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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Improved precision in As speciation analysis with HERFD-XANES at the As K -edge: the case of As speciation in mine waste

High-energy-resolution fluorescence-detected (HERFD) X-ray absorption near-edge spectroscopy (XANES) is a spectroscopic method that allows for increased spectral feature resolution, and greater selectivity to decrease complex matrix effects compared with conventional XANES. XANES is an ideal tool for speciation of elements in solid-phase environmental samples. Accurate speciation of As in mine waste materials is important for understanding the mobility and toxicity of As in near-surface environments. In this study, linear combination fitting (LCF) was performed on synthetic spectra generated from mixtures of eight measured reference compounds for both HERFD-XANES and transmission-detected XANES to evaluate the improvement in quantitative speciation with HERFD-XANES spectra. The reference compounds arsenolite (As 2 O 3 ), orpiment (As 2 S 3 ), getchellite (AsSbS 3 ), arsenopyrite (FeAsS), kaňkite (FeAsO 4 ·3.5H 2 O), scorodite (FeAsO 4 ·2H 2 O), sodium arsenate (Na 3 AsO 4 ), and realgar (As 4 S 4 ) were selected for their importance in mine waste systems. Statistical methods of principal component analysis and target transformation were employed to determine whether HERFD improves identification of the components in a dataset of mixtures of reference compounds. LCF was performed on HERFD- and total fluorescence yield (TFY)-XANES spectra collected from mine waste samples. Arsenopyrite, arsenolite, orpiment, and sodium arsenate were more accurately identified in the synthetic HERFD-XANES spectra compared with the transmission-XANES spectra. In mine waste samples containing arsenopyrite and either scorodite or kaňkite, LCF with HERFD-XANES measurements resulted in fits with smaller R -factors than concurrently collected TFY measurements. The improved accuracy of HERFD-XANES analysis may provide enhanced delineation of As phases controlling biogeochemical reactions in mine wastes, contaminated soils, and remediation systems.

58 GEOSCIENCES↗
DOE OSTI2020

Generating MCNP Input Files for Unstructured Mesh Geometries

Los Alamos National Laboratory's (LANL) Monte Carlo N-Particle (MCNP) transport code version 6 has the capability for tracking particles on unstructured mesh (UM) geometry models. The MCNP UM feature has been developed for performing calculations of complex geometry models. This capability tracks particles on hybrid geometries where finite element meshes are embedded into constructive solid geometry (CSG) cells. The MCNP UM feature was originally designed to read UM models created by Abaqus/CAE software suite. MCNP versions 6.2.0 and later can process UM models read from Abaqus input les or MCNPUM les converted from Abaqus input les. Sandia National Laboratory's Cubit Toolkit and other finite element analysis software packages may generate UM models and then convert these models into Abaqus input formats.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2024

Solid Sorbent Cost Sensitivity Analysis: A Framework for UNF Reprocessing Sorbent Cost Comparison

Solid sorbents have been the subject of research and development across the U.S. Department of Energy national laboratory complex for many years. They are generally accepted as a safer alternative to cryogenic distillation for noble gas capture, and they present an easier pathway in development of long-term waste forms after iodine capture. As more types of sorbents have been proposed for capture of volatile radionuclides, it has become necessary to compare them based on performance and cost criteria. This report details cost and performance information for three promising sorbents and provides a cost sensitivity analysis. The goal of this analysis is to establish a framework which can be utilized to directly compare future sorbents, with differing properties, to the sorbents discussed in this report. Direct comparison is instrumental to making informed decisions to efficiently guide research and minimize laborious detours. In all cases, sorbent capacity is a major cost driver as it influences the mass of sorbent, operational footprint, and disposal cost requirements., However, sorbent price can greatly increase the cost of a capture technology. For sorbents used in krypton capture, the purity of krypton released to storage is the highest cost driver.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

