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At least 1,279 records · Page 71

Raidiation-Induced Fragmentation of Diamide Extraction Agents in Ionic Liquid Diluents

N,N,N',N'-Tetraalkyldiglycolamides are extracting agents that are used for liquid-liquid extraction of trivalent metal ions in wet processing of spent nuclear fuel. This application places such agents in contact with the decaying radionuclides, causing radiolysis of the agent in the organic diluent. Recent research seeks to replace common molecular diluents (such as n-dodecane) with hydrophobic room-temperature ionic liquids (ILs), which have superior solvation properties. In alkane diluents, rapid radiolytic deterioration of diglycolamide agents can be inhibited by addition of an aromatic cosolvent that scavenges highly reactive alkane radical cations before these oxidize the extracting agent. Do aromatic ILs exhibit a similar radioprotective effect? To answer this question, we used electron paramagnetic resonance spectroscopy to study the fragmentation pathways in radiolysis of neat diglycolamides, their model compounds, and their solutions in the ILs. Our study indicates that aromatic ILs do not protect these types of solutes from extensive radiolytic damage. Previous research indicated a similar lack of protection for crown ethers, whereas the ILs readily protected di- and trialkyl phosphates (another large class of metal-extracting agents). Our analysis of these unanticipated failures suggests that new types of organic anions are required in order to formulate ILs capable of radioprotection for these classes of solutes. This study is a cautionary tale of the fallacy of analogical thinking when applied to an entirely new and insufficiently understood class of chemical materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Image Charge Method for Reaction Fields in a Hybrid Ion-Channel Model

A multiple-image method is proposed to approximate the reaction-field potential of a source charge inside a finite length cylinder due to the electric polarization of the surrounding membrane and bulk water. When applied to a hybrid ion-channel model, this method allows a fast and accurate treatment of the electrostatic interactions of protein with membrane and solvent. To treat the channel/membrane interface boundary conditions of the electric potential, an optimization approach is used to derive image charges by fitting the reaction-field potential expressed in terms of cylindric harmonics. Meanwhile, additional image charges are introduced to satisfy the boundary conditions at the planar membrane interfaces. In the end, we convert the electrostatic interaction problem in a complex inhomogeneous system of ion channel/membrane/water into one in a homogeneous free space embedded with discrete charges (the source charge and image charges). The accuracy of this method is then validated numerically in calculating the solvation self-energy of a point charge.

59 BASIC BIOLOGICAL SCIENCES↗

The Kinetics and Thermodynamics of CO2 Capture by Aqueous Ammonia Derived Using Meta-GGA Density Functional Theory and Wavefunction-Based Model Chemistry Methods

A meta GGA-DFT study of CO{sub 2} activation in aqueous ammonia solutions, with an emphasis on the reaction barrier and molecularity, has been undertaken using the M06-2X functional with an augmented triple-zeta split-valence basis set (6-311++G(d,p)). Up to five base molecules were treated explicitly in order to establish the effects of solvent catalysis in the chemical capture process. Aqueous free energies of solvation were determined for optimized reactant and transition structures using SM8/M06-2X/6-311++G(d,p). The concept of the solvent pre-complex as presented by Dixon and coworkers (Nguyen, M. T.; Matus, M. H.; Jackson, V. E.; Ngan, V. T.; Rustad, J. R.; Dixon, D. A. J. Phys. Chem. A 2008, 112, 10386-10398) was exploited to account for the energetics of disruption of the hydrogen-bonding solvent nano-network prior to the CO{sub 2} activation step. Selected gas- and aqueous-phase thermodynamic quantities have also been derived.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of TiO{sub 2} and TiO{sub 2}/Au nanoparticles as a Potential Radiosensitizers by Decomposition of Methylene Blue

