RESUMEN
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.
RESUMEN
Ionic liquids (ILs) and deep eutectic solvents (DESs) have tremendous potential for reactive capture and conversion (RCC) of CO2 due to their wide electrochemical stability window, low volatility, and high CO2 solubility. There is environmental and economic interest in the direct utilization of the captured CO2 using electrified and modular processes that forgo the thermal- or pressure-swing regeneration steps to concentrate CO2, eliminating the need to compress, transport, or store the gas. The conventional electrochemical conversion of CO2 with aqueous electrolytes presents limited CO2 solubility and high energy requirement to achieve industrially relevant products. Additionally, aqueous systems have competitive hydrogen evolution. In the past decade, there has been significant progress toward the design of ILs and DESs, and their composites to separate CO2 from dilute streams. In parallel, but not necessarily in synergy, there have been studies focused on a few select ILs and DESs for electrochemical reduction of CO2, often diluting them with aqueous or non-aqueous solvents. The resulting electrode-electrolyte interfaces present a complex speciation for RCC. In this review, we describe how the ILs and DESs are tuned for RCC and specifically address the CO2 chemisorption and electroreduction mechanisms. Critical bulk and interfacial properties of ILs and DESs are discussed in the context of RCC, and the potential of these electrolytes are presented through a techno-economic evaluation.
RESUMEN
Ionic liquids (ILs) are considered functional electrolytes for the electrocatalytic reduction of CO2 (ECO2R) due to their role in the double-layer structure formation and increased CO2 availability at the electrode surface, which reduces the voltage requirement. However, not all ILs are the same, considering the purity and degree of the functionality of the IL. Further, there are critical experimental factors that impact the evaluation of ILs for ECO2R including the reference electrode, working electrode construction, cosolvent selection, cell geometry, and whether the electrochemical cell is a single compartment or a divided cell. Here, we describe improved synthesis methods of imidazolium cyanopyrrolide IL for electrochemical studies in consideration of precursor composition and reaction time. We explored how IL with cosolvents (i.e. acetonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate, and n-methyl-2-pyrrolidone) affects conductivity, CO2 mass transport, and ECO2R activation overpotential together with the effects of electrode materials (Sn, Ag, Au, and glassy carbon). Acetonitrile was found to be the best solvent for lowering the onset potential and increasing the catalytic current density for the production of CO owing to the enhanced ion mobility in combination with the silver electrode. Further, the ECO2R activity of molecular catalysts Ni(cyclam)Cl2 and iron tetraphenylsulfonato porphyrin (FeTPPS) on the carbon cloth electrode maintained high Faradaic efficiencies for CO in the presence of the IL. This study presents best practices for examining nontraditional multifunctional electrolytes amenable to integrated CO2 capture and conversion technologies for homogeneous and heterogeneous ECO2R.
RESUMEN
Developing unconventional electrolytes such as ionic liquids (ILs) and deep eutectic solvents (DESs) has led to remarkable advances in electrochemical energy storage and conversion devices. However, the understanding of the electrode-electrolyte interfaces of these electrolytes, specifically the liquid structure and the charge/electron transfer mechanism and rates, is lacking due to the complexity of molecular interactions, the difficulty in studying the buried interfaces with nanometer-scale resolution, and the distribution of the time scales for the various interfacial events. This Feature Article outlines the standing questions in the field, summarizes some of the exciting approaches and results, and discusses our contributions to probing the electrified interfaces by electrochemical impedance spectroscopy (EIS), surface-enhanced Raman spectroscopy (SERS), and neutron reflectivity (NR). The related findings are analyzed within electrical double-layer models to provide a framework for studying ILs, DESs, and, more broadly, the concentrated hydrogen-bonded electrolytes.
RESUMEN
Electrochemical CO2 reduction (CO2 RR) on copper (Cu) shows promise for higher-value products beyond CO. However, challenges such as the limited CO2 solubility, high overpotentials, and the competing hydrogen evolution reaction (HER) in aqueous electrolytes hinder the practical realization. We propose a functionalized ionic liquid (IL) which generates ion-CO2 adducts and a hydrogen bond donor (HBD) upon CO2 absorption to modulate CO2 RR on Cu in a non-aqueous electrolyte. As revealed by transient voltammetry, electrochemical impedance spectroscopy (EIS), and in situ surface-enhanced Raman spectroscopy (SERS) complemented with image charge augmented quantum-mechanical/molecular mechanics (IC-QM/MM) computations, a unique microenvironment is constructed. In this microenvironment, the catalytic activity is primarily governed by the IL and HBD concentrations; former controlling the double layer thickness and the latter modulating the local proton availability. This translates to ample CO2 availability, reduced overpotential, and suppressed HER where C4 products are obtained. This study deepens the understanding of electrolyte effects in CO2 RR and the role of IL ions towards electrocatalytic microenvironment design.
RESUMEN
Electrochemical conversion of CO2 requires selective catalysts and high solubility of CO2 in the electrolyte to reduce the energy requirement and increase the current efficiency. In this study, the CO2 reduction reaction (CO2RR) over Ag electrodes in acetonitrile-based electrolytes containing 0.1 M [EMIM][2-CNpyr] (1-ethyl-3-methylimidazolium 2-cyanopyrolide), a reactive ionic liquid (IL), is shown to selectively (>94%) convert CO2 to CO with a stable current density (6 mA·cm-2) for at least 12 h. The linear sweep voltammetry experiments show the onset potential of CO2 reduction in acetonitrile shifts positively by 240 mV when [EMIM][2-CNpyr] is added. This is attributed to the pre-activation of CO2 through the carboxylate formation via the carbene intermediate of the [EMIM]+ cation and the carbamate formation via binding to the nucleophilic [2-CNpyr]- anion. The analysis of the electrode-electrolyte interface by surface-enhanced Raman spectroscopy (SERS) confirms the catalytic role of the functionalized IL where the accumulation of the IL-CO2 adduct between -1.7 and -2.3 V vs Ag/Ag+ and the simultaneous CO formation are captured. This study reveals the electrode surface species and the role of the functionalized ions in lowering the energy requirement of CO2RR for the design of multifunctional electrolytes for the integrated capture and conversion.