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DOE OSTI2024

Pairing a Global Optimization Algorithm with EXAFS to Characterize Lanthanide Structure in Solution

Ensemble-average sampling of structures from ab initio molecular dynamics (AIMD) simulations can be used to predict theoretical extended X-ray absorption fine structure (EXAFS) signals that closely match experimental spectra. However, AIMD simulations are time-consuming and resource-intensive, particularly for solvated lanthanide ions, which often form multiple nonrigid geometries with high coordination numbers. Here, to accelerate the characterization of lanthanide structures in solution, we employed the Northwest Potential Energy Surface Search Engine (NWPEsSe), an adaptive-learning global optimization algorithm, to efficiently screen first-shell structures. As case studies, we examine two systems: Eu(NO 3 ) 3 dissolved in acetonitrile with a terpyridine ligand (terpyNO 2 ), and Nd(NO 3 ) 3 dissolved in acetonitrile. The theoretical spectra for structures identified by NWPEsSe were compared to both experimental and AIMD-derived EXAFS spectra. The NWPEsSe algorithm successfully identified the proper solvation structure for both Eu(NO 3 ) 3 (terpyNO 2 ) and Nd(NO 3 )(acetonitrile) 3 , with the calculated EXAFS signals closely matching the experimental spectra for the Eu-ligand complex and showing good similarity for the Nd salt; the better agreement with the ligand-containing structure is attributed to a less dynamic coordination environment due to the rigid ligand. The key advantage of the global optimization algorithm lies in its ability to sample the coordination environment across the potential energy surface and reduce the time required to identify structures from generally a month to within a week. Additionally, this approach is versatile and can be adapted to characterize main-group metal complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Integrated Quantum-Classical Protocol for the Realistic Description of Solvated Multinuclear Mixed-Valence Transition-Metal Complexes and Their Solvatochromic Properties

Linear cyanide-bridged polymetallic complexes, which undergo photoinduced metal-to-metal charge transfer, represent prototypical systems for studying long-range electron-transfer reactions and understanding the role played by specific solute–solvent interactions in modulating the excited-state dynamics. Here, to tackle this problem, while achieving a statistically meaningful description of the solvent and of its relaxation, one needs a computational approach capable of handling large polynuclear transition-metal complexes, both in their ground and excited states, as well as the ability to follow their dynamics in several environments up to nanosecond time scales. Here, we present a mixed quantum classical approach, which combines large-scale molecular dynamics (MD) simulations based on an accurate quantum mechanically derived force field (QMD-FF) and self-consistent QMD polarized point charges, with IR and UV–vis spectral calculations to model the solvation dynamics and optical properties of a cyano-bridged trinuclear mixed-valence compound (trans-[(NC) 5 Fe III (μ-CN)Ru II (pyridine) 4 (μ-NC)Fe III (CN) 5 ] 4– ). We demonstrate the reliability of the QMD-FF/MD approach in sampling the solute conformational space and capturing the local solute–solvent interactions by comparing the results with higher-level quantum mechanics/molecular mechanics (QM/MM) MD reference data. The IR spectra calculated along the classical MD trajectories in different solvents correctly predict the red shift of the CN stretching band in the aprotic medium (acetonitrile) and the subtle differences measured in water and methanol, respectively. By explicitly including the solvent molecules around the cyanide ligands and calculating the thermal averaged absorption spectra using time-dependent density functional theory calculations within the Tamm–Dancoff approximation, the experimental solvatochromic shift is quantitatively reproduced going from water to methanol, while it is overestimated for acetonitrile. This discrepancy can likely be traced back to the lack of important dispersion interactions between the solvent cyano groups and the pyridine substituents in our micro solvation model. The proposed protocol is applied to the ground state in water, methanol, and acetonitrile and can be flexibly generalized to study excited-state nonequilibrium solvation dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Directed Gas-Phase Formation of the 1-Cyanovinyl Radical (H 2 CCCN, X 2 A′) in the Interstellar Medium

