Single-Frequency Impedance Studies on an Ionic Liquid-Based Miniaturized Electrochemical Sensor toward Continuous Low-Temperature CO 2 Monitoring.

Continuous greenhouse gas monitoring at sub-zero temperatures is needed for monitoring greenhouse gas emission in cold environments such as the Arctic tundra. This work reports a single-frequency electrochemical impedance sensing (SF-EIS) method for real-time continuous monitoring of carbon dioxide (CO 2 ) at a wide range of temperatures (-15 to 40 °C) by using robust ionic liquid (IL) sensing materials and noninvasive, low-power, and low-cost impedance readout mechanisms since they cause minimal changes in the sensing interface, avoiding the baseline change for long-term continuous sensing. In addition, a miniaturized planar electrochemical sensor was fabricated that incorporates a hydrophobic 1-butyl-1-methylpyrrolidinium bis(trifluromethylsulfonyl)imide ([Bmpy][NTf 2 ]) IL electrolyte and Pt black electrode materials. The high viscosity of the ILs facilitates the formation of thin, ordered, and concentrated layers of ionic charges, and the inverse relationship of IL viscosity with temperature makes them especially suited for impedance sensing at low temperatures. The unique low-temperature properties of ILs together with EIS transduction mechanisms are shown to be sensitive and selective for continuously monitoring CO 2 at a -15 to 40 °C temperature range via impedance changes at a specifically selected frequency at the open circuit potential (OCP). Molecular dynamics simulations revealed insights into the structure and dynamics of the IL at varying temperatures in the presence of methane and CO 2 and provided potential explanations for the observed sensing results. The miniaturized and flexible planar electrochemical sensor with the [Bmpy][NTf 2 ] electrolyte was tested repeatedly at subzero temperatures over a 58-day period, during which good stability and repeatability were obtained. The CO 2 impedance sensor was further tested for sensing CO 2 from soil samples and shows promising results for their use in real-time monitoring of greenhouse gas emissions in cold temperatures such as permafrost soils.