Continuous and Polarization-Tuned Redox Capacitive Anion Sensing at Electroactive Interfaces.

Continuous, real-time ion sensing is of great value across various environmental and medical scenarios but remains underdeveloped. Herein, we demonstrate the potential of redox capacitance spectroscopy as a sensitive and highly adaptable ion sensing methodology, exemplified by the continuous flow sensing of anions at redox-active halogen bonding ferrocenylisophthalamide self-assembled monolayers. Upon anion binding, the redox distribution of the electroactive interface, and its associated redox capacitance, are reversibly modulated, providing a simple and direct sensory readout. Importantly, the redox capacitance can be monitored at a freely chosen, constant electrode polarization, providing a facile means of tuning both the sensor analytical performance and the anion binding affinity, by up to 1 order of magnitude. In surpassing standard voltammetric methods in terms of analytical performance and adaptability, these findings pave the way for the development of highly sensitive and uniquely tunable ion sensors. More generally, this methodology also serves as a powerful and unprecedented means of simultaneously modulating and monitoring the thermodynamics and kinetics of host-guest interactions at redox-active interfaces.