The formation pathways to nitrogen-containing molecules and radicals are crucial to the understanding of the carbon–nitrogen chemistry in interstellar and atmospheric environments. While over 65 nitrogen-containing neutral species have been observed in deep space to date, their formation mechanisms─in particular, those of radical species─remain largely speculative. The crossed molecular beam technique in conjunction with electronic structure and statistical calculations was utilized to offer a detailed overview of the fundamental pathways in the gas-phase bimolecular reaction of ground-state atomic carbon (C, 3 P) with acetonitrile-d 3 (CD 3 CN, X 1 A 1 ) under single-collision conditions leading to the formation of the 1-cyanovinyl radical (D 2 CCCN, X 2 A′) coupled with deuterium atom loss. Here, the indirect reaction was initiated by barrierless carbon-atom addition, with the most probable route involving carbon addition across the carbon–nitrogen nitrile triple bond of acetonitrile, forming a three-membered ring intermediate followed by ring-opening and unimolecular decomposition via atomic deuterium loss from the C3 carbon atom. The reaction was overall exoergic, and intermediates and transition states lie lower in energy than the separated reactants, unlocking the reaction of carbon with acetonitrile in low-temperature environments such as cold molecular clouds, e.g., Taurus Molecular Cloud (TMC-1), and planetary atmospheres, e.g., Saturn’s moon Titan. In these environments, the 1-cyanovinyl radical may act as a building block for cyano-substituted polycyclic aromatic hydrocarbons and N-heterocycles, thus furthering our understanding of the complex carbon–nitrogen chemistry in deep space.

Chemical reactions↗
DOE OSTI2022

Beyond Simple Dilution: Superior Conductivities from Cosolvation of Acetonitrile/LiTFSI Concentrated Solution with Acetone

Concentrated solutions of Li salts in acetonitrile are promising alternative electrolytes for the next generation of Li batteries as they may exhibit superior electrochemical properties. However, the reduced mobility of the chemical species is a barrier yet to be overcome, and for this, we explore the utilization of acetone as a cosolvent. Although acetone is a polar compound, we find that its addition to the LiTFSI/acetonitrile solution does not follow the trends expected for a simple dilution process. At a low concentration, acetone subtly shifts acetonitrile from the first to extended solvation sheaths of the ions. Still, most of the original structure of the solution is preserved, and mobile high-concentration clusters are formed in the solution. At higher concentrations, the cosolvation promotes cation–anion interactions but with a different nature from those in the original solution and still allows for a further increase in conductivity. Additionally, the non-coordinating fraction of acetonitrile acquires features resembling the pure solvent, which is a possible additional facilitating factor for ionic diffusion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Molecular Origin of Nanoscale Anion Ordering of LiTFSI Electrolytes Revealed through SAXS/WAXS and Molecular Dynamics Simulations

Recent developments in “water-in-salt” electrolytes have precipitated a renewed effort to study imide-based electrolytes. While previous small-/wide-angle X-ray scattering (SAXS/WAXS) studies have attributed the emergence of a low-Q peak in the SAXS profile of aqueous LiTFSI electrolytes to nanometer-scale anion clustering, a molecular-level understanding of the root of these clusters remains unclear. Here, in this study, we combined molecular dynamics simulations and SAXS/WAXS to study the solvation structures of LiTFSI in acetonitrile, methanol, and water. We concluded that hydrogen bonding in water and MeOH stabilizes anion clusters, while nonpolar methyl groups on methanol and acetonitrile interrupt the nanoscale ordering of TFSI anions. This causes LiTFSI in water and MeOH electrolytes to exhibit two low-Q SAXS profile peaks while LiTFSI in acetonitrile exhibits only a single peak below Q = 1 Å –1 . These findings shed light on the underlying molecular origins of nanoscale anion clusters, which may help in the design of the next generation of electrolyte chemistries.

