The correlation between structural properties, geometrical features, and photoactivity of freestanding TiO₂ nanotubes in comparative degradation of 2,4-dichlorophenol and methylene blue

Freestanding TiO₂ nanotubes (FSNTs) with various physical dimensions were fabricated by two-step anodization process with different voltages and anodization times. The detachment method employed in this study involved voltage reduction at the end of the second step and ultrasonic chemical treatment. The results demonstrated that this detachment method is a beneficial technique to create thin open-mouthed and closed-end FSNTs (with lengths of 6–14 μm). Moreover, the influences of anodization conditions on photocatalytic activity, structural properties and geometrical features of FSNTs in comparative degradation of two non-colored (2,4-dichlorophenol) and colored (methylene blue) pollutants were investigated. Findings revealed that the quantity of the photocatalyst utilized is an effective parameter and using the optimum weight (10 mg/100 ml of 2,4-dichlorophenol) could increase the efficiency of the process up to 21%. Further, the results demonstrated that if equal optimum weights of FSNTs are chosen, decreases in voltage and anodization time significantly influence the structural properties, geometrical features, and photodegradation efficiency. The enhancement achieved in the degradation of both 2,4-dichlorophenol and methylene blue using the nanotubes with the shortest diameter (54 nm) and length (6.5 μm), which possess the lowest porosity (0.5) and also the highest surface area (0.53 m² g⁻¹), nanotubes' density (19 cm² cm⁻²) and wall thickness to length ratio (2). In addition, the results obtained indicated that the degradation reactions follow first-order kinetics in the degradation of the both pollutants. The apparent degradation rate constant of methylene blue was approximately 1.2 times greater than of the 2,4-dichlorophenol due to the negative charge of the nanotubes' surface and electrostatic adsorptions. (paper)