Mechanistic study of visible light driven photocatalytic degradation of clofibric acid using Fe-based metal organic frameworks (MOFs)

• Published in: Chemosphere (Oxford) Vol. 359; p. 142365
• Main Authors: Chae, Seung Hee, Lee, Hosub, Nam, Kyoungphile
• Format: Journal Article
• Language: English
• Published: England Elsevier Ltd 01.07.2024
• Subjects: Adsorption; Catalysis; Clofibric Acid - chemistry; Iron - chemistry; Kinetics; Light; Metal organic framework; Metal-Organic Frameworks - chemistry; Personal care product; Pharmaceutical product; Photocatalyst; Photolysis; Sorption; Water Pollutants, Chemical - chemistry; Metal organic framework; Sorption; Personal care product; Photocatalyst; Pharmaceutical product
• ISSN: 0045-6535; 1879-1298
• DOI: 10.1016/j.chemosphere.2024.142365

Although a series of past studies proved the potential usage of Fe-based metal-organic frameworks (MOFs) as photocatalysts, there remains a knowledge gap of the photocatalytic mechanism stemming from the challenge to separate the simultaneous sorption and photocatalytic degradation. Thus, this article aimed to suggest a novel approach by desorbing target molecules during photocatalysis to excavate the underlying mechanisms of sorption and photocatalytic degradation. In this study, two Fe-based MOFs, MIL-101(Fe) and MIL-101(Fe)–NH2, were selected to remove clofibric acid under visible light irradiation. Prior to photocatalysis, sorption mechanism was uncovered based on the sorption kinetic, isotherm, thermodynamic interpretation, and of its dependence on solution pH. The results inferred that the primary sorption mechanism was through the π-π interaction between the benzene ring of clofibric acid and the organic ligand of Fe-based MOFs. Based on these results, photocatalytic mechanism could be independently or jointly assessed during the photocatalytic degradation of clofibric acid. Subsequently, the application of the Tauc method and XPS spectra revealed that the bandgap structure of Fe-based MOFs had the potential to oxidize clofibric acid by producing ROS through the electron excitation upon visible-light illumination. On top of that, the amine functionalization of Fe-based MOF altered the structural moiety that led to an additional strong acid-base interaction with clofibric acid but a decrease in the bandgap limiting the ROS production during photocatalytic activity. [Display omitted] •Simultaneous sorption and photocatalytic degradation of clofibric acid using Fe-based MOFs was analyzed separately.•98.8% of clofibric acid was removed with MIL-101(Fe) in 24 h; 49.7% by photocatalysis, the rest by sorption.••OH was the dominant reactive species in photocatalytic degradation using MIL-101(Fe).•Amine functionalization of Fe-based MOF had a smaller bandgap, limiting photocatalytic activity.•Sorption during photocatalysis was critical for overall catalytic efficiency.