Nanomaterials are constantly used in several applications of science and engineering. Nanoparticles are currently utilized in computer circuits, clothes, luminescent devices, catalysis, medicine, among many others uses. In the clinical field nanomaterials have become an innovative alternative for early diagnosis and treatment of a significant number of medical conditions. Nanoparticles can be utilized in applications ranging from contrast agents for imaging purposes to carriers for drug delivery in cancerous tumors. The use of nanoparticles made of high atomic number elements as noble metals, is becoming an attractive approach for enhancing the radiation dose delivered to a tissue during radiation therapy. The enhancement effect that makes the cells more sensitive to radiation is known as radiosensitization. Materials such as gold (Au) and titanium dioxide (TiO{sub 2}) at the nanoscale have become promising radiosensitizers. When TiO{sub 2} is irradiated with high energy photons, electron-holes are created within the material. This species interacts with surrounding medium generating reactive oxygen species (ROS). ROS create a toxic environment for cancerous cells, ultimately causing their death. On the other hand gold has a different interaction with ionizing radiation. Upon radiation, gold releases a spray of secondary products such as photoelectrons, auger electrons, and characteristic X-rays. The energy created by the escaping electrons leads to DNA strands breaks in the cells causing their death. Therefore, if these nanoparticles are initially accumulated in the tissue to be treated, the dose delivered during radiation therapy is amplified. This represents a synergistic approach to enhance radiation therapy while substantially reducing side effects. Radiosensitization by nanoparticles often depends on their particle size, morphology and synthesis route. The most commonly used methods to synthesize metallic nanoparticles such as gold involves chemical reduction of a metal precursor. In this case, reducing agents are used in order to transform the metallic ions to metal atoms that will subsequently coalesce and grow to form the nanoparticles . Nevertheless there are alternative methods that do not require a chemical reducing agent. Radiation synthesis is one of those processes. The interaction of ionizing radiation with an aqueous solution containing a metal precursor, leads to a phenomena known as radiolysis of water. Radiolysis of water produces chemical species such as solvated electrons (e{sup -}{sub aq}), and hydrogen atoms (H{sup +}). These species are strong reducing agents that bring the metal ions existing in solution into stable metal atoms that will form nanoparticles. Radiation synthesis is a novel method that offers significant advantages over conventional approaches such as wet chemistry routes. In this approach, no further chemical reducing agents are needed, thus it does not generate byproducts that may affect the nanoparticles properties. This is particularly important in medical applications. Furthermore, this technique is designed to work at room temperature and under atmospheric pressures. Nonetheless the most outstanding feature of radiation synthesis is the possibility to control the particle size and size distribution. This route allows for narrow particle size distributions with size ranging from 2 to 30 nm. Furthermore, the availability of different ionizing radiation producing devices such as synchrotrons, X-ray irradiators, and gamma irradiators enables the possibility of manufacturing nanomaterials under various conditions. In this work, Au nanoparticles were deposited onto TiO{sub 2} using the radiation synthesis method. In addition, the radiosensitization characteristics of TiO{sub 2} and TiO{sub 2}/Au nanoparticles were evaluated through the decomposition of the organic dye Methylene Blue (MB). In order to analyze the degradation of the dye the TiO{sub 2} and TiO{sub 2}/Au nanoparticles were placed in an aqueous solution along with MB and subjected to X-ray irradiation. The samples were irradiated for 30 and 60 minutes. The degradation of the MB after irradiation in the presence and absence of the nanomaterials was measured by UV-Vis spectroscopy following the decrease in the absorbance of the dye at 664 nm. (authors)

36 MATERIALS SCIENCE↗

Integrating advanced materials simulation techniques into an automated data analysis workflow at the Spallation Neutron Source

This presentation will review developments on the integration of advanced modeling and simulation techniques into the analysis step of experimental data obtained at the Spallation Neutron Source. A workflow framework for the purpose of refining molecular mechanics force-fields against quasi-elastic neutron scattering data is presented. The workflow combines software components to submit model simulations to remote high performance computers, a message broker interface for communications between the optimizer engine and the simulation production step, and tools to convolve the simulated data with the experimental resolution. A test application shows the correction to a popular fixed-charge water model in order to account polarization effects due to the presence of solvated ions. Future enhancements to the refinement workflow are discussed. This work is funded through the DOE Center for Accelerating Materials Modeling.

