the sensitizing effect of polyaniline and the charge transfer from the photoexcited PANI sensitizer to TiO2. Moreover, the PANI–TiO2–HA composite nanotubes synthesized by one-step at pH 0.5 with 1% volume ratio of ANI to TTIP exhibit higher visible light photocatalytic activity than those synthesized by the two-step. Heterogeneous PANI–TiO2–HA composite nanotubes prepared at pH 0.5 exhibit a higher degradation activity than that prepared at pH 1.5. The redoped experiment proves that the PANI redox state plays the main contribution to the enhanced visible light catalytic degradation efficiency of PANI–TiO2–HA prepared at pH 0.5. Furthermore, the heterogeneous PANI-crystalline TiO2–HA nanotubes have good photocatalytic stability and can be reused four times with only gradual loss of activity under visible light irradiation.