In Situ Monitoring of the Polymerization Kinetics of Organic Pollutants during Persulfate-Based Advanced Oxidation Processes Using Plasmonic Colorimetry.

Abstract

Using sulfate radicals to initiate polymer production in persulfate-based advanced oxidation processes (AOPs) is an emerging strategy for organics removal. However, our understanding of this process remains limited due to a dearth of efficient methods for in situ and real time monitoring of polymerization kinetics. This study leverages plasmonic colorimetry to monitor the polymerization kinetics of an array of aromatic pollutants in the presence of sulfate radicals. We observed that the formation of polymer shells on the surfaces of gold nanoparticles (AuNPs) led to an increase and red shift in their localized surface plasmon resonance (LSPR) band as a result of an increased refractive index surrounding the AuNP surfaces. This observation aligns with Mie theory simulations and transmission electron microscopy-electron energy loss spectroscopy characterizations. Our study demonstrated that the polymerization kinetics exhibits a significant reliance on the electrophilicity and quantity of benzene rings, the concentration of aromatic pollutants, and the dosage of oxidants. In addition, we found that changes in LSPR band wavelength fit well into a pseudo-first-order kinetic model, providing a comprehensive and quantitative insight into the polymerization kinetics involving diverse organic compounds. This technique holds the potential for optimizing AOP-based water treatment by facilitating the polymerization of aromatic pollutants.