Borreguero Calvo, Jose M↗

Enhanced Cycling Stability of Rechargeable Li-O2 Batteries Using High Concentration Electrolytes

The electrolyte stability against reactive reduced-oxygen species is crucial for the development of rechargeable Li-O2 batteries. In this work, we systematically investigated the effect of lithium salt concentration in 1,2-dimethoxyethane (DME)-based electrolytes on the cycling stability of Li-O2 batteries. Cells with high concentration electrolyte illustrate largely enhanced cycling stability under both the full discharge/charge (2.0-4.5 V vs. Li/Li+) and the capacity limited (at 1,000 mAh g-1) conditions. These cells also exhibit much less reaction-residual on the charged air electrode surface, and much less corrosion to the Li metal anode. The density functional theory calculations are conducted on the molecular orbital energies of the electrolyte components and the Gibbs activation barriers for superoxide radical anion to attack DME solvent and Li+-(DME)n solvates. In a highly concentrated electrolyte, all DME molecules have been coordinated with salt and the C-H bond scission of a DME molecule becomes more difficult. Therefore, the decomposition of highly concentrated electrolyte in a Li-O2 battery can be mitigated and both air-cathodes and Li-metal anodes exhibits much better reversibility. As a results, the cyclability of Li-O2 can be largely improved.

Environmental Molecular Sciences Laboratory↗

Addressing Passivation in Lithium-Sulfur Battery Under Lean Electrolyte Condition

Reducing the electrolyte amount is critical for high practical specific energy of Li-S batteries. The lean electrolyte condition raises a complex situation for sulfur redox reactions since they rely on the electrolyte mediation. The insulating nature of discharge product Li 2 S and its uncontrollable accumulation (passivation) at the cathode interface is one of the major challenges for stable cycling of a Li-S battery under lean electrolyte condition. Here, we present that the NH 4 TFSI additive in electrolyte solution greatly alleviates the passivation issue in Li-S batteries under lean electrolyte condition. The ammonium additive enhances the solvation between sulfide anion and NH 4 + cation, and greatly reduces the amount of large insoluble and insulting Li 2 S particles in the sulfur cathodes, which greatly facilitates the reversible and sustainable redox reactions of sulfur. Therefore, the cycle life of Li-S battery under lean electrolyte condition was greatly improved. In addition, we found that the morphology of Li anode is dependent on the cathode structures. Ammonium additive enables a homogeneous surface of cathode and Li anode and extended cycle life.

Pan, Huilin↗

Superhydrophobic Phosphonium Modified Robust 3D Covalent Organic Framework for Preferential Trapping of Charge Dispersed Oxoanionic Pollutants

Abstract Charge dispersed and less hydrophilic anionic pollutants are often difficult to be preferentially captured by common cationic framework materials. A gamma radiation modification approach is employed to anchor a superhydrophobic phosphonium‐containing coating on a robust crystalline 3D covalent organic framework (COF). By regulating the surface hydrophobicity, the prepared 3DCOF‐ g ‐VBPPh 3 Cl is endowed with a strong affinity for charge dispersed and less hydrophilic oxoanions, such as MnO 4 − , TcO 4 − and ReO 4 − , to surmount the Hofmeister bias, which much favors remediation of oxoanionic pollutants in complex aqueous systems. Batch and column experiments with 3DCOF‐g‐VBPPh 3 Cl in both tap water and simulated groundwater are performed, and rapid sequestration is achieved with removal efficacy up to 99.995%, record‐high distribution coefficient of 1.0 × 10 8 mL g −1 , and desirable priority over competing anions such as Cl − , SO 4 2− , HCO 3 − , and NO 3 − , confirming promise for remediation of charge dispersed anionic pollutants. Theoretical calculations reveal a mechanism of preferential capture based on electrostatic and dispersion interaction between charge dispersed anions and 3DCOF‐g‐VBPPh 3 Cl that effectively competes with solvation of the aqueous anions.

