Enhanced malachite green photolysis at the colloidal-aqueous interface

Colloids, such as natural particulate matter and microplastics, can play a significant role in the fate and transport of organic contaminants. Specifically, these small nano-to micron-sized particles provide large surface area; thus, particle-aqueous interfacial chemistry becomes significant. In this work, we present an experimental investigation of interfacial photokinetics of malachite green cation (MG⁺) adsorbed at the surface of polystyrene carboxyl (PSC) microspheres suspended in aqueous solution. Second harmonic generation (SHG), an interfacial selective laser spectroscopic tool, has been used to probe the buried interface. It is revealed that relative to the bulk, photoinduced degradation of MG⁺ is accelerated by approximately 10-fold at this noncatalytic particle surface. By measuring the SHG-based surface electronic spectra, we have also demonstrated that N-demethylated intermediates of MG⁺ remain at the interface until they are further decomposed. MG⁺ exhibits a bathochromic shift at the interface. Together with strong binding affinity and faster initial rate of photodegradation of MG⁺ at the interface, this work highlights that adsorption and surface photolysis are important pathways by which organic compounds can be transformed within the aquatic environment. Moreover, this research also stimulates further questions on the enrichment of reactive species at the colloidal-aqueous interface and their influence on facilitating decompositions of organic pollutants.