Trojanowski, Lucas [Univ. of Michigan, Ann Arbor, ↗
DOE OSTI2022

Vitrification of Hanford Tank 241-AP-101 Waste and Simulant

Hanford tank 241-AP-101 (referred to herein as AP-101) is the second Hanford radioactive tank waste planned to be processed and vitrified. A simulant version of AP 101 waste was formulated from the best-basis inventory (BBI) for the Hanford Tank 241-AP-101 liquid with an assumed target dilution of the waste from the BBI sodium molarity of 8.61 M to the desired 5.5 M Na. After the addition of glass-forming chemicals (GFCs), the simulant melter feed was processed in a non-radioactive, continuous laboratory-scale melter (CLSM) system. The AP-101 simulant melter feed was charged into the CLSM for 6.11 h of processing, which produced 6.55 kg of glass, for an average glass production rate of 2275 kg m 2 d -1 . Since there were no processing issues with the AP-101 simulant melter feed, AP-101 melter feed made with actual waste was then processed in a CLSM system built into a contamination area in a radioactive environment. The melting behavior characteristics appeared similar for both the simulant and waste melter feeds. The AP-101 waste melter feed was charged into the CLSM for 12.14 h of processing, which produced 8.75 kg of glass, for an average glass production rate of 1530 kg m 2 d -1 . During the AP-101 waste melter feed charging, the pump used to move the feed reached a maximum and it is believed that if the pump had a greater capacity, a greater average glass production rate could have been achieved. A constituent of interest present in low quantities in the AP-101 waste is 99 Tc or its non-radioactive surrogate, Re, added to the AP-101 simulant. Analysis for the quantities of 99 Tc and Re in the AP-101 glass product resulted in an average single-pass retention from the melter feed during relative chemical steady state of 55 ± 2 % for 99 Tc and 45 ± 2 % for Re. Compared to the processing of other melter feeds, the retention of 99 Tc in the AP-101 glass was greater than in both AP-107 and AP-105 glass, while the retention of Re in the AP-101 was less than in the AP-107 glass, but greater than in the AP-105 glass. A spike of I was added into the AP-101 melter feed that could be detected above the analysis detection limits. However, the iodine was only detectable above the ~6 ppm limit in one glass pour: the pour immediately following the burn off of the cold cap, where the I level reached ~30 ppm. This event was significant because the glass was poured immediately after burn off and thus it is presumed that the iodine had yet to volatilize from the glass melt while idling. It is recommended to perform future tests with I spikes at greater levels so that it can be detected in additional glass pours to determine if the expected 50 % retention of I used in the Kim et al. glass models can be confirmed. Offgas liquid samples were analyzed for acetonitrile, which was present at greater concentrations in CLSM liquids than in other scaled melter systems. This result was expected based on unique conditions with the CLSM system including a small plenum space leading to low residence time for offgas and the rapidity of offgas cooling upon exiting the CLSM vessel due to the location and environment. About 90 % of the total acetonitrile captured during both the AP-101 simulant and waste CLSM runs was found in the offgas condensate and demister liquids, thus it is recommended that only those liquids be sent for analysis if future testing to study the presence of acetonitrile in offgas products is desired.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

New Spectroelectrochemical Insights into Manganese and Rhenium Bipyridine Complexes as Catalysts for the Electrochemical Reduction of Carbon Dioxide

This study aimed to demonstrate the behavior of different complexes using IR spectroelectrochemistry (SEC), a technique that combines IR spectroscopy with electrochemistry. Four different Mn and Re catalysts for electrochemical CO 2 reduction were studied in dry acetonitrile. In the case of Mn(apbpy)(CO) 3 Br (apbpy = 4(4-aminophenyl)-2,2'-bipyridine), SEC suggested that a very slow catalytic reduction of CO 2 also occurs in acetonitrile in the absence of proton donors, but at rather negative potentials. In contrast, the corresponding Re(apbpy)(CO) 3 Br clearly demonstrated slow catalytic conversion at the first reduction potential. Switching to saturated CO 2 solutions in a mixture of acetonitrile and 5% water as a proton donor, the SEC of Mn(apbpy)(CO) 3 Br displayed a faster catalytic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Eco–Friendly Solvent Engineered CsPbI 2.77 Br 0.23 Ink for Large–Area and Scalable High Performance Perovskite Solar Cells

