Mechanistic Insight into Electrode Processes by Operando Visualization of Interfacial pH Using Fluorescent Nanosensors.

Operando visualization of interfacial pH is crucial, yet challenging in electrochemical processes. Herein, we report the fabrication and utilization of ratiometric, fluorescent pH-sensitive nanosensors for operando quantification of fast-dynamic, interfacial pH changes in electrochemical processes and environments where unprotected fluorescent dyes would be degraded. Spatio-temporal pH changes were detected using an electrochemically coupled laser scanning confocal microscope (EC-LSCM) during the electrocoagulation treatment of model and field samples of oil-sands-produced water. Operando visualization of interfacial pH provided new insights into the electrode processes, including ion speciation, electrode fouling, and Faradaic efficiency. We provide compelling evidence that formed metal complexes precipitate at the edge of the pH boundary layer and that there is a strong coupling between the thickness of the interfacial pH layer and the electrode fouling. Furthermore, these findings provide a powerful pathway for optimizing the operating conditions, minimizing electrode passivation, and enhancing the efficiency of electrochemical processes, e.g., electrocoagulation, flow batteries, capacitive deionization, and electrolyzes.