Membraneless Ionic Liquid Droplet Nanoprobe for Vapor Sensing and Gas Phase Scanning Electrochemical Microscopy

Abstract

Gas phase sensing of volatile chemicals is a critical area of research relevant to biomedical diagnosis and environmental hazard assessment. Among various types of sensors, electrochemical sensors garnered attention as cost-effective and portable methods. Most electrochemical sensors needed the membrane to prevent solvent evaporation for detecting the gaseous species. However, the presence of the membrane induced slow response time due to the penetration of gas molecules through the membrane. To improve the systems, a membraneless ionic liquid droplet nanoprobe was developed. Gaseous species can permeate the thin ionic liquid layer, which was also used as the electrolytes, and react on the electrode in extremely fast response. Furthermore, nano-sized electrode makes available to detect sensitively with low charging capacitance. Using the probe type form factor, application to gas phase scanning electrochemical microscopy (SECM) was attempted with high spatial resolution. Oxygen detection, the most commonly studied, was implemented for the first application of the ionic liquid nanoprobe. The limit of detection of this probe was 13 ppm, which is extremely good for electrochemical oxygen sensors. Also, the fast response (< 0.1 s) made the mapping of oxygen concentration using SECM. The nanoprobe showed more than a hundred times better spatial resolution (several micrometer scale) than the previous gas phase SECM study mapping the oxygen. As the application of this oxygen probe, Li-air battery analysis can be conducted. Oxygen was used in the reaction at the cathode of the Li-air battery. As mapping the oxygen concentration above the cathode, It is expected that structural causes for the irreversibility at the cathode can also be found. As oxygen sensing, other electrochemical active gaseous species can be detected with the electrochemical sensor. Trinitrotoluene is a well-known explosive compound, and it can be detected in electrochemistry. Due to its low vapor pressure, di-nitroaromatic compounds, like dinitrotoluene (DNT), dinitrobenzene (DNB), and dinitrophenol (DNP), were used as explosive footprints, which have higher vapor pressure and have often been identified as marker molecules. Using our ionic liquid nanoprobe, we developed the nitroaromatic compounds (NACs) sensor for real-time detection of trace vapors, without any sample pre-treatment and at room temperature. Furthermore, in a simulated airport carousel, real-time and preemptive NACs detection was demonstrated with fast response time. As oxygen detection, gas phase SECM was conducted and 3D mapping capability of the differential vapor pressure was demonstrated, exercising the potential of the NACs nanoprobe in locating the source of an explosive risk. With the sensitive sensing performance of nanoprobe, it can be used as breath analysis. There are several biomarkers to indicate certain diseases. For example, acetone is a representative biomarker of diabetes. Using this sensing platform, acetone sensing was implemented, and it may be used for the initial detection of diabetes.