The performance of large-area perovskite solar cells (PSCs) has been assessed for typical compositions, such as methylammonium lead iodide (MAPbI 3 ), using a blade coater, slot-die coater, solution shearing, ink-jet printing, and thermal evaporation. However, the fabrication of large-area all-inorganic perovskite films is not well developed. This study develops, for the first time, an eco-friendly solvent engineered all-inorganic perovskite ink of dimethyl sulfoxide (DMSO) as a main solvent with the addition of acetonitrile (ACN), 2-methoxyethanol (2-ME), or a mixture of ACN and 2-ME to fabricate large-area CsPbI 2.77 Br 0.23 films with slot-die coater at low temperatures (40–50 °C). The perovskite phase, morphology, defect density, and optoelectrical properties of prepared with different solvent ratios are thoroughly examined and they are correlated with their respective colloidal size distribution and solar cell performance. Here, the optimized slot-die-coated CsPbI 2.77 Br 0.23 perovskite film, which is prepared from the eco-friendly binary solvents dimethyl sulfoxide:acetonitrile (0.8:0.2 v/v), demonstrates an impressive power conversion efficiency (PCE) of 19.05%. Moreover, the device maintains ≈91% of its original PCE after 1 month at 20% relative humidity in the dark. It is believed that this study will accelerate the reliable manufacturing of perovskite devices.

binary and ternary solvent↗
DOE OSTI2022

Theoretical and Experimental Investigation of Functionalized Cyanopyridines Yield an Anolyte with an Extremely Low Reduction Potential for Nonaqueous Redox Flow Batteries

Abstract Cyanopyridines and cyanophenylpyridines were investigated as anolytes for nonaqueous redox flow batteries (RFBs). The three isomers of cyanopyridine are reduced at potentials of −2.2 V or lower vs. ferrocene +/0 (Fc +/0 ), but the 3‐CNPy⋅ − radical anion forms a sigma‐dimer that is re‐oxidized at E ≈−1.1 V, which would lead to poor voltaic efficiency in a RFB. Bulk electrochemical charge‐discharge cycling of the cyanopyridines in acetonitrile and 0.50 M [NBu 4 ][PF 6 ] shows that 2‐CNPy and 4‐CNPy lose capacity quickly under these conditions, due to irreversible chemical reaction/decomposition of the radical anions. Density‐functional theory (DFT) calculations indicated that adding a phenyl group to the cyanopyridines would, for some isomers, limit dimerization and improve the stability of the radical anions, while shifting their E 1/2 only about +0.10 V relative to the parent cyanopyridines. Among the cyanophenylpyridines, 3‐CN‐6‐PhPy and 3‐CN‐4‐PhPy are the most promising as anolytes. They exhibit reversible reductions at E 1/2 =−2.19 and −2.22 V vs. ferrocene +/0 , respectively, and retain about half of their capacity after 30 bulk charge‐discharge cycles. An improved version of 3‐CN‐6‐PhPy with three methyl groups (3‐cyano‐4‐methyl‐6‐(3,5‐dimethylphenyl)pyridine) has an extremely low reduction potential of −2.50 V vs. Fc +/0 (the lowest reported for a nonaqueous RFB anolyte) and loses only 0.21 % of capacity per cycle during charge‐discharge cycling in acetonitrile.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Manganese(II) complexes of 1,1'-bis[(pyridin-2-yl)methyl)]-2,2'-bipiperidine (PYBP): Synthesis, structure, catalytic properties in alkene epoxidation with hydrogen peroxide, and related mechanistic studies

