Degradation of Carbamazepine by HF-Free-Synthesized MIL-101(Cr)@Anatase TiO₂ Composite under UV-A Irradiation: Degradation Mechanism, Wastewater Matrix Effect, and Degradation Pathway

Abstract

TiO2 has been hampered by drawbacks such as rapid photoelectron and hole recombination and a wide energy band gap of 3.2 eV. In this study, MIL-101(Cr)@TiO2 was synthesised without any mineraliser (HF) as part of material modification approach to overcome those pitfalls. The composite was well characterized by XRD, FT-IR, TEM, XPS, BET, TGA, and Raman spectroscopy. Under optimal synthesis conditions, the 9.17% MIL-101(Cr)@TiO2 composite exhibited 99.9% CBZ degradation after 60 min under UV-A irradiation. This can be attributed to the delayed recombination of photo-generated h+ and e− and a reduced band gap energy of 2.9 eV. A Type II heterojunction structure was proposed for the composite using the Mulligan function of electronegativity with the calculated Ecb and Evb. Besides, trapping experiments and ESR spectroscopy confirmed O2•− as the main ROS for CBZ degradation. The effects of the operating parameters such as pH, UV intensity, composite dosage, and initial pollutant concentration were also evaluated. The scavenging effects of inorganic and organic constituents of pharmaceutical wastewater on the process were also evaluated, with HCO3−, CO32−, and THF having more significant inhibition on the overall CBZ degradation. The degradation pathways of CBZ were also proposed based on detected intermediates with the aid of LC/MS/MS. The composite illustrated reusability and stability without considerable loss in the degradation performance after repeated runs. This work builds on the development of more effective photocatalysts and provides a glimpse into applications for similar MOF heterojunction photocatalysts.

Keywords

• photocatalysis
• MOF
• carbamazepine
• pharmaceutical wastewater
• anatase TiO₂