Ionic Liquid-based Electrowinning for Refining of Rare Earth Oxides/Salts
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25 ENERGY STORAGE↗
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Response of Pseudomonas putida to Complex, Aromatic-Rich Fractions from Biomass
There is strong interest in the valorization of lignin to produce valuable products; however, its structural complexity has been a conversion bottleneck. Chemical pretreatment liberates lignin-derived soluble fractions that may be upgraded by bioconversion. Here, cholinium ionic liquid pretreatment of sorghum produced soluble, aromatic-rich fractions that were converted by Pseudomonas putida (P. putida), a promising host for aromatic bioconversion. Growth studies and mutational analysis demonstrated that P. putida growth on these fractions was dependent on aromatic monomers but unknown factors also contributed. Proteomic and metabolomic analyses indicated that these unknown factors were amino acids and residual ionic liquid; the oligomeric aromatic fraction derived from lignin was not converted. A cholinium catabolic pathway was identified, and the deletion of the pathway stopped the ability of P. putida to grow on cholinium ionic liquid. This work demonstrates that aromatic-rich fractions obtained through pretreatment contain multiple substrates; conversion strategies should account for this complexity.
09 BIOMASS FUELS↗
A contrastive study of three graphite anodes in the piperidinium based electrolytes for lithium ion batteries
Graphical abstract: The fitting results of R{sub sei} and R{sub ct} of three graphite/Li cells. Besides three graphite/Li cells show the similar R{sub sei}, the NG198/Li cell demonstrates a higher R{sub ct} value in all test temperatures. Especially, the R{sub ct} at 333 K is even up to 355.8 Ω cm{sup 2}. Obviously, the narrow distribution of edge plane for NG198 caused this result, and then greatly restricts its cell capacity. By contrast, CMB with bigger specific surface area and more Li{sup +} insertion points shows lower resistance at room temperature, which should help to improve its capacity. - Highlights: • SEI film is closely related to graphite structures and formation temperature. • The graphite with bigger surface area and more Li{sup +} insertion points behaves better. • The graphite with narrow edge plane is uncompetitive for ionic liquid electrolyte. - Abstract: The electrochemical behaviors of natural graphite (NG198), artificial graphite (AG360) and carbon microbeads (CMB) in an ionic liquid based electrolyte are investigated by cyclic voltammetry (CV). The surface and structure of three graphite materials are characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD) before and after cycling. It is found that solid electrolyte interface (SEI) is closely related to graphite structure. Benefiting from larger specific surface area and more dispersed Li{sup +} insertion points, CMB shows a better Li{sup +} insertion/de-insertion behavior than NG198 and AG360. Furthermore, electrochemical impedance spectra (EIS) prove that the SEI of different graphite electrodes has different intrinsic resistance and Li{sup +} penetrability. By comparison, CMB behaves better cell performances than AG360, while the narrow edge plane makes NG198 uncompetitive as a potential anode for the ionic liquids (ILs)-type Li-ion battery.
36 MATERIALS SCIENCE↗
Synthesis and characterization of low viscosity carbon dioxide binding organic liquids for flue gas clean up
Climate change is partly attributed to global anthropogenic carbon dioxide (CO2) emission to the atmosphere. These environmental effects can be mitigated by CO2 capture, utilization and storage. Alkanolamine solvents, such as monoethanolamine (MEA), which bind CO2 as carbamates or bicarbonate salts are used for CO2 capture in niche applications. These solvents consist of approximately 30 wt% of MEA in water, exhibiting a low, CO2-rich viscosity, fast kinetics and favorable thermodynamics. However, these solvents have low CO2 capacity and high heat capacity of water, resulting in prohibitively high costs of thermal solvent regeneration. Effective capture of the enormous amounts of CO2 produced by coal-fired plants requires a material with high CO2 capacity and low regeneration energy requirements. To this end, several water-lean transformational solvents systems have been developed in order to reduce these energy penalties. These technologies include nano-material organic hybrids (NOHMs), task-specific, protic and conventional ionic liquids, phase change solvents. As part of an ongoing program in our group, we have developed new water lean transformational solvents known as CO2 binding organic liquids (CO2BOLs) which have the potential to be energy efficient CO2 capture solvents. These solvents, also known as switchable ionic liquids meaning, are organic solvents that can reversibly transform from non- ionic to ionic form and back. The zwitterionic state in these liquids is formed when low polarity non-ionic alkanolguanidines or alkanolamidines react with CO2 or SO2 to form ionic liquids with high polarity. These polar ionic liquids can be thermally converted to the less polar non-ionic solvent by releasing CO2.
Koech, Phillip K.↗
Room temperature electrodeposition of actinides from ionic solutions
Uranic and transuranic metals and metal oxides are first dissolved in ozone compositions. The resulting solution in ozone can be further dissolved in ionic liquids to form a second solution. The metals in the second solution are then electrochemically deposited from the second solutions as room temperature ionic liquid (RTIL), tri-methyl-n-butyl ammonium n-bis(trifluoromethansulfonylimide) [Me.sub.3N.sup.nBu][TFSI] providing an alternative non-aqueous system for the extraction and reclamation of actinides from reprocessed fuel materials. Deposition of U metal is achieved using TFSI complexes of U(III) and U(IV) containing the anion common to the RTIL. TFSI complexes of uranium were produced to ensure solubility of the species in the ionic liquid. The methods provide a first measure of the thermodynamic properties of U metal deposition using Uranium complexes with different oxidation states from RTIL solution at room temperature.
36 MATERIALS SCIENCE↗
Advanced Electrochemical Separations of Actinide/Fission Products via the Control of Nucleation and Growth of Electrodeposits. Final Report
This is the final report to the NEUP regarding the “Advanced Electrochemical Separations of Actinide/Fission products via the Control of Nucleation and Growth of Electrodeposits” project. This report describes the project activities conducted during the period October 01, 2016 through September 30, 2019. The report includes a brief statement of the project objectives and approach, followed by the details of the performed research activities and suggestion for the future work. It is well known that according to current knowledge the pyroprocessing of spent nuclear fuels invariably leads to the dendritic form of electrodeposits, which from technological point of view is undesirable for many reasons. The aim of this research was to study and preclude the formation of electrodeposits with dendritic morphology (of essential importance to FC-1 Program). This project is characterized with four novel study categories: (1) exploring electrodeposit morphology control by controlling the electrochemical deposition reaction rate, (2) the use of rotating disk electrode technique to distinguish the electrodeposition control modes (reaction rate vs. diffusion), (3) morphology studies of lanthanides (La) and actinides (U) in characteristic stages of nucleation and growth, (4) exploring the need for separation of electrochemical cell in compartments for cathodic and anodic reactions. All these study categories were applied on two distinct electrolyte systems (a) high temperature ionic liquids, i.e. molten LiCl-KCl salts, and (b) room temperature ionic liquids (compounds exclusively made of organic cations, and organic/inorganic anions). Because the quality (dense and smooth) of electrodeposits is a direct function of the electrochemical reduction rate (slower the better), the major expectation was that addition of organic molecules would provide the desired slowing down of electroreduction effect, avoiding the undesired dependence on mass transfer. What was learned is summarized in seven key areas.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Computational Studies of [Bmim][PF6]/n-Alcohol Interfaces with Many-Body Potentials
In this paper, we present the results from molecular-dynamics simulations of the equilibrium properties of liquid/liquid interfaces of room temperature ionic liquid [bmim][PF6] and simple alcohols (i.e., methanol, 1-butanol, and 1-hexanol) at room temperature. Polarizable potential models are employed to describe the interactions among species. Results from our simulations show stable interfaces between the ionic liquid and n-alcohols, and we found that the interfacial widths decrease from methanol to 1-butanol systems, and then increase for 1-hexanol interfaces. Angular distribution analysis reveals that the interface induces a strong orientational order of [bmim] and n-alcohol molecules near the interface, with [bmim] extending its butyl group into the alcohol phase while the alcohol has the OH group pointing into the ion liquid region, which is consistent with the recent sum-frequency-generation experiments. We found the interface to have a significant influence on the dynamics of ionic liquids and n-alcohols. The orientational autocorrelation functions illustrate that [bmim] rotate more freely near the interface than in the bulk, while the rotation of n-alcohol is hindered at the interface. Additionally, the time scale associated with the diffusion along the interfacial direction is found to be faster for [bmim] but slowed down for n-alcohols approaching the interface. We also calculate the dipole moment of n-alcohols as a function of the distance normal to the interface. We found that, even though methanol and 1-butanol have different dipole moments in bulk phase, they reach a similar value at the interface. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory is a multiprogram national laboratory operated for the Department of Energy by Battelle. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.