In this study, several manganese(II) complexes with the stereoisomers of ligand PYBP (1,1'-bis[(pyridin-2-yl)methyl]-2,2'-bipiperidine) and different anions were prepared and characterized by X-ray diffractometry. Complex [Mn II (rac-PYBP)] 2+ (1) was found to be an efficient catalyst of alkene epoxidation by hydrogen peroxide in the presence of acetic acid in acetonitrile at room temperature. Cyclooctene was converted to its epoxide with up to 91 % yield, 99.6 % selectivity, and the turnover number of 180 within 5 min. Fast epoxidations of cyclohexene, 1-decene, styrene, and cis-stilbene were also achieved. Isomeric complex [Mn II (meso-PYBP)] 2+ (2) was catalytically inactive under the same experimental conditions. Stopped-flow spectrophotometry and freeze-quenched EPR spectra show that complex 2 is not oxidized by H 2 O 2 in the presence of acetic acid (AcOH) but instead undergoes partial ligand protonation and liberation of the Mn 2+ cations due to the relatively poor chelating ability of ligand meso-PYBP. The rac-PYBP isomer acts as a better ligand and retains the coordinated Mn center when complex 1 is treated with the H 2 O 2 /AcOH mixture in acetonitrile solution yielding a mixture of intensely colored intermediates likely involving Mn III , Mn IV , and Mn V complexes. Magnetic susceptibility measurements, UV–vis and EPR spectra suggest that dinuclear complexes [Mn III 2 (μ-O)(μ-OAc)(rac-PYBP) 2 ] 3+ and [Mn III Mn IV (μ-O) 2 (rac-PYBP) 2 ] 3+ gradually accumulate in the reaction mixture as inactivated states of the catalyst. Complex 1 also causes fast decomposition of hydrogen peroxide into O 2 gas and H 2 O, which competes with the epoxidation of alkenes and requires gradual addition of H 2 O 2 for its efficient use. The catalytic activity of complex 1 is strongly influenced by its counterions and decreases in order ClO 4 - ≈ SbF 6 - > NO 3 – > Cl - indicating that labile ligands in the coordination sphere of Mn are required for the activation of H 2 O 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Kinetic study of the azo – Hydrazone photoinduced mechanism in complexes with a -Re(CO) 3 L 0/+ core by flash photolysis

The photoprocesses of three rhenium(I) tricarbonyl complexes, fac-Re(NN)(CO) 3 L 0/+ , bearing an azo/hydrazone ligand, NN, and L = Cl, Br or CH 3 CN as axial ligand, were studied by time-resolved spectroscopic techniques. Flash irradiation of deaerated solutions of the complexes in acetonitrile photogenerated intermediates with intense optical absorptions in the UV–vis spectral region of the hydrazone ligand. The decay of the intermediates photogenerated with the Cl, Br and CH 3 CN ligands in the axial position proceeds by three different mechanisms. For the fac-Re(NN)(CO) 3 Cl, a three-step mechanism involving isomerization, tautomerization and rotation accounts for the spectroscopic transformations. In contrast to the flash photolysis result, the continuous photolysis of the complex in acetonitrile does not show spectroscopic changes associated with the generation of a stable product, i.e., the complex exhibits a photoreversible behavior. The first step observed in the flash irradiation of fac-Re(NN)(CO) 3 Cl, is missing in the decay of the photogenerated intermediates with fac-Re(NN)(CO) 3 Br and fac-[Re(NN)(CO) 3 CH 3 CN] + . A possible reason for this absence is that the process is too fast for the time-response of the flash photolysis set-up. Time-resolved spectra and associated reaction rate data for the Re(I) complexes are communicated and discussed. Finally, DFT calculations support a plausible E → Z mechanism with thermal back-isomerization mediated by tautomerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Effect of feed composition on the production of off-gases during vitrification of simulated low-activity nuclear waste

