Fabrication of ZnAl-LDH mixed metal-oxide composites for photocatalytic degradation of 4-chlorophenol

Abstract

In this work, two different types of ZnAl-layered double hydroxide (LDH) mixed metal-oxide composites (CeO₂ and SnO₂) were synthesized and applied for the photodegradation of 4-chlorophenol (4-CP) in wastewater. The fabricated CeO₂/ZnAl-LDH and SnO₂/ZnAl-LDH were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, UV-visible diffuse reflectance spectroscopy (UV-vis DRS), and theoretical density functional theory (DFT) calculations, suggesting that the band gaps of the synthesized hybrid composites were much lower than those of traditional ZnAl-LDH. In addition, the photocatalytic activity for 4-CP degradation and reaction kinetics were investigated to evaluate the catalytic behavior of the prepared composites. The results indicated that the photocatalytic process in this case followed a pseudo-first-order kinetic model, and SnO₂/ZnAl-LDH illustrated the optimum performance for 4-CP degradation with an efficiency of 95.2% due to its stability and recyclability. Additionally, the reaction mechanism of 4-CP photodegradation was studied over SnO₂/ZnAl-LDH; it presented that 4-CP could be oxidized by hydroxyl radicals, holes, and superoxide radicals, where hydroxyl radicals were identified as the dominant active species during the degradation process. Finally, decomposition intermediates were measured to deduce the reaction pathway of 4-CP, and three tentative pathways were proposed and discussed.

Keywords: 4-Chlorophenol; Density functional theory; Metal-oxides composites; Photocatalysis; ZnAl-LDH.