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Abstract This study examines the activity of chemisorbed CO2 species in the microenvironment formed by bifunctional ionic liquids (ILs) in the reactive capture and conversion (RCC) of CO2 to CO on silver. Comparative electroanalytical measurements with imidazolium based ILs were performed to probe the impact of electrostatic interactions, anion and cation basicity, and hydrogen bonding on RCC. Particularly, ILs with 1-ethyl,3-methylimidazolium ([EMIM]+) and 1-ethyl, 2,3-methylimidazolium ([EMMIM]+) cations and aprotic heterocyclic anions of 2-cyanopyrrolide ([2-CNpyr]) and 1,2,4-triazolide ([1,2,4-Triz]) were examined for RCC. It was found that anion–CO2 carbamate complexes facilitate RCC at significantly lower overpotentials compared to cation–CO2 carboxylate complexes. Additionally, [EMIM]+ was found to better stabilize anion–CO2 complexes than [EMMIM]+. Furthermore, it was found that 2-CNpyrH that naturally forms in CO2 absorption competes for electrode surface adsorption with the anion–CO2 carbamate complex, thereby reducing the electrochemical activity of the anion–CO2 complex. These results highlight the importance of IL structure in tuning the interfacial interactions and suggest that ILs with anion-dominated CO2 chemisorption enhances CO2 utilization in RCC applications. 

Enabled by the fine tuning of the potassium ion solvation through water-in-bisalt approach, wide electrochemical stability and enhanced ionic conductivity are simultaneously achieved in a 36 molal electrolyte suited for potassium batteries. 

Formation of C‐N bonds through the electrochemical utilization of CO2 and nitrogen containing compounds (N‐compounds) is appealing for the purpose of converting waste and readily available sources or pollutants into value added chemicals at ambient conditions. Existing research predominantly explores these electrochemical reactions independently, often in aqueous electrolytes, leading to challenges associated with competitive hydrogen evolution reaction (HER), low product selectivity, and yield. Functional electrolytes such as those containing ionic liquids (ILs) present selective solubility to the solute reactants and present unique interactions with the electrode surface that can suppress the undesired side reaction HER while simultaneously co‐catalyzing the conversion of CO2 and N‐compounds such as N2, NO, NO2, andNO3. In this concept paper, we discuss how the microenvironment enabled by ILs can be  leveraged to stabilize reaction intermediates at the electrode‐electrolyte interface, thereby promoting C‐N bond formation on an active electrode surface at reduced overpotential, with the case study of CO2 and N‐compounds co‐catalysis to generate urea. 

The roles of the ionic liquid (IL), 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]), and water in controlling the mechanism, energetics, and electrocatalytic activity of CO2 reduction to CO on silver in nonaqueous electrolytes were investigated. The first electron transfer occurs to CO2 at reduced overpotentials when it is trapped between the planes of the [EMIM]+ ring and the electrode surface due to cation reorientation as determined from voltammetry, in situ surface-enhanced Raman spectroscopy, and density functional theory calculations. Within this interface, water up to 0.5 M does not induce significant Faradaic activity, opposing the notion of it being a free proton source. Instead, water acts as a hydrogen bond donor, and the proton is sourced from [EMIM]+. Furthermore, this study demonstrates that alcohols with varying acidities tune the hydrogen bonding network in the interfacial microenvironment to lower the energetics required for CO2 reduction. The hydrogen bonding suppresses the formation of inactive carboxylate species, thus preserving the catalytic activity of [EMIM]+. The ability to tune the hydrogen bonding network opens new avenues for advancing IL-mediated electrocatalytic reactions in nonaqueous electrolytes. 

Microencapsulation of pristine core liquids in polymer shells has critical applications in thermal energy storage and management, targeted drug delivery, and carbon capture, among others. Herein, we report a novel encapsulation approach based on a double emulsion soft-template to produce microcapsules comprised of an ionic liquid (IL) core in a degradable polymer shell. We demonstrate the production of [IL-in-oil1]-in-oil2 (IL/O1/O2) double emulsions, in which the oil interphase (O1) contains a CO2-derived polycarbonate bearing vinyl pendant groups, tetrathiol small molecule crosslinker, and photoinitiator; upon irradiation of the double emulsion under low shear, thiol–ene crosslinking of the loaded species results in the formation of a robust shell around the pure IL droplets. The core–shell structures have enhanced physisorption for CO2 uptake compared to the bulk IL, which is consistent with the combined capacity of the IL/shell alone and demonstrates more rapid uptake due to an enhanced gas–liquid interface. This approach to microencapsulation of functional liquids offers researchers a distinct route to fabricate composite architectures with a pristine core for applications in separations, transport of cargo, and gas uptake. 

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. 

Ionic liquids (ILs) and deep eutectic solvents (DESs) have tremendous potential for reactive capture of CO₂, due to their highly properties, including a wide electrochemical stability window, low volatility, and high CO₂solubility.