High Order Wall-Modeled Large-Eddy Simulation on Mixed Unstructured Meshes

In the present study, an algebraic equilibrium wall model previously developed for hexahedral elements is extended to handle mixed meshes including prismatic, tetrahedral, and pyramidal elements in the context of a discontinuous high-order method. This extension is needed for complex geometries, for which high-order mixed elements (e.g., tetrahedral and pyramidal elements) are often necessary near solid walls to avoid meshing challenges. Various design decisions are discussed to achieve the best performance on massively parallel CPU/GPU architectures for a production-level high-order large-eddy simulation solver based on the flux reconstruction/correction procedure via reconstruction method, hpMusic. The extension to other elements is first evaluated using a benchmark channel flow problem at various Reynolds numbers. After that, flow over the NASA high-lift Common Research Model (CRM-HL) from the 4th AIAA High-lift Prediction Workshop is computed to further test the new implementation. Computational results at the third- and fourth-order accuracies are compared with experimental data.

Engineering↗
DOE OSTI2023

A level-set immersed boundary method for reactive transport in complex topologies with moving interfaces

A simulation framework based on the level-set and the immersed boundary methods (LS-IBM) has been developed for reactive transport problems in porous media involving a moving solid-fluid interface. The interface movement due to surface reactions is tracked by the level-set method, while the immersed boundary method captures the momentum and mass transport at the interface. The proposed method is capable of accurately modeling transport near evolving boundaries in Cartesian grids. The framework formulation guarantees second order accuracy in space. Since the interface velocity is only defined at the moving boundary, an interface velocity propagation method is also proposed. The method can be applied to other moving interface problems of the “Stefan” type. Here, we validate the proposed LS-IBM both for flow and transport close to an immersed object with reactive boundaries as well as for crystal growth. Lastly, the proposed method provides a powerful tool to model more realistic problems involving moving reactive interfaces in complex domains.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Structural mapping and tuning of mixed halide ions in amorphous sulfides for fast Li-ion conduction and high deformability

Amorphous sulfides are among the most promising candidates for solid electrolytes (SEs) owing to their excellent deformability and acceptable Li-ion conductivity (σion) at room temperature. However, the complex atomic structure of these amorphous materials without long-range ordering results in a lack of structural understanding and difficulties in tuning material properties. Here, in this study, we performed structural mapping of glassy sulfide SEs composed of various anion clusters using a combinatorial atomic level analysis of synchrotron X-ray-based pair distribution function (PDF) and reverse Monte-Carlo (RMC) methods, demonstrating the potential to tune σ ion in glass SEs. First, we prepared a new glassy sulfide with a mixed anion framework of two halogens (Br and I) as atomic anions, with PS 4 3- molecular anions in a Li 2 S–P 2 S 5 -based glass SE. At a specific Br content, [(Li 2 S) 0.658 (LiI 0.9 LiBr 0.1 ) 0.342 ] 0.825 [P 2 S 5 ] 0.175 recorded a σ ion of 2.27 mS cm -1 , the highest value for any glass sulfides reported to date; however, its elastic modulus was still suppressed to 14.48 GPa. PDF and RMC calculations successfully provided structural mapping of anion clusters, including two halogens. Molecular dynamics simulations of each composition confirmed that flexible coordination caused by the rattling of small polarizable Br ions in the mixed halogens of glassy SEs contributed to the superior σ ion . Our results may provide new insights into the design of superior glassy SEs that play key roles in all-solid-state batteries requiring fast Li-ion conduction and high deformability.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A sharp interface Lagrangian-Eulerian method for rigid-body fluid-structure interaction

