Nanoelectrochemistry Reveals Selective Interactions of Perfluoroalkyl Substances (PFASs) with Silver Nanoparticles

Nanoelectrochemistry allows for the investigation of the interaction of per‐ and polyfluoroalkyl substances (PFASs) with silver nanoparticles (AgNPs) and the elucidation of the binding behaviour of PFASs to nanoscale surfaces with high sensitivity. Mechanistic studies supported by single particle collision electrochemistry (SPCE), spectroscopic and density functional theory (DFT) calculations indicate the capability of polyfluorooctane sulfonic acid (PFOS), a representative PFAS, to selectively bind and induce aggregation of AgNPs. Single‐particle measurements provide identification of the “discrete” AgNPs agglomeration (e.g. 2–3 NPs) formed through the inter‐particles F−F interactions and the selective replacement of the citrate stabilizer by the sulfonate of the PFOS. Such interactions are characteristic only for long chain PFAS (‐SO3−) providing a means to selectively identify these substances down to ppt levels. Measuring and understanding the interactions of PFAS at nanoscale surfaces are crucial for designing ultrasensitive methods for detection and for modelling and predicting their interaction in the environment. Nanoelectrochemistry using single‐particle‐on‐microelectrode collisions supported by spectroscopic and theoretical studies provide insight into the molecular behavior of PFAS at single‐particle scale. The new approach can be used for the ultrasensitive measurement of selected PFASs and accelerate the design of materials and methods that can bind and detect these substances.