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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Metabolic engineering of Synechococcus elongatus 7942 for enhanced sucrose biosynthesis

The capability of cyanobacteria to produce sucrose from CO 2 and light has a remarkable societal and biotechnological impact since sucrose can serve as a carbon and energy source for a variety of heterotrophic organisms and can be converted into value-added products. However, most metabolic engineering efforts have focused on understanding local pathway alterations that drive sucrose biosynthesis and secretion in cyanobacteria rather than analyzing the global flux re-routing that occurs following induction of sucrose production by salt stress. Here, we investigated global metabolic flux alterations in a sucrose-secreting (cscB-overexpressing) strain relative to its wild-type Synechococcus elongatus 7942 parental strain. Here we used targeted metabolomics, 13 C metabolic flux analysis (MFA), and genome-scale modeling (GSM) as complementary approaches to elucidate differences in cellular resource allocation by quantifying metabolic profiles of three cyanobacterial cultures - wild-type S. elongatus 7942 without salt stress (WT), wild-type with salt stress (WT/NaCl), and the cscB-overexpressing strain with salt stress (cscB/NaCl) - all under photoautotrophic conditions. We quantified the substantial rewiring of metabolic fluxes in WT/NaCl and cscB/NaCl cultures relative to WT and identified a metabolic bottleneck limiting carbon fixation and sucrose biosynthesis. This bottleneck was subsequently mitigated through heterologous overexpression of glyceraldehyde-3-phosphate dehydrogenase in an engineered sucrose-secreting strain. Our study also demonstrates that combining 13 C-MFA and GSM is a useful strategy to both extend the coverage of MFA beyond central metabolism and to improve the accuracy of flux predictions provided by GSM.

09 BIOMASS FUELS↗
NASA NTRS1984

Characteristics of the Fe II and C II emission in high-resolution IUE spectra (2300-3000 A) of Alpha Orionis

A study is presented of Fe II and C II emission features in the 2300-3000 A region of four high-resolution IUE spectra of Alpha Ori obtained during the period 1978 April-1982 November. A set of 42 unmutilated, unblended Fe II lines of multiplets UV 1-3, 32-33, 35-36, and 60-64 and the C II (UV 0.01) intercombination lines have been identified and measured to determine their velocities, fluxes, and asymmetries. A correlation of Fe II line asymmetry with intrinsic line strength indicates a velocity field which is initially constant, then algebraically increases with radius to a maximum value and then decreases significantly before reaching an asymptotic flow speed far from the star. The mean velocity of the chromospheric regions emitting Fe II does not appear to differ substantially from the time-average of the photospheric velocity, but there is evidence that the two regions are not strongly coupled and thus that the chromosphere does not strictly follow the semiperiodic 6 year pulsations of the photosphere. An analysis of the C II line fluxes produces estimates of the electron density in the chromosphere in the range 3.2 x 10 to the 7th-1.3 x 10 to the 8th per sq cm and indicates that the region emitting C II is geometrically thick, extending at least one-tenth, and perhaps as far as 1.2, photospheric radii from the base of the chromosphere.

Carpenter, K. G.↗
DOE OSTI2020

Multiscale and Multimodal Characterization of 2D Titanium Carbonitride MXene

Here, a comprehensive study on the prototype solid solution phase carbonitride MXene Ti 3 CN is conducted using nuclear magnetic resonance, electron spin resonance, total and quasi-elastic neutron scattering, combined with density functional theory-based electronic structure and molecular dynamic calculations. The combination of experiment and theory lead toward rational atomic structural models of Ti 3 CN. The remnant Al ions from the etching process significantly tune the interlayer spacing, distinct from the more typical MXene, Ti 3 C 2 , prepared similarly. Neutron scattering indicates the surface terminations of Ti 3 CN display high oxygen and fluorine concentrations and rather low hydroxyl and hydrogen concentrations. Calculations show that the structure including both the residual Al ions and mixed surface terminations give the best agreement with the measurements. The water molecules in Ti 3 CN are highly immobile, in strong contrast to those in Ti 3 C 2 . The analysis of the electronic structure suggests that the nitride MXene displays higher conductivity than the carbides. Finally, the absence of hydroxyl groups in terminations, the solid-solution in the anion sites, the remnants within layers, and immobile water altogether make the carbonitrides a unique series in the MXene family, implying a further exploration of their exotic properties and applications in energy storage.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Ring-opening of a thorium cyclopropenyl complex generates a transient thorium-bound carbene