Herein this paper introduces a sharp interface method to simulate fluid-structure interaction (FSI) involving rigid bodies immersed in viscous incompressible fluids. The capabilities of this methodology are benchmarked using a range of test cases and demonstrated using large-scale models of biomedical FSI. The numerical approach developed herein, which we refer to as an immersed Lagrangian-Eulerian (ILE) method, integrates aspects of partitioned and immersed FSI formulations by solving separate momentum equations for the fluid and solid subdomains, as in a partitioned formulation, while also using non-conforming discretizations of the dynamic fluid and structure regions, as in an immersed formulation. A simple Dirichlet-Neumann coupling scheme is used, in which the motion of the immersed solid is driven by fluid traction forces evaluated along the fluid-structure interface, and the motion of the fluid along that interface is constrained to match the solid velocity and thereby satisfy the no-slip condition. To develop a practical numerical method, we adopt a penalty approach that approximately imposes the no-slip condition along the fluid-structure interface. In the coupling strategy, a separate discretization of the fluid-structure interface is tethered to the volumetric solid mesh via stiff spring-like penalty forces. Our fluid-structure coupling scheme relies on an immersed interface method (IIM) for discrete geometries, which enables the accurate determination of both velocities and stresses along complex internal interfaces. Numerical methods for FSI can suffer from instabilities related to the added mass effect, but computational tests indicate that the methodology introduced here remains stable for selected test cases across a broad range of solid-fluid mass density ratios, including extremely small, nearly equal, equal, and large density ratios. Biomedical FSI demonstration cases include results obtained using this method to simulate the dynamics of a bileaflet mechanical heart valve in a pulse duplicator, and to model transport of blood clots in a patient-averaged anatomical model of the inferior vena cava.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Deeper Understanding of Mononuclear Manganese(IV)–Oxo Binding Brønsted and Lewis Acids and the Manganese(IV)–Hydroxide Complex

Binding of Lewis acidic metal ions and Brønsted acid at the metal–oxo group of high-valent metal–oxo complexes enhances their reactivities significantly in oxidation reactions. However, such a binding of Lewis acids and proton at the metal–oxo group has been questioned in several cases and remains to be clarified. In this work, we report the synthesis, characterization, and reactivity studies of a mononuclear manganese(IV)–oxo complex binding triflic acid, {[(dpaq)Mn IV (O)]–HOTf} + (1–HOTf). First, 1–HOTf was synthesized and characterized using various spectroscopic techniques, including resonance Raman (rRaman) and X-ray absorption spectroscopy/extended X-ray absorption fine structure. In particular, in rRaman experiments, we observed a linear correlation between the Mn–O stretching frequencies of 1–HOTf (e.g., ν Mn–O at ~793 cm –1 ) and 1–M n+ (Mn + = Ca 2+ , Zn 2+ , Lu 3+ , Al 3+ , or Sc 3+ ) and the Lewis acidities of H + and M n+ ions, suggesting that H+ and Mn+ bind at the metal–oxo moiety of [(dpaq)Mn IV (O)] + . Interestingly, a single-crystal structure of 1–HOTf was obtained by X-ray diffraction analysis, but the structure was not an expected Mn(IV)–oxo complex but a Mn(IV)–hydroxide complex, [(dpaq)Mn IV (OH)](OTf) 2 (4), with a Mn–O bond distance of 1.8043(19) Å and a Mn–O stretch at 660 cm –1 . More interestingly, 4 reverted to 1–HOTf upon dissolution, demonstrating that 1–HOTf and 4 are interconvertible depending on the physical states, such as 1–HOTf in solution and 4 in isolated solid. The reactivity of 1–HOTf was investigated in hydrogen atom transfer (HAT) and oxygen atom transfer (OAT) reactions and then compared with those of 1–Mn+ complexes; an interesting correlation between the Mn–O stretching frequencies of 1–HOTf and 1–M n+ and their reactivities in the OAT and HAT reactions is reported for the first time in this study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Data-Driven Discovery and Experimental Validation of Solvent Polarity Effects on Conjugated Polymer Solution-to-Film Assembly Pathways