Wang, Yue↗

High Current-Density-Charging Lithium Metal Batteries Enabled by Double-Layer Protected Lithium Metal Anode

The practical application of lithium (Li) metal anode (LMA) is still hindered by non-uniformity of solid electrolyte interphase (SEI), formation of "dead" Li, and continuous consumption of electrolyte although LMA has an ultrahigh theoretical specific capacity and a very low electrochemical redox potential. Herein, we report a facile protection strategy for LMA using a double layer (DL) coating that consists of a polyethylene oxide (PEO)-based bottom layer which is highly stable with LMA and promotes uniform ion flux, and a cross-linked polymer-based top layer which prevents solvation of PEO layer in electrolytes. Li deposited on DL-coated Li (DL@Li) exhibits a smoother surface and much larger size than that deposited on bare Li. The LiF/Li 2 O enriched SEI layer generated by the salt decomposition on top of DL@Li further suppresses the side reactions between Li and electrolyte. Driven by the abovementioned advantageous features, the DL@Li||LiNi 0.6 Mn 0.2 Co 0.2 O 2 cells demonstrate capacity retention of 92.4% after 220 cycles at a current density of 2.1 mA cm -2 (C/2 rate) and stability at a high charging current density of 6.9 mA cm -2 (1.5C rate). These results indicate that the DL protection is promising to overcome the rate limitation of LMAs and high energy-density Li metal batteries.

25 ENERGY STORAGE↗

Enhanced Ion Transport and Molecular Packing Stability in Asymmetric 2D Nanostructured π‐Conjugated Thieno[3,2‐b]Thiophene‐Based Liquid Crystal

Organic semiconductors based on liquid crystal (LC) molecules have attracted increasing interest. Here, in this work, two linear LCs based on 2,5‐bis(thien‐2‐yl)thieno[3,2‐b]thiophene (BTTT) mesogen are designed and synthesized, including BTTT/dEO3 with two symmetrically attached tri(ethylene oxide) groups and BTTT/mEO6 with one asymmetrically attached hexa(ethylene oxide) group. These two molecules have comparable functional‐group compositions but different molecular geometries, leading to their moderately different material performances. Both LCs show smectic mesophases with relatively low transition temperatures as confirmed by differential scanning calorimetry and polarized optical microscopy. A combination of experimental grazing incidence wide‐angle X‐ray scattering and molecular dynamics (MD) simulations reveals a herringbone packing motif of BTTT segments in both LCs while a smaller molecular tilt angle in BTTT/mEO6. Ionic conductivities are measured by doping LCs with different amounts of ionic dopants, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). BTTT/mEO6 shows better smectic phase stability to higher LiTFSI doping ratios. Both LCs exhibit similar ionic conductivities in the smectic phases, but BTTT/mEO6 outperforms BTTT/dEO3 by a factor of three in the amorphous phase at higher temperatures. MD simulations, performed to examine the ion solvation environment, reveal that BTTT/mEO6 is more efficient in coordinating Li‐ions and screening their interactions with TFSI‐ions which further promote ionic transport.

grazing incidence wide-angle X-ray scattering↗

Insight Into Sulfur‐Containing Additive to Boost Anti‐Oxidation Ability of the Ether‐Based Electrolyte for Sodium‐Ion Full Batteries

Ether-based electrolytes are considered as promising candidates for sodium-ion batteries (SIBs) due to their high ionic conductivity and good compatibility with hard carbon (HC) anode. However, they suffer from poor anti-oxidative ability with unstable cathode electrolyte interface, inducing successive electrolyte decomposition and rapid capacity fading. Herein, the sulfur-containing additive (1,3-propanediol cyclic sulfate, PCS) is introduced to boost the stability of the electrode-electrolyte interface (EEI) in ether-based electrolyte. PCS largely participates in the inner Na + sheath, causing more diglyme (G2) molecules and fewer PF 6 - anions to occupy the inner Na + solvation sheath, avoiding the decomposition of G2 molecules at high operation voltage. Moreover, PCS is beneficial for simultaneously constructing thin and robust sulfur-containing EEI on both Prussian blue (PB) cathode and HC anode, maintaining the structural stability of PB and alleviating the dissolution of transition metals. These enable PB||HC pouch cells to deliver a capacity retention of 60.3% after 400 cycles, significantly higher than the 32.1% in PCS-free electrolytes. In conclusion, this work discloses the underlying mechanism of PCS to evoke the anti-oxidation ability of ether-based electrolyte and provides a promising method for realizing advanced sodium-ion full cells.

