Effects of doping amounts of potassium ferricyanide with titanium dioxide and calcination durations on visible-light degradation of pharmaceuticals.

Acetaminophen (ACT) is one of the most frequently detected pharmaceuticals in aqueous environments, and treatment of ACT were generally carried out by photocatalytic degradations under high energy UV irradiation. In this study, potassium ferricyanide was utilized as a quadruple-elemental dopant in a TiO2 photocatalyst in order to enhance its visible-light activity. Two critical parameters (amounts of dopants and durations of calcination) of the synthesis of the photocatalyst by a sol-gel method were systematically evaluated. Crystal structure of the doping TiO2 was examined by X-ray diffraction while the effects of the two parameters on the photocatalytic activity were elucidated by various characterizations. Increasing the amount of dopant or the duration of calcination red-shifted the UV-vis DRS of the doped TiO2. The estimated band gap energy of the doped TiO2 decreased slightly as the amount of dopant increased, but it increased as the duration of calcination increased. The FT-IR yielded characteristic peaks that revealed the effects of the two parameters, whereas the SEM images revealed the morphological evolutions of each effect. The photocatalyst, synthesized at optimum conditions was able to remove 99.1 % acetaminophen with rate constant of 7.9 × 10-3 min-1, which was 4.88 times greater than virgin TiO2. In general, this study not only optimized synthetic conditions of the new visible-light active photocatalyst for ACT degradation but also presented characterizations conducted by SEM, XRD, UV-vis DRS, and FTIR to elucidate the relationship between modified structure and the photocatalytic activity. Graphical abstract Effects of doping amounts of K3[Fe(CN)6] and calcunation duration on visible light absorbance of TiO2 photocatalysts.

Kinetic study of acetaminophen degradation by visible light photocatalysis.

In this work, a novel photocatalyst K3[Fe(CN)6]/TiO2 synthesized via a simple sol-gel method was utilized to degrade acetaminophen (ACT) under visible light with the use of blue and green LED lights. Parameters (medium pH, initial concentration of reactant, catalyst concentration, temperature, and number of blue LED lights) affecting photocatalytic degradation of ACT were also investigated. The experimental result showed that compared to commercially available Degussa P-25 (DP-25) photocatalyst, K3[Fe(CN)6]/TiO2 gave higher degradation efficiency and rate constant (kapp) of ACT. The degradation efficiency or kapp decreased with increasing initial ACT concentration and temperature, but increased with increased number of blue LED lamps. Additionally, kapp increased as initial pH was increased from 5.6 to 6.9, but decreased at a high alkaline condition (pH 8.3). Furthermore, the degradation efficiency and kapp of ACT increased as K3[Fe(CN)6]/TiO2 loading was increased to 1 g L(-1) but decreased and eventually leveled off at photocatalyst loading above this value. Photocatalytic degradation of ACT in K3[Fe(CN)6]/TiO2 catalyst system follows a pseudo-first-order kinetics. The Langmuir-Hinshelwood equation was also satisfactorily used to model the degradation of ACT in K3[Fe(CN)6]/TiO2 catalyst system indicated by a satisfactory linear correlation between 1/kapp and Co, with kini = 6.54 × 10(-4) mM/min and KACT = 17.27 mM(-1).