Understanding how solvent properties influence the solution-to-film assembly of conjugated polymers remains a critical challenge due to the complex and intertwined nature of polymer–solvent interactions. In this study, we integrate a data-driven framework with experimental validation to identify key parameters influencing the assembly and performance of poly[2,5-(2-octyldodecyl)-3,6-diketopyrrolopyrrole-alt-5,5-(2,5-di(thien-2-yl)thieno[3,2-b]thiophene)] (DPP-DTT) in organic field-effect transistors (OFETs). A machine learning (ML) approach identified the normalized Reichardt polarity parameter (E T N ) as a significant descriptor correlated with DPP-DTT hole mobility (μ). Systematic DPP-DTT devices fabricated using solvents across a wide E T N range revealed that higher E T N solvents yield enhanced μ. To elucidate the structural origins of high μ, we conducted comprehensive analyses using UV–vis–NIR spectroscopy and grazing incidence wide angle X-ray scattering (GIWAXS) measurements. The results revealed that films processed from high E T N solvents exhibit reduced paracrystallinity. By analyzing the solution-state behavior using optical microscopy and solution WAXS, we revealed polymer solubility differences in the various solvents and associated distinct polymer assembly pathways, elucidating why the high E T N solvent produces long-range ordered films. Notably, the high E T N solvent shows a pronounced preference for liquid-crystal (LC)-mediated assembly, providing a mechanistic explanation for the enhanced structural order. Therefore, these results demonstrate that solvent polarity, as evaluated by E T N , serves as an important parameter that plays a significant role in the DPP-DTT assembly pathway and resultant solid-state morphology. This work provides a strategy for integrating data science with experiments to identify critical parameters associated with complex polymer systems and helps guide rational process design for high-performance organic electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2022

iClick synthesis of network metallopolymers

Described is an approach to preparing the first iClick network metallopolymers with porous properties. Treating digoldazido complex 2-AuN 3 with trigoldacetylide 3-AuPPh 3 or 3-AuPEt 3 , trialkyne 3-H, tetragoldacetylide 4-AuPPh 3 , or tetraalkyne 4-H in CH 2 Cl 2 affords five iClick network metallopolymers 5-AuPPh 3 , 5-AuPEt 3 , 5-H, 6-AuPPh 3 , and 6-H. Additionally, confirmation of the iClick network metallopolymers comes from FTIR, 13 C solid-state cross-coupling magic angle spinning (CPMAS) NMR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and nitrogen and CO 2 sorption analysis. Employing model complexes 7-AuPPh 3 , 7-AuPEt 3 , 7-H, 8-AuPPh 3 , and 8-H provides structural insights due to the insolubility of iClick network metallopolymers.

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

Targeted Adjusting Molecular Arrangement in Organic Solar Cells via a Universal Solid Additive

The incorporation of solid additive has been considered as an effective strategy for developing organic photovoltaics with multi-components, which is independent of dynamics, playing unique roles in morphology adjustment. However, their complex working mechanisms involving specific chemical structures are selective to material systems, hence limiting their university and flexibility in application. Herein, an inert small-molecular compound naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole (NT) is introduced into the bulk-heterojunction blend as the solid additive, which can function with various material systems and solvents, depending on its simple π-conjugated structure and S⋯N interaction for adjusting molecular alignment. It is interesting to note that the introduced NT can not only improve device performance, but also simplify complicated pre- or post-processing methods, reduce impact from batch-to-batch differences, construct sufficient energy transfer channel as well as improve device stability. The resulting devices based on PTzBI-dF:Y6-BO system show an impressive power conversion efficiency of 17.4% with obviously enhanced T 80 lifetime of >1200 h. These findings provide useful guidelines for exploring potential universal solid additives benefitting toward commercial application.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Linear Free Energy Relationships Associated with Hydride Transfer From [(6,6'-R 2 -bpy)Re(CO) 3 H]: A Cautionary Tale in Identifying Hydrogen Bonding Effects in the Secondary Coordination Sphere