During the vitrification of nuclear waste, hazardous and radioactive emissions are generated from the feed-to-glass conversion reactions, in addition to discharges from forced air bubbling and air inleakage. Although the major gaseous emissions are water vapor, nitrogen, and carbon dioxide, various monitored environmental pollutants are also released, such as nitrogen oxides or sulfur dioxide. In addition, reactions between organics and nitrates in the feed may also form products of incomplete combustion such as carbon monoxide and acetonitrile. Although off-gas emissions are commonly measured during both laboratory- and pilot-scale melter testing, no predictive tool is currently available to a priori estimate the composition of gaseous emissions during nuclear waste vitrification. This work forms a basis for the development of such predictive tool by measuring gas evolution from a broad range of simulated low-activity waste melter feeds using evolved gas analysis data and developing correlations between the feed and off-gas compositions. Using reaction stoichiometry and regression analysis, we demonstrate that next to the content of nitrogen and organic carbon in the feed, the gaseous emissions are affected by the feed reduction-oxidation conditions – the more the feed is reduced, the less nitrogen monoxide, and more carbon monoxide and acetonitrile evolves. In conclusion, the results presented in this work provide a first step towards reducing the amount of expensive physical melter testing and the regression analysis provides a simple tool for rapid optimization of feed composition with respect to off-gas composition.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Relationship of the Molecular Structure and Transport Properties of Imide-Based Lithium Salts of “Acetonitrile/Water-in-Salt” Electrolytes

“Water-in-salt” (WIS) electrolytes exhibit excellent safety and electrochemical performance. However, they possess high concentrations, relatively low diffusion coefficient, and high viscosity. “Acetonitrile/water in salt” (AWIS) electrolytes can overcome the disadvantages of WIS electrolytes. Under relatively low concentrations, AWIS electrolytes show good electrochemical performance comparable to WIS electrolytes and low conductivity. Herein, we investigate the relationship between the solvation structures and the transport properties using small-angle X-ray scattering and molecular dynamics simulation. We observed two solvation behaviors of AWIS: anions dissolved in acetonitrile forming small acetonitrile/anion clusters and additional water further dissolving the small acetonitrile/anion clusters. The introduction of acetonitrile weakens the water–solute interaction and enhances the cation–anion interaction, which results in an enhanced dynamical slowdown as the concentration increases. In conclusion, this work provides molecular-level understanding of the connection between two-stage solvation structures and transport properties for imide-based lithium salt solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Coordination Chemistry and Photoluminescence of Sm(II) Dibenzo-24-crown-8 Complexes

Three Sm(II) dibenzo-24-crown-8 (db24c8) complexes were synthesized in anhydrous, air-free conditions via the reaction of SmI 2 with db24c8 and tetrabutylammonium tetraphenylborate ([TBA][BPh 4 ]; where needed) in acetonitrile (CH 3 CN), dimethoxyethane (DME), and tetrahydrofuran (THF) to yield [Sm(db24c8)(CH 3 CN) 2 ][BPh 4 ][I]·CH 3 CN, [Sm(db24c8)(DME)]I 2 , and [Sm(db24c8)(THF) 2 ]I 2 , respectively. In each case, a 10-coordinate, staggered dodecahedral (2:6:2) environment is formed around the Sm 2+ center that is completed by either two solvent molecules (CH 3 CN or THF) or one bidentate solvent molecule (DME). Inner-sphere solvent molecules can be excluded by reacting SmI 2 with db24c8 in 1:3 THF:toluene to yield Sm(db24c8)I 2 . Here, this molecule features a distorted, eight-coordinate, hexagonal pyramidal Sm 2+ metal center, where the coordinated db24c8 molecule shows a torsion angle unexpectedly close to the 180° antiperiplanar arrangement and two uncoordinated db24c8 oxygen atoms. Solution UV–vis–NIR measurements demonstrate that Sm 2+ is a good size match for the cavity of various db24c8 conformations and that Eu 2+ and Yb 2+ exhibit competition between acetonitrile solvation and the Eu 2+ and Yb 2+ /db24c8 complexes in solution. During excitation by 546 nm light, both [Sm(db24c8)(DME)]I 2 and [Sm(db24c8)(THF) 2 ]I 2 exhibit mixed 5d → 4f and 4f → 4f emission at 20 °C and exclusively 4f → 4f at −180 °C, whereas Sm(db24c8)I 2 only shows 5d → 4f emission regardless of temperature. Photoluminescence from [Sm(db24c8)(CH 3 CN) 2 ][BPh 4 ][I]·CH 3 CN is quenched.

