Witnessing a discrete microdroplet freezing event <i>via</i> real-time electrochemical monitoring of solution temperature

Temperature monitoring has immediate relevance to many areas of research, from atmospheric environmental studies to biological sample and food preservation to chemical reactions. Here, we use a triple-barrel electrode to provide temperature readouts in bulk solution and microdroplets, as well as electrochemically monitor freezing events in a microdroplet. Using this method, we are able to identify distinct characteristics of a freezing aqueous droplet (supercooling, ice formation beginning and end, temperature change, and thawing) with greater temporal resolution than a standard thermocouple and without the use of microscopy. By correlating the amperometric signal change caused by alterations in the diffusion coefficient of the electrochemical system in response to temperature changes, we can calculate the instantaneous temperature at our electrode, as well as the physical behavior of ice formation and expansion. Our results suggest that these electrochemical techniques can provide real-time monitoring of the physical processes involved in aqueous temperature change and ice nucleation events. Here, we employ a novel technique using triple-barrel electrodes to provide temperature readouts in bulk solution and microdroplets, as well as electrochemically monitor freezing events in a microdroplet. Because ice nucleation spans many research fields, it is important to have a variety of tools that can be used to better understand these frozen systems. Our data shows that electrochemistry can provide real-time information on the thermal properties of aqueous environments, and these types of measurements can be extended to microdroplets. The electrochemical signal details all the significant moments in a droplet freezing event, allowing us to use electrochemistry as a stand-alone tool for monitoring freezing events with excellent temporal and spatial resolution.