Photodegradation of 4-chlorophenoxyacetic acid under visible LED activated N-doped TiO₂and the mechanism of stepwise rate increment of the reused catalyst

Photodegradation of 4-chlorophenoxyacetic acid (4-CPA) was systematically investigated using N-doped TiO2(N-TiO2) under commercially available visible light emitting diode (Vis LED) as a novel Vis LED illumination in photocatalysis applications. The synergetic effect of Vis LED/N-TiO2process was studied in detail by varying reaction conditions including the initial concentration of 4-CPA, catalyst dosage, light intensity, and initial pH. Additionally, the influence of inorganic anions and radical scavengers on the performance of the Vis LED/N-TiO2process was also evaluated. The Vis LED/N-TiO2was found to be a promising process in terms of mineralization of 4-CPA. It is interesting to note that the performance of this process was not reduced after successive usage of the recycled catalyst; instead, the reaction rate of 4-CPA decay actually increased by using the spent catalyst. The mechanism behind rate enhancement after/during reuse was explored by XPS and FT-IR analyses and it was proven that hydroxyl groups can be incorporated into the catalyst surface by the repeated wetting of N-TiO2after each reuse. This facilitates the formation of hydrogen bonds between the 4-CPA molecules and N-TiO2, thereby allowing more collisions between the trapped 4-CPA and radicals at the interface of bulk solution and catalyst, respectively.