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 (CO2) 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][NTf2]) 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 CO2 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 CO2 and provided potential explanations for the observed sensing results. The miniaturized and flexible planar electrochemical sensor with the [Bmpy][NTf2] electrolyte was tested repeatedly at subzero temperatures over a 58-day period, during which good stability and repeatability were obtained. The CO2 impedance sensor was further tested for sensing CO2 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.
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This content will become publicly available on August 1, 2024
Ionic Liquid-Packed Microfluidic Device with Non-Planar Microelectrode as a Miniaturized Electrochemical Gas Sensor
Integrating transducer/sensing materials into microfluidic platforms has enhanced gas sensors′ sensitivity, selectivity, and response time while facilitating miniaturization. In this manuscript, microfluidics has been integrated with non-planar microelectrode array and functionalized ionic liquids (ILs) to develop a novel miniaturized electrochemical gas sensor architecture. The sensor employs the IL 1-ethyl-3-methylimidazolium 2-cyanopyrolide ([EMIM][2-CNpyr]) as the electrolyte and capture molecule for detecting carbon dioxide (CO 2 ). The three-layer architecture of the sensor consists of a microchannel with the IL sandwiched between glass slides containing microelectrode arrays, forming a non-planar structure. This design facilitates electric field penetration through the IL, capturing CO 2 binding perturbations throughout the channel volume to enhance sensitivity. CO 2 binding with [EMIM][2-CNpyr] generates carboxylate ([EMIM] + -CO2 − ]), carbamate ([2-CNpyr]-CO2 − ]), and pyrrole-2-carbonitrile (2-CNpyrH) species, significantly decreasing the conductivity. The viscosity is also increased, leading to a further decrease in conductivity. These cumulative effects increase charge transfer resistance in the impedance spectrum, allowing a linear calibration curve obtained using Langmuir Isotherm. The sensitivity and reproducibility in CO 2 detection are demonstrated by two electrode configurations using the calibration curve. The developed sensor offers a versatile platform for future applications.
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- NSF-PAR ID:
- 10462653
- Date Published:
- Journal Name:
- Journal of The Electrochemical Society
- Volume:
- 170
- Issue:
- 8
- ISSN:
- 0013-4651
- Page Range / eLocation ID:
- 087508
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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