Here, six rhenium hydride complexes, [(6,6'-R 2 -bpy)Re(CO) 3 H] (bpy = 2,2'-bipyridine, R = OEt, OMe, NHMe, Me, F, Br), were synthesized. These complexes insert CO 2 to form rhenium formate complexes of the type [(6,6'-R 2 -bpy)Re(CO) 3 {OC(O)H}]. All the rhenium formate species were characterized using X-ray crystallography, which revealed that the bpy ligand is not coplanar with the metal coordination plane containing the two nitrogen donors of the bpy ligand but tilted. A solid-state structure of [(6,6'-Me 2 -bpy)Re(CO) 3 H] determined using MicroED also featured a tilted bpy ligand. The kinetics of CO 2 insertion into complexes of the type [(6,6'-R 2 -bpy)Re(CO) 3 H] were measured experimentally and the thermodynamic hydricities of [(6,6'-R 2 -bpy)Re(CO) 3 H] species were determined using theoretical calculations. A Brønsted plot constructed using the experimentally determined rate constants for CO 2 insertion and the calculated thermodynamic hydricities for [(6,6'-R 2 -bpy)Re(CO) 3 H] revealed a linear free energy relationship (LFER) between thermodynamic and kinetic hydricity. This LFER is different to the previously determined relationship for CO 2 insertion into complexes of the type [(4,4'-R 2 -bpy)Re(CO) 3 H]. At a given thermodynamic hydricity, CO 2 insertion is faster for complexes containing a 6,6'-substituted bpy ligand. This is likely in part due to the tilting observed for systems with 6,6'-substituted bpy ligands. Notably, the 6,6'-(NHMe) 2 -bpy ligand could in principle stabilize the transition state for CO 2 insertion via hydrogen bonding. This work shows that if only the rate of CO 2 insertion into [(6,6'-(NHMe) 2 -bpy)Re(CO) 3 H] is compared to [(4,4'-R 2 -bpy)Re(CO) 3 H] systems, the increase in rate could be easily attributed to hydrogen bonding, but in fact all 6,6'-substituted systems lead to faster than expected rates.

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

Molecular structures of dissolved and colloidal As V –Fe III complexes and their roles in the mobilization of As V under strongly acidic conditions

The effect of high concentration of iron (Fe III ) on the speciation and mobility of arsenic (As) under strongly acidic conditions remains unclear. This work studied the redistribution and speciation of As V and Fe III at Fe/As molar ratio of 1–14 and pH 1.5–2.0 in the dissolved, colloidal, and solid phases. Results showed that the elevated Fe III induced the decomposition of the precipitated poorly crystalline ferric arsenate by forming dissolved (< 3 kDa) and colloidal (3 kDa–0.1 µm) As–Fe complexes. The fraction of particulate As (> 0.1 µm) decreased from 70–90% to less than 20% when the Fe/As molar ratio increased from 1 to 14. The particle size of the bulk samples decreased significantly with the increase of Fe III concentration. The FTIR results suggested that AsV in dissolved/colloidal As–Fe complexes dominantly occurred as HAsO 4 2– species. The EXAFS results indicated that each HAsO 4 2– coordinated with approximately two Fe atoms in dissolved/colloidal As–Fe complexes at Fe/As ≥ 2. Furthermore, the findings suggest that high aqueous Fe III concentration can promote the mobility of As by forming dissolved/colloidal Fe–As complexes in acidic waters, potentially accelerating As transport from source to downstream in acid mine drainage systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Synthesis and Single Crystals of Refractory Oxides of Lanthanides and Thorium