Chang, Tsun-Mei↗
Ionic Liquid-Assisted Sonochemical Preparation of CeO 2 Nanoparticles for CO Oxidation
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Synthesis of ruthenium metal doped titanium dioxide nanoparticles for CO{sub 2} hydrogenation
Two different types of Ru metal doped TiO{sub 2} nanoparticles were synthesized using a sole gel method with and without ionic liquid. It was clearly observed during characterizing the Ru-TiO{sub 2}-IL catalyst with respect to Ru-TiO{sub 2} catalyst that Ru metal is dispersed while using ionic liquid as reaction medium for catalyst synthesis. TEM image also reveals the presence of agglomeration free, stable and well dispersed Ru metal doped TiO{sub 2} nanoparticles in Ru-TiO{sub 2}-IL over a Ru-TiO{sub 2} catalyst. Such unique feature of the Ru-TiO{sub 2}-IL catalyst reflected in terms of high TON /TOF value of formic acid during the hydrogenation reaction of CO{sub 2} in task specific ionic liquid medium. Low catalysts loading, moisture/air stability, high selectivity, an easy reaction protocol for catalyst synthesis as well as stress-free reaction condition along with 6 times catalysts recycling is the major outcomes of the proposed protocol.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Recover Gas from Liquids in Low Gravity
This document is the final report resulting from the work conducted by undergraduate students at the University of South Alabama during the 2019/2020 academic year. Currently, on the International Space Station a solid adsorbent material is used to remove CO 2 from cabin air; however, liquid absorbent/reactive based systems are appealing because they may offer greater CO 2 capture efficiency. When liquids are used to capture CO 2 a regeneration step is required to release the CO 2 from the fluid for subsequent processing. During regeneration aerosolized droplets of water and liquid amines are produced creating a 2-phase fluid stream. Because the CO 2 stream is to be sent to a Sabatier reactor for conversion into methane, the droplets of the water and amines must be removed, necessitating the need for a vapor/liquid separation process in a microgravity environment. This class was tasked with designing a system to separate the aerosolized droplets from the gas stream. An ionic liquid was assumed to be the amine based absorber fluid that was used to capture the CO 2 , which is a key assumption because the ionic liquid has vanishingly low vapor pressure. The lack of volatility of the ionic liquid eliminates the need to manage an aerosolized amine resulting in only an aerosolized water air separation. To solve this challenge an undergraduate class used systems engineering to design and construct a hydrophobic screen separation apparatus for a 2-phase, vapor/liquid flow. The apparatus was constructed, but initial testing was not possible due to the closure of the University labs due to the corona-virus pandemic.
T Grant Glover↗
Solvent Dependence of Ionic Liquid-Based Pt Nanoparticle Synthesis: Machine Learning-Aided In-Line Monitoring in a Flow Reactor
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Effects of Strain Rate and Temperature on the Mechanical Properties of Simulated Silica Ionogels
Ionogels are hybrid materials formed by impregnating the pore space of a solid matrix with a conducting ionic liquid. By combining the properties of both component materials, ionogels can act as self-supporting electrolytes in Li batteries. In this study, molecular dynamics simulations are used to investigate the dependence of mechanical properties of silica ionogels on solid fraction, temperature, and pore width. Comparisons are made with corresponding aerogels. We find that the solid matrix fraction increases the moduli and strength of the ionogel. This varies nonlinearly with temperature and strain rate, according to the contribution of the viscous ionic liquid to resisting deformation. Additionally, owing to the temperature and strain sensitivity of the ionic liquid viscosity, the mechanical properties approach a linear mixing law at high temperature and low strain rates. The median pore width of the solid matrix plays a complex role, with its influence varying qualitatively with deformation mode. Narrower pores increase the relevant elastic modulus under shear and uniaxial compression but reduce the modulus obtained under uniaxial tension. Conversely, shear and tensile strength are increased by narrowing the pore width. All of these pore size effects become more pronounced as the silica fraction increases. Pore size effects, similar to the effects of temperature and strain rate, are linked to the ease of fluid redistribution within the pore space during deformation-induced changes in the geometry of the pores.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Funneled Depolymerization of Ionic Liquid-Based Biorefinery “Heterogeneous” Lignin into Guaiacols over Reusable Palladium Catalyst
The efficient utilization of lignin, the direct source of renewable aromatics, into value-added renewable chemicals is an important step towards sustainable biorefinery practices. Nevertheless, owing to the random heterogeneous structure and limited solubility, lignin utilization has been primarily limited to burning for energy. The catalytic depolymerization of lignin has been proposed and demonstrated as a viable route to sustainable biorefinery, however, low yields and poor selectivity of products, high char formation, and limited to no recycling of transition-metal-based catalyst involved in lignin depolymerization demands attention to enable practical-scale lignocellulosic biorefineries. In this study, we demonstrate the catalytic depolymerization of ionic liquid-based biorefinery poplar lignin into guaiacols over a reusable zirconium phosphate supported palladium catalyst. The essence of the study lies in the high conversion (>80 %), minimum char formation (7–16 %), high yields of guaiacols (up to 200 mg / g of lignin), and catalyst reusability. In conclusion, both solid residue, liquid stream, and gaseous products were thoroughly characterized using ICP-OES, PXRD, CHN analysis, GC-MS, GPC, and 2D NMR to understand the hydrogenolysis pathway.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Electrochromic device based on electrospun WO{sub 3} nanofibers
Highlights: • WO{sub 3} electrochromic nanofibers were prepared by electrospinning technique. • WO{sub 3} nanofibers switched reversibly from transparent to blue color. • Electrochromic device was assembled using ionic liquid based gel electrolyte. • Significant optical modulation and excellent cycling stability were achieved for ECD. - Abstract: The tungsten oxide (WO{sub 3}) nanofibers were grown directly onto an ITO-coated glass via an electrospinning method for electrochromic applications. The electrochromic properties of WO{sub 3} nanofibers were investigated in the presence of different electrolytes including a series of ionic liquids and classic LiClO{sub 4}-PC system. A significant optical modulation of 20.82% at 760 nm, reversible coloration with efficiency of 64.58 cm{sup 2}/C and excellent cycling stability were achieved for the nanofiber electrochromic device (ECD) with ionic liquid based gel electrolyte.
36 MATERIALS SCIENCE↗
Rare earth amide compositions
A method for extracting a rare earth element from a rare earth-containing substance, the method comprising mixing the rare earth-containing substance with a protic ionic liquid, such as: wherein R1 is selected from hydrogen atom and hydrocarbon groups containing 1 to 6 carbon atoms; R2 and R3 are independently selected from hydrocarbon groups containing 1 to 12 carbon atoms; and X− is an anionic species; to produce a composition of the formula (RE)(amide)yXz at least partially dissolved in the protic ionic liquid, wherein RE is at least one rare earth element having an atomic number selected from 39, 57-71, and 90-103; y is 2-6; z is a number that charge balances the total positive charge of RE; and the amide is the conjugate base of the cationic portion of the protic ionic liquid of Formula (1) and has the following formula:
Freiderich, John William↗
Modifying Interface Solvation and Oxygen Reduction Electrocatalysis with Hydrophobic Species
Ionic liquid interlayers improve the oxygen reduction reaction (ORR) kinetics on bulk and nanostructured catalysts for both Pt and alloyed-Pt materials. Despite the demonstrated performance enhancement at the half-cell and membrane electrode assembly level, the mechanism of the improvement is not fully understood. In this work, we combine single-crystal experiments with microkinetic modeling to uncover the origin of the ORR kinetic improvement on Pt(111) in the presence of ionic liquids and hydrophobic cations. With the incorporation of a modified Frumkin isotherm, our model accurately simulates the disorder–order transition observed in hydroxyl and bisulfate adsorption on Pt(111) under acidic conditions. Voltametric analysis shows that ionic liquids impact solvation to break so-called scaling relations between the adsorption strength of OH ad and O ad , but these effects have little impact on ORR activity. Instead, destabilized OH ad reduces the overall hydroxyl (spectator) coverage, resulting in higher availability of active sites.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ion movement in thin Nafion films under an applied electric field
In this study, the electromechanical response of Nafion films with and without an ionic liquid (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) ([emim]Tf 2 N) additive were characterized under an applied electric field in situ using neutron reflectometry (NR) and voltage modulated atomic force microscopy (VM-AFM). NR showed that pure Nafion films exhibited no response under field strengths of ~0.18 V/μm, while VM-AFM measurements showed a minimal response at higher field strengths (~200 V/μm), which is ascribed to the residual water presence in the films. The addition of ionic liquid resulted in clear electroresponsiveness seen in both NR and VM-AFM. NR results indicated mass migration away from the cathodic interface driven by the [emim] + movement in the direction of the electric field. The lack of ionic liquid accumulation at the electrode interfaces contrasts the bulk electromechanical behavior of similar systems reported in the literature. VM-AFM measurements were able to resolve the relative contributions of the [emim] + cation and Tf 2 N - anion to film deformation by alternating the direction of the applied field and support the [emim] + dominant migration seen in the NR results. Lastly, the findings presented here emphasize the need for the nanoscale analysis of material properties of electroresponsive thin film systems and demonstrate the potential for probing electric field effects using in situ techniques.
36 MATERIALS SCIENCE↗
A Rayleighian approach for modeling kinetics of ionic transport in polymeric media
Here, we report a theoretical approach for analyzing impedance of ionic liquids (ILs) and charged polymers such as polymerized ionic liquids (PolyILs) within linear response. The approach is based on the Rayleigh dissipation function formalism, which provides a computational framework for a systematic study of various factors, including polymer dynamics, in affecting the impedance. We present an analytical expression for the impedance within linear response by constructing a one-dimensional model for ionic transport in ILs/PolyILs. This expression is used to extract mutual diffusion constants, the length scale of mutual diffusion, and thicknesses of a low-dielectric layer on the electrodes from the broadband dielectric spectroscopy (BDS) measurements done for an IL and three PolyILs. Also, static dielectric permittivities of the IL and the PolyILs are determined. The extracted mutual diffusion constants are compared with the self diffusion constants of ions measured using pulse field gradient (PFG) fluorine nuclear magnetic resonance (NMR). For the first time, excellent agreements between the diffusivities extracted from the Electrode Polarization spectra (EPS) of IL/PolyILs and those measured using the PFG-NMR are found, which allows the use of the EPS and the PFG-NMR techniques in a complimentary manner for a general understanding of the ionic transport.
36 MATERIALS SCIENCE↗