Cations↗
DOE OSTI2024

Key Experimental Considerations When Evaluating Functional Ionic Liquids for Combined Capture and Electrochemical Conversion of CO 2

Ionic liquids (ILs) are considered functional electrolytes for the electrocatalytic reduction of CO 2 (ECO 2 R) due to their role in the double-layer structure formation and increased CO 2 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 ECO 2 R 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, CO 2 mass transport, and ECO 2 R 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 ECO 2 R activity of molecular catalysts Ni(cyclam)Cl 2 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 CO 2 capture and conversion technologies for homogeneous and heterogeneous ECO 2 R.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A Bifunctional Ionic Liquid for Capture and Electrochemical Conversion of CO 2 to CO over Silver

Electrochemical conversion of CO 2 requires selective catalysts and high solubility of CO 2 in the electrolyte to reduce the energy requirement and increase the current efficiency. In this study, the CO 2 reduction reaction (CO 2 RR) 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 CO 2 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 CO 2 reduction in acetonitrile shifts positively by 240 mV when [EMIM][2-CNpyr] is added. This is attributed to the pre-activation of CO 2 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-CO 2 adduct between –1.7 and –2.3 V vs Ag/Ag + and the simultaneous CO formation are captured. Furthermore, this study reveals the electrode surface species and the role of the functionalized ions in lowering the energy requirement of CO 2 RR for the design of multifunctional electrolytes for the integrated capture and conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Stable, Impermeable Hexacyanoferrate Anolyte for Nonaqueous Redox Flow Batteries

Redox-active molecules, or redoxmers, in nonaqueous redox flow batteries often suffer from membrane crossover and low electrochemical stability. Transforming inorganic polyionic redoxmers established for aqueous batteries into nonaqueous candidates is an attractive strategy to address these challenges. Here, in this study, we demonstrate such tailoring for hexacyanoferrate (HCF) by pairing the anions with tetra-n-butylammonium cation (TBA + ). TBA 3 HCF has good solubility in acetonitrile and >1 V lower redox potential vs the aqueous counterpart; thus, the familiar aqueous catholyte becomes a new nonaqueous anolyte. The lowering of redox potential correlates with replacement of water by acetonitrile in the solvation shell of HCF, which can be traced to H-bond formation between water and cyanide ligands. Symmetric flow cells indicate exceptional stability of HCF polyanions in nonaqueous electrolytes and Nafion membranes completely block HCF crossover in full cells. Ion pairing of metal complexes with organic counterions can be effective for developing promising redoxmers for nonaqueous flow batteries.

25 ENERGY STORAGE↗
DOE OSTI2025

Effects of Cofeeding Hydrogen on Propane Dehydrogenation Catalyzed by Isolated Iron Sites Incorporated into Dealuminated BEA

Iron sites dispersed on nonacidic siliceous supports have been reported to be catalytically active for propane dehydrogenation (PDH), yet the precise relationship between site structure and catalytic activity remains elusive. Here, this study provides a comprehensive understanding of the catalytic performance of iron supported on dealuminated BEA (DeAlBEA) zeolites for PDH. Using XAS, UV-vis, and IR spectroscopy of adsorbed pyridine and deuterated acetonitrile, it was found that, at an Fe/Al 0 of 0.04, isolated Fe sites form. These isolated sites exhibit a forward rate of PDH of 213 mol propene/mol Fe·h at 823 K and a feed containing 15 kPa propane. When 15 kPa of H 2 is added to the feed, the forward rate of PDH rises to 391 mol of propene/mol of Fe·h. In both cases, the propene selectivity is over 99%. IR spectroscopy of d 3 -acetonitrile suggests that the open Lewis acid site ((-Si-O-) 2 Fe 3+ -OH) serves as the active site responsible for PDH, while Brønsted acid sites (≡Fe 3+ -O(H)-Si≡) contribute to propane cracking with increasing Fe/Al 0 ratios. Kinetic analysis of the effects of H 2 addition to the propane feed on PDH kinetics shows that H 2 enhances the activity of 0.04FeDeAlBEA primarily by enhancing the strength of the propane adsorption.

Alghannam, Afnan [University of California, Berkel↗