At the completion of this program, we can report that we developed a considerable degree of technical improvements in our ability to perform hydrothermal reactions at high temperatures and pressures. We can now routinely perform reactions at 700-750°C and 200 MPa. Currently we are in the process of exploiting this new technology synthesizing a range of exotic new materials investigating relatively poorly understood materials. Our initial efforts focused on the chemistry of rare earth oxides with tetravalent and pentavalent oxides. We recently published a study of the lanthanides with Nb 5+ and Ta 5+ ions, where we grew oxides such as RENdO 4 and RETaO 4 as high quality single crystals. These compounds were targeted as potential hosts for luminescent and scintillation materials, particularly given that they are among the densest oxide hosts and hence have good potential as absorbers for high energy radiation like X-rays and gamma rays. We also isolated a range of unusual new rare earth tantalates with very complex structures. indicating that the chemistry is very sensitive to conditions. We performed some fairly comprehensive examinations of the solid-state chemistry of rare earth ions with various tetravalent metal ions especially Si 4+ , Ge 4+ , Sn 4+ and Ti 4+ . Given the potential role of rare earth silicates in immobilizing radioactive waste elements in long-term storage, and the similarity of our hydrothermal fluids with known geological conditions, this chemistry continues to be relevant. We prepared an extensive series of new lanthanide germanates (e.g. RE 13 Ge 6 O 31 (OH), BaRE 10 (GeO 4 ) 4 O 8 ). and found that there is there is almost no overlap between the chemistry of the rare earth silicates. Stannic oxide (SnO 2 ) is much more refractory and requires higher temperatures and of mineralizer concentrations. One significant result is the growth of RE 2 Sn 2 O 7 pyrochlore single crystals. These are of interest because the rare earth stannate pyrochlores are known to display a wide range of magnetic frustration such as spin ice behavior. We grew high quality single crystals of rare earth germanate and stannate pyrochlores and this led to a collaboration with Professor Kate Ross at Colorado State. Preliminary measurements, indicate that the crystals contain no detectable defects or site disorder. Initial neutron diffraction on single crystals was performed at Oak Ridge, and more detailed experiments involving the Ross group are underway at both NIST and ORNL. This particular chemistry has turned out to be the most potentially significant work on this project and the collaborative effort with Prof. Ross is the topic of a DoE renewal project on quantum materials. Our initial foray into the hydrothermal chemistry of rare earth titanates has also been very promising and a range of cubic and polar ferroic phases of the light rare earths RE 2 Ti 2 O 7 (RE = La - Pr) in the P2 1 phase. We also discovered an interesting new phase Ce 2 Ti 4 O 11 that can have implications in heavy metal immobilization and storage. along with a series of new rare earth titanates (La 5 Ti 4 O 15 (OH) Sm 3 TiO 5 (OH) 3 and Lu 5 Ti 2 O 11 (OH) with exceptionally complex structures. One interesting sidelight has been high temperature hydrothermal chemistry terbium, including the growth of large crystals of TbO(OH). This is not a new compound but it is the first time it has been grown as large single crystals. The Tb atom density is almost as high as that in Tb 2 O 3 and has a very high Verdet constant (ca. 70), making it a very attractive candidate as a Faraday rotator. Unfortunately it is not in a cubic structure but he material is hard, stable, pure and inexpensive, so should still be an attractive Faraday oscillator. We recently received a patent on this material. We also synthesized K 2 Tb(Ge 2 O 7 ) containing stable octahedral Tb 4+ ions, which appears to be the first example of a well-characterized Tb 4+ complex. Given that Tb 4+ has been proposed as a benign surrogate for more treacherous tetravalent ions such as Cf 4+ and Bk 4+ , we think that Tb 4+ silicates can be a particularly useful study for actinide immobilization and related work. We also began reaction studies with rare earths and both ReO 2 and RuO 2 . These resulted in large single crystals of species like RE 5 Ru 2 O 12 , RE 4 Re 2 O 11 , REReO 4 and RE 2 ReO 5 . Several of these samples have already been sent to ORNL for magnetic and neutron diffraction studies.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Phase-field modeling of rate-dependent fluid-driven fracture initiation and propagation

The rate-dependent behavior associated with deformation and fracturing of materials, such as natural rocks, poses significant challenges for modeling. In addition to the complications of the viscoelastic response, the speed of fracture propagation reflects micromechanical mechanisms in the fracture process zone(FPZ). In order to represent these complicated behaviors, a thermodynamically consistent, rate-dependent fracture model is required. Based on rigorous thermodynamic principles, we derive a rate-dependent phase-field mechanical model coupled with single-phase fluid flow in both the matrix and the fracture. The model is guaranteed to satisfy energy conservation during fracture propagation. Here, the system of equations is solved using the introduced solution procedure and a novel preconditioner that accounts for the complex fluid-structure interaction. The proposed phase-field model is tested against several benchmark problems on solid-fluid coupling, fluid-driven fracture propagation and rate-dependent viscoelastic deformation. The model serves as a strong basis for investigating rate-dependent fracturing experiments and for making predictions of material behaviors under new conditions.

42 ENGINEERING↗
DOE OSTI2022

Medium-independent hydrogen atom binding isotherms of nickel oxide electrodes

Adsorption and transfer of hydrogen atoms at solid/solution interfaces are fundamental to heterogeneous catalysis for chemical energy transformations and other processes. Reported here are electrochemical and spectroelectrochemical measurements of the thermodynamics of H-atom binding to nickel oxide electrodes, both the average and the distribution of NiO–H bond dissociation free energies (BDFEs). These are perhaps the first measurements of binding isotherms at non-metal electrodes. Remarkably, both the BDFEs and the non-Langmuirian isotherms are the same in water, acetonitrile, and dimethylformamide, and with different buffers and proton activities. Such medium independence of the BDFEs and isotherms has not been previously reported for any binary material. The medium independence supports the common use of computed hydrogen binding energies as intrinsic descriptors of surface reactivity, while the broadened isotherms add a level of complexity to such analyses. Furthermore, this work demonstrates the capability to derive key thermodynamic parameters at chemically reactive solid-liquid interfaces.

13 HYDRO ENERGY↗
DOE OSTI2026

Ion Transport and Crystal Rotation in Plastic Crystal Electrolytes Under Applied Electric Fields

Organic ionic plastic crystal electrolytes, containing a plastic crystal and lithium salt, offer a potential balance between mechanical and electrochemical properties for solid state lithium-ion battery electrolytes. These electrolytes contain multiple mobile ionic species (three or four), resulting in complex transport mechanisms which have not yet been established. Plastic crystals are defined by long-range positional order and short-range rotational disorder. It is therefore necessary to quantify changes in the local crystal structure of the electrolyte as current flows through it. Herein, we examine the electrochemical properties of pyrrolidinium-based plastic crystal electrolytes containing lithium salt and zwitterion additives, including measurements of current fraction and limiting current. We obtain species-specific insight into electrolyte transport using pulsed-field gradient nuclear magnetic resonance spectroscopy and find that, while the zwitterion additive increases ionic conductivity, it decreases lithium diffusivity with respect to other ionic components. With operando spatiotemporally resolved wide-angle X-ray scattering we observe location-specific crystal rotations due to the passage of ionic current. In conclusion, we posit that reducing energy dissipation due to rotation is essential for using plastic crystal electrolytes in practical applications.

Yap, Kyra M. K. [University of California, Berkele↗
DOE OSTI2022

Nanophotonics for Chemical Imaging and Spectroscopy

The manipulation of light and light-matter interactions on the nanoscale is enabled by the unique optical properties of plasmonic metal nanostructures and nanoparticles. Indeed, engineered hybrid molecular-plasmonic nanostructures have enabled single molecule detection and identification via surface-enhanced Raman scattering (SERS). Further, the same effect is at the core of visualizing single molecules with sub-nanometer spatial resolution via tip-enhanced Raman scattering (TERS). More generally, modern applications of plasmon-enhanced spectroscopy and microscopy fueled advances in fields as diverse as quantum and semiconductor materials, heterogeneous catalysis, and the health sciences, to name a few. All these exciting developments and many more are touched in this virtual special issue (VSI) on nanophotonics. From ultra-precise chemical imaging measurements performed in a scanning tunneling microscope chamber to single molecule spectroscopic measurements performed at solid-air and solid-liquid interfaces, this VSI includes contributions from active practitioners that are all striving to better-understand increasingly complex interfaces encountered in the biological, materials, and chemical sciences.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