anti-oxidation ability↗

Peak‐in‐Valley Metal Nano‐Architectures via E‐Beam‐Guided Metal Oxide Redox

Focused electron beams enable nanoscale material modification via localized etching or deposition. In liquid-phase electron-beam-mediated processing, radiolysis-driven redox reactions present an opportunity to control both etching and deposition simultaneously. Here, this duality using a water-ammonia solvent as a tunable redox mediator on copper surfaces is demonstrated. At lower ammonia concentrations, the oxidation process dominates, etching copper to sub-50-nm depths. The copper ions and ion-complexes released during this initial oxidation step are reduced by solvated electrons resulting in metal deposition into the etched sites, over longer e-beam exposures, producing characteristic peak-in-valley nanostructures. Conversely, at higher ammonia concentrations copper-ammine ion complexation and radiolytic oxidizing species scavenging by ammonia occur at higher rates, creating a reducing environment conducive to rapid beam-guided copper deposition. Reaction-transport simulations and experiments are performed to show the effects of ammonia-mediated radiolysis chemistry, describing the direct influence of solvent concentration on redox balance and the outcome of e-beam guided processing. By uniting both etching and deposition within a single framework, this work provides a versatile route for controlled surface nanostructuring.

copper nanostructures↗

Phase Transition Control for High Performance Ruddlesden-Popper Perovskite Solar Cells

Ruddlesden–Popper reduced-dimensional hybrid perovskite (RDP) semiconductors have attracted significant attention recently due to their promising stability and excellent optoelectronic properties. Here, the RDP crystallization mechanism in real time from liquid precursors to the solid film is investigated, and how the phase transition kinetics influences phase purity, quantum well orientation, and photovoltaic performance is revealed. An important template-induced nucleation and growth of the desired (BA) 2 (MA) 3 Pb 4 I 13 phase, which is achieved only via direct crystallization without formation of intermediate phases, is observed. As such, the thermodynamically preferred perpendicular crystal orientation and high phase purity are obtained. At low temperature, the formation of intermediate phases, including PbI 2 crystals and solvate complexes, slows down intercalation of ions and increases nucleation barrier, leading to formation of multiple RDP phases and orientation randomness. These insights enable to obtain high quality (BA) 2 (MA) 3 Pb 4 I 13 films with preferentially perpendicular quantum well orientation, high phase purity, smooth film surface, and improved optoelectronic properties. The resulting devices exhibit high power conversion efficiency of 12.17%. This work should help guide the perovskite community to better control Ruddlesden–Popper perovskite structure and further improve optoelectronic and solar cell devices.

14 SOLAR ENERGY↗

A Highly Stretchy, Transparent Elastomer with the Capability to Automatically Self-Heal Underwater

Polymer materials that are able to self-heal in humid conditions or even in water are highly desirable for their industrial applications. However, the development of underwater self-healing polymer materials is very challenging since water molecules can readily disturb traditional noncovalent bonds, such as saturate the hydrogen bonds, coordinate with the metal cation, as well as solvate the ions. Here, a new type of dipole–dipole interactions is employed as the driving force, combining with highly polar and hydrophobic fluorinated polymers, to successfully demonstrate an underwater self-healing elastomer. Additionally, the polymer materials are transparent and stretchable. They can remain stable underwater for months without significant decay of mechanical properties. Upon mechanical damage, the material is able to self-heal automatically in air, underwater, and under very harsh aqueous conditions (including seawater, highly acidic media, and highly basic media, etc.).

