RTILs as Electrolytes in Electrochemical Gas Sensors for O₂ and Other Gases

Oxygen is the third-most abundant element on this planet and is essential to life, the lifestyle of humans and virtually all sentient life. We need O 2 to live and additionally use it for both heating and transportation. Since O 2 is so essential in our everyday life, there are several applications where the oxygen levels need to be controlled or maintained within a certain range. To make sure that the O 2 level is within the necessary range, devices are needed that can monitor and feedback/communicate O 2 levels continuously. There are several types of chemical gas sensors for O 2 which include chemoresistive gas sensors and electrochemical gas sensors. The Clark-type electrochemical sensor is the oldest and probably the most used sensor for oxygen especially in medical applications. One of the most well-known industrial applications for gas-phase oxygen sensors is probably the control of oxygen levels in combustion engines with the help of a Lambda probe, a solid-state electrochemical cell operated in amperometric and potentiometric modes. Electrochemical sensors have evolved over the past decades. By finding the suitable combination of electrolyte, electrode material, cell design and operation conditions, electrochemical sensors are tunable to meet the specific requirements of the many different applications. For example, by changing the electrode material from gold to platinum while keeping everything else the same, you can reduce the response to CO by orders of magnitude improving the selectivity in low level measurements. Further, by adjusting the thermodynamic voltage of the sensing electrode, the electrochemical reactivity is adjusted to maximize the sensor’s selectivity for the target analyte. While these developments have occurred over time, recent work implements room temperature ionic liquids (RTILs) as electrolytes. This idea has some serious merit to it for multiple reasons. Firstly, many electrochemical sensors have aqueous electrolytes which freeze at low temperatures and rapidly evaporate at elevated temperatures. Additionally, aqueous electrolytes can change in real time with variations in background humidity levels. To be more exact, aqueous electrolytes dry out when operated in low humidity backgrounds and significantly increase in volume (swell) in high humidity background levels. While drying out is an issue because this leads to poor ionic conductivities, swelling is an issue because the electrolyte needs expansion room in the sensor, typically an extensive cavity within the cell body. RTILs have shown promise because they can extend the operating temperature range as well as lead to new sensor designs operatable over a wider range of environmental conditions. The implementation of RTILs might even allow for smaller sensor designs due to a smaller volume change of the electrolyte in dependence of changing humidity levels. Several research groups have investigated the oxygen sensing capabilities of RTILs in electrochemical devices. Silvester et al. investigated the oxygen solubility in several different imidazolium cations combined with [bis(trifluoromethylsulfonyl)imide] ([NTf 2 ] - ) anions and found a high oxygen solubility in 3-butyl-1-methyl imidazolium [NTf 2 ] - [1]. They further investigated the influence of humidity on the oxygen reduction reaction and found the most stable behavior for [3-etyhl-1-methyl imidiazolium] [NTf 2 ] - over a broad range of different humidity levels [2]. Yin et al. investigated 1-butyl-1-methylpyrrolidinium [NTf 2 ] - as an electrolyte in oxygen sensors and found good linear correlation of the sensor output to the oxygen concentration [3]. In this work, we investigated different RTILs, including the before mentioned 1-butyl-1-methylpyrrolidinium [NTf 2 ] - and 3-butyl-1-methyl imidazolium [NTf 2 ] - , regarding their suitability for thin layer electrochemical oxygen sensors in a background of mostly nitrogen. The performance was investigated using CV (cyclic voltammetry) and other time dependent voltametric techniques. The ability to detect oxygen of sensors with different RTILs as electrolyte was compared to that of aqueous H 2 SO 4 . [1] S. Doblinger, D.S. Silvester, M. Costa Gomes, Functionalized Imidazolium Bis(trifluoromethylsulfonyl)-imide Ionic Liquids for Gas Sensors: Solubility of H2, O2 and SO2, Fluid Phase Equilib. 549 (2021). https://doi.org/10.1016/j.fluid.2021.113211. [2] S. Doblinger, J. Lee, D.S. Silvester, Effect of Ionic Liquid Structure on the Oxygen Reduction Reaction under Humidified Conditions, Journal of Physical Chemistry C. 123 (2019) 10727–10737. https://doi.org/10.1021/acs.jpcc.8b12123. [3] H. Yin, H. Wan, L. Lin, X. Zeng, A.J. Mason, Miniaturized Planar RTIL-based Electrochemical Gas Sensor for Real-Time Point-of-Exposure Monitoring, 2016 IEEE Healthcare Innovation Point-Of-Care Technologies Conference (HI-POCT). (2016) 85–88. https://doi.org/10.1109/HIC.2016.7797703.