Abstract

The study is about the degradation of a common pharmaceutical and personal care product (PPCP) caffeine by photocatalysis under UV–visible light using pristine TiO2 (P-25) and a lab-made nanocomposite of sepiolite–TiO2. It was found that the dark adsorption of caffeine on P-25 was insignificant, but considerably high on the nanocomposite, owing to the high porosity and unique structure of sepiolite. The degradation of the compound in the presence of P-25 and Sep–TiO2 followed the pseudo-first order and exponential decay kinetics, with a rate constant of 0.12 min−1 and 0.50 min−1, respectively. The efficiency of both catalysts for carbon mineralization was better at acidic pH, but that of the nanocomposite was significantly higher at all pH than that of the unmodified P-25 (36.1 against 9.6% at pH 6.0). The loading of TiO2 on sepiolite was an important factor in the activity of the catalyst, as the maximum activity was observed at a loading ratio of 12.5 mmol per g sepiolite, which decreased at higher ratios of the semiconductor to sepiolite. Exposure of the treated samples to high-frequency ultrasound at pH 6 was found to enhance the degree of mineralization to 65.1 and 52.1% in the presence of the nanocomposite and P-25, respectively. The outcome was attributed to the unique properties of ultrasound for the cleaning of solid surfaces, for enhancing the mass transfer of solutes to heterogeneous interfaces, and for generation of excess hydroxyl radicals. Finally, the nanocomposite was found to be considerably stable, as it was easily recovered and used four times without a significant loss in activity.

Highlights

  • Pharmaceuticals and personal care products (PPCPs) are used for personal health, cosmetics and agribusiness, comprising of thousands of organic compounds

  • Caffeine is one of the most common PPCPs as it is an ingredient of coffee, tea, chocolate, cocoa and beverages, and widely used in the production of the prescription medicine and personal care products [1]

  • The present study aims to investigate the degradation of caffeine by sonolysis and photocatalysis using particles of P-25 obtained from the market, and a nanocomposite thereof, sonolytically synthesized by the immobilization of the metal on sepiolite, which is a highly abundant clay mineral in Central Anatolia

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Summary

Introduction

Pharmaceuticals and personal care products (PPCPs) are used for personal health, cosmetics and agribusiness, comprising of thousands of organic compounds. Being a highly soluble compound, caffeine is rapidly discharged (via wash water and excretion) into sewage treatment facilities with low biodegradability. As such, it is frequently detected in effluents of wastewater treatment operations, soil, groundwater systems and fresh water bodies, [2], where it exhibits toxic effects to aquatic organisms, and imposes a health threat to humans (hyperactivity and cardiovascular diseases) if the water is reclaimed and used in water supply systems [3]. Photocatalysis with TiO2 has serious limitations, owing to the high bandgap energy, a rapid combination of e−h+ pairs and the corroded surface of the metal [10]. Much research has focused on increasing the efficiency of TiO2 via immobilizing it on transition/noble metals and/or rare earth minerals, which by inhibiting the combination of e−h+ pairs and photo-corrosion of the surface lead to significant enhancements in the activity of the semiconductor in the UV–visible band [10,11,12]

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