36 MATERIALS SCIENCE↗

Controlling Interfacial Properties of Lithium-Ion Battery Cathodes with Alkylphosphonate Self-Assembled Monolayers

In this paper, the preparation and characterization of modified LiMn 2 O 4 (LMO) cathodes utilizing chemisorbed alkylphosphonic acids to chemically modify their surfaces are reported. Electrochemical methods to study ionic and molecular mobility through the alkylphosphonate self-assembled monolayers (SAMs) for different alkyl chain compositions, in order to better understand their impact on the lithium-ion electrochemistry, are utilized. Electrochemical trends for different chains correlate to trends observed in contact angle measurements and solvation energies obtained from computational methods, indicating that attributes of the microscopic wettability of these interfaces with the battery electrolyte have an important impact on ionic mobility. The effects of surface modification on Mn dissolution are also reported. The alkylphosphonate layer provides an important mode of chemical stabilization to the LMO, suppressing Mn dissolution by 90% during extended immersion in electrolytes. A more modest reduction in dissolution is found upon galvanostatic cycling, in comparison to pristine LMO cathodes. Finally, taken together, the data suggest that alkylphosphonates provide a versatile means for the surface modification of lithium-ion battery cathode materials allowing the design of specific interfaces through modification of organic chain functionalities.

25 ENERGY STORAGE↗

Closo ‐Borate Gel Polymer Electrolyte with Remarkable Electrochemical Stability and a Wide Operating Temperature Window

Abstract A major challenge in the pursuit of higher‐energy‐density lithium batteries for carbon‐neutral‐mobility is electrolyte compatibility with a lithium metal electrode. This study demonstrates the robust and stable nature of a closo ‐borate based gel polymer electrolyte (GPE), which enables outstanding electrochemical stability and capacity retention upon extensive cycling. The GPE developed herein has an ionic conductivity of 7.3 × 10 −4 S cm −2 at room temperature and stability over a wide temperature range from −35 to 80 °C with a high lithium transference number ( = 0.51). Multinuclear nuclear magnetic resonance and Fourier transform infrared are used to understand the solvation environment and interaction between the GPE components. Density functional theory calculations are leveraged to gain additional insight into the coordination environment and support spectroscopic interpretations. The GPE is also established to be a suitable electrolyte for extended cycling with four different active electrode materials when paired with a lithium metal electrode. The GPE can also be incorporated into a flexible battery that is capable of being cut and still functional. The incorporation of a closo ‐borate into a gel polymer matrix represents a new direction for enhancing the electrochemical and physical properties of this class of materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly Stable Operation of Lithium Metal Batteries Enabled by the Formation of a Transient High Concentration Electrolyte Layer

Lithium (Li) metal has been extensively investigated as an anode for rechargeable battery applications due to its ultrahigh specific capacity and the lowest redox potential. However, significant challenges including dendrite growth and low Coulombic efficiency are still hindering the practical applications of rechargeable Li metal batteries. Here, we demonstrate that long-term cycling of Li metal batteries can be realized by the formation of a transient high concentration electrolyte layer near the surface of Li metal anode during high rate discharge process. The highly concentrated Li+ ions in this transient layer will immediately solvate with the available solvent molecules and facilitate the formation of a stable and flexible SEI layer composed of a poly(ethylene carbonate) framework integrated with other organic/inorganic lithium salts. This SEI layer largely suppresses the corrosion of Li metal anode by free organic solvents and enables the long-term operation of Li metal batteries. The fundamental findings in this work provide a new direction for the development and operation of Li metal batteries that could be operated at high current densities for a wide range of applications.

Environmental Molecular Sciences Laboratory↗

Direct Recycling of Spent NCM Cathodes through Ionothermal Lithiation

Ionic liquids (ILs) are a family of nonconventional molten salts that offer many advantages, such as negligible vapor pressures, negligible flammability, wide liquidus ranges, good thermal stability, and much synthesis flexibility. The unique solvation environment of these ILs provides new reaction or flux media for controlling formation of solid-state materials with a minimum perturbation of morphologies. A successful lithiation via ionothermal synthesis using a cost-effective Li halide as Li source and recyclable ILs as solvents is reported in this study for the direct recycling of LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM 111) cathodes. In addition, the ionic liquids can be readily recycled and reused after ionothermal lithiation. The lithiation of spent cathodes can enable the direct recycling of spent cathode materials in lithium-ion batteries.

25 ENERGY STORAGE↗