The reaction of [Cp 3 ThCl] with in situ generated 1-lithium-3,3-diphenylcyclopropene results in the formation of [Cp 3 Th(3,3-diphenylcyclopropenyl)] (1), in good yields. Thermolysis of 1 results in isomerization to the ring-opened product, [Cp 3 Th(3-phenyl-1H-inden-1-yl)] (3) via a hypothesized carbene intermediate. This transformation represents a new mode of reactivity of 3,3-diphenylcyclopropene with the actinides, improving our ability to use this reagent as a carbene source. Here, a combined DFT and 13 C{ 1 H} NMR analysis of 1 shows a spin–orbit induced downfield shift at C α due to participation of the 5f orbitals in the Th–C bond.

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

A 13‐Year Record Indicates Differences in the Duration and Depth of Soil Carbon Accrual Among Potential Bioenergy Crops

Six years after replacing a maize/soybean cropping system, perennial grasses miscanthus (Miscanthus × giganteus) and switchgrass (Panicum virgatum), and a 28-species restored prairie increased particulate organic carbon in surface soils without increasing soil organic carbon (SOC). To resolve potential changes in the quantity and distribution of SOC, soils were resampled after seven to thirteen years to measure bulk density, carbon (C) content, and stable C isotopes to a depth of 1 m. SOC stocks increased between 1.75 and 2.5 Mg ha −1 year −1 in all perennial crops between 2008 and 2016 (nine growing seasons). Despite relatively low litter inputs and belowground biomass, the highest rate of SOC accrual was in restored prairie (2.5 Mg ha −1 year −1 ), followed by miscanthus (2.0 Mg ha −1 year −1 ) and switchgrass (1.75 Mg ha −1 year −1 ). The change in SOC in maize/soybean was not significant. After 2016, total SOC decreased in maize/soybean and miscanthus, resulting in slower overall rates of SOC accumulation over the full sampling period for miscanthus (0.8 Mg ha −1 year −1 ). The rate of SOC accumulation was greatest below 50 cm depth for restored prairie and switchgrass but in the top 10 cm for miscanthus. Stable isotope analysis showed 13 C enrichment in all depths of switchgrass soils, an indication of new organic C accumulation, but mixed results in all other crops. Planting perennial crops on land formerly in an annual maize/soybean cropping system can slow or reverse soil carbon losses, with the greatest increases in SOC from species-rich prairie.

agriculture↗
DOE OSTI2025

Low Temperature CO 2 Hydrogenation on Unsupported Mo 2 C Catalysts

CO 2 hydrogenation to methanol, a key reaction for decarbonizing the fuel and chemical industries, requires catalyst formulations that hydrogenate CO 2 selectively to methanol at temperatures where methanol conversion is not significantly equilibrium limited (<423 K). Herein we report continuous CO 2 hydrogenation at low temperatures (348-408 K, H 2 /CO 2 = 0.1-50, 5-35 bar) with high selectivity to methanol (up to ca. 80%) over unsupported β-Mo 2 C catalysts. Active site density quantification via titration with trifluoroacetic acid at reaction temperatures enables an assessment of site-specific rates. Methanation and reverse water gas shift (RWGS) occur concurrently with methanol synthesis during CO 2 hydrogenation over Mo 2 C. Reaction pathway analysis, product cofeeds, and reversibility formalisms show that all products form through primary reaction pathways from CO 2 , but secondary reactions of CO contribute significantly to rates of methanation. Dependences of forward rates on reactant and product concentration determined by independently varying the CO 2 , H 2 , CO, H 2 O, CH 3 OH, and CH 4 pressure in conjunction with reversibility formalisms reveal that all products form through H-assisted CO 2 activation and involve partially hydrogenated CO 2 -derived intermediates. Here, these inferences were verified by quantitative agreement between measured site-time yields and site-time yields predicted by closed form kinetic rate expressions in an integral reactor model over widely varying conditions (85-2000 kPa H 2 , 80-1500 kPa CO 2 , 0-45 kPa H 2 O, 0-21 kPa CO, 0-25 kPa CH 3 OH, 0-75 kPa CH 4 , 5-87 mol Mo s s mol CO 2 -1 ). Coverages calculated based on the kinetic model reveal that the Mo 2 C surface is covered with bidentate CO- and CO 2 -derived intermediates of the stoichiometry H 2 CO 2 and H 2 CO, indicating that H 2 and CO x do not compete for surface occupancy but instead adsorb cooperatively to form partially hydrogenated intermediates. Hydrogenation of the CO-derived H 2 CO** intermediate favors methanation, while hydrogenation of CO 2 -derived H 2 CO 2 ** favors methanol synthesis. Together, these findings demonstrate the ability of unsupported Mo 2 C to catalyze the hydrogenation of CO 2 to methanol at low temperatures and provide insight into the reaction network and mechanisms involved in its formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

Analysis of Delamination Growth from Matrix Cracks in Laminates Subjected to Bending Loads

A major source of delamination damage in laminated composite materials is from low-velocity impact. In thin composite laminates under point loads, matrix cracks develop first in the plies, and delaminations then grow from these cracks at the ply interfaces. The purpose of this study was to quantify the combined effects of bending and transverse shear loads on delamination initiation from matrix cracks. Graphite-epoxy laminates with 90 deg. plies on the outside were used to provide a two-dimensional simulation of the damage due to low-velocity impact. Three plate bending problems were considered: a 4-point bending, 3-point bending, and an end-clamped center-loaded plate. Under bending, a matrix crack will form on the tension side of the laminate, through the outer 90 deg. plies and parallel to the fibers. Delaminations will then grow in the interface between the cracked 90 deg. ply and the next adjacent ply. Laminate plate theory was used to derive simple equations relating the total strain energy release rate, G, associated with the delamination growth from a 90 deg. ply crack to the applied bending load and laminate stiffness properties. Three different lay-ups were tested and results compared. Test results verified that the delamination always formed at the interface between the cracked 90 deg. ply and the next adjacent ply. Calculated values for total G sub c from the analysis showed good agreement for all configurations. The analysis was able to predict the delamination onset load for the cases considered. The result indicated that the opening mode component (Mode I) for delamination growth from a matrix crack may be much larger than the component due to interlaminar shear (Mode II).

Murri, G. B.↗
NASA NTRS1988

Analysis of delamination growth from matrix cracks in laminates subjected to bending loads

A major source of delamination damage in laminated composite materials is from low-velocity impact. In thin composite laminates under point loads, matrix cracks develop first in the plies, and delaminations then grow from these cracks at the ply interfaces. The purpose of this study was to quantify the combined effects of bending and transverse shear loads on delamination initiation from matrix cracks. Graphite-epoxy laminates with 90 deg plies on the outside were used to provide a two-dimensional simulation of the damage due to low-velocity impact. Three plate bending problems were considered: a 4-point bending, 3-point bending, and an end-clamped center-loaded plate. Under bending, a matrix crack will form on the tension side of the laminate, through the outer 90 deg plies and parallel to the fibers. Delaminations will then grow in the interface between the cracked 90 deg ply and the next adjacent ply. Laminate plate theory was used to derive simple equations relating the total strain energy release rate, G, associated with the delamination growth from a 90 deg ply crack to the applied bending load and laminate stiffness properties. Three different lay-ups were tested and results compared. Test results verified that the delamination always formed at the interface between the cracked 90 deg ply and the next adjacent ply. Calculated values for total G sub c from the analysis showed good agreement for all configurations. The analysis was able to predict the delamination onset load for the cases considered. The result indicated that the opening mode component (Mode I) for delamination growth from a matrix crack may be much larger than the component due to interlaminar shear (Mode II).

Murri, Gretchen Bostaph↗
NASA NTRS1996

CLMNANAL: A C++ program for application of the Coleman stability analysis to rotorcraft

This program is an adaptation of the theory of Robert P. Coleman and Arnold M. Feingold as presented in NACA Report 1351, 1958. This theory provided a method for the analysis of multiple-bladed rotor systems to determine the system susceptibility to ground resonance. Their treatment also provided a simple means for determining the required product of rotor and chassis damping factors to suppress the resonance. This C++ program is based on a FORTRAN 77 version of a similar code.

Lance, Michael B.↗
NASA NTRS1991

Analysis of rolling contact spall life in 440 C steel bearing rims

The results of a two year study of the mechanisms of spall failure in the HPOTP bearings are described. The objective was to build a foundation for detailed analyses of the contact life in terms of: cyclic plasticity, contact mechanics, spall nucleation, and spall growth. Since the laboratory rolling contact testing is carried out in the 3 ball/rod contact fatigue testing machine, the analysis of the contacts and contact lives produced in this machine received attention. The results from the experimentally observed growth lives are compared with calculated predictions derived from the fracture mechanics calculations.

Bastias, P. C.↗
NASA NTRS1976

Crystal growth from the vapour phase (ASTP experiment MA-085)

The positive effects of microgravity on crystal quality and fundamental properties of the vapor transport reaction were established by analyzing the results of three transport experiments on multi-component systems performed during the Apollo Soyuz Test Project (ASTP) mission. The systems employed were GeSe(0.99)Te(0.01) - GeI4 (A), GeS(0.98)Se(0.02) - GeCl4 (B), and GeS - GeCl4-Ar (C). The crystallographic analysis is based on a direct comparison of space and ground-based (prototype) crystals, employing X-ray diffraction, microprobe, microscopic, and chemical etching techniques. The results demonstrate a considerable improvement of the space-grown crystals in terms of chemical and crystalline homogeneity, surface morphology, and bulk perfection relative to ground specimens. The confirmation of greater mass transport rates than predicted for micro-gravity by present vapor transport models is of basic scientific and practical importance for the improvement of transport models and techniques on earth and for the development of a transport model for space conditions. The internal consistency and agreement between ASTP and Skylab results obtained for different compounds, transport agents, and temperature gradients strongly support the validity of these observations. The combined findings of improved crystal quality and high mass transport rates are of technological significance for space-processing applications.

Wiedemeier, H.↗
NASA NTRS1995

The Development and Use of a Flight Optimization System Model of a C-130E Transport Aircraft

The Systems Analysis Branch at NASA Langley Research Center conducts a variety of aircraft design and analyses studies. These studies include the prediction of characteristics of a particular conceptual design, analyses of designs that already exist, and assessments of the impact of technology on current and future aircraft. The FLight OPtimization System (FLOPS) is a tool used for aircraft systems analysis and design. A baseline input model of a Lockheed C-130E was generated for the Flight Optimization System. This FLOPS model can be used to conduct design-trade studies and technology impact assessments. The input model was generated using standard input data such as basic geometries and mission specifications. All of the other data needed to determine the airplane performance is computed internally by FLOPS. The model was then calibrated to reproduce the actual airplane performance from flight test data. This allows a systems analyzer to change a specific item of geometry or mission definition in the FLOPS input file and evaluate the resulting change in performance from the output file. The baseline model of the C-130E was used to analyze the effects of implementing upper wing surface blowing on the airplane. This involved removing the turboprop engines that were on the C-130E and replacing them with turbofan engines. An investigation of the improvements in airplane performance with the new engines could be conducted within the Flight Optimization System. Although a thorough analysis was not completed, the impact of this change on basic mission performance was investigated.

Desch, Jeremy D.↗
DOE OSTI2020

LA17-V-InverseRadTransportProblem-PD2Kb. Final Project Report

In the inverse radiation transport problem, a radiation signal emanating from an unknown object is used to reconstruct geometric and material parameters of the object , e.g., the mass of special nuclear material (SNM), the isotopic composition of the SNM (e.g., the enrichment of 235U), the thickness of shielding, etc. The inverse radiation transport problem is one of the most fundamental and important in the emergency response mission, and has been addressed in previous NA-22 and NA-42/84 investments by using derivative-free optimization methods. Our project was aimed at (i) consolidating previous work by applying polynomial chaos expansion (PCE) for reducing significantly the number of forward model simulations required by derivative-free optimization methods; (ii) developing a general-purpose framework and stand-alone software for solving the inverse radiation transport problem by applying a new “predictive modeling” methodology (predictive modeling of coupled multi-physics systems, PM_CMPS) which enables the fusing of experimental and computational information; and (iii) developing several benchmarks (for unscattered gamma rays) for demonstrating the quantification of non-Gaussian features (e.g., skewness and kurtosis, which characterize asymmetries and long tails) of response distributions by deterministically and efficiently propagating parameter uncertainties (covariances and higher-order moments, where available) using high-order sensitivities computed by the recently developed comprehensive adjoint sensitivity analysis methodology (C-ASAM). With regard to (i), application of PCE, the most significant accomplishment of this project was an implementation of PCE into INVERSE that significantly reduced computation time for the DiffeRential Evolution Adaptive Metropolis (DREAM) and Differential Evolution (DE) methods. For inverse transport problems with measurements of neutron leakage, neutron multiplication, and neutron-induced gamma-rays, the solution times for the DREAM and DE methods were reduced by factors of 30-300, reducing run times from hours to minutes while maintaining the same accuracy as the standard (non-PCE) DREAM and DE. Speedups were further improved by exploring sparse grid quadrature sets using the Toolkit for Adaptive Stochastic Modeling and Non-Intrusive ApproximatioN (Tasmanian) toolset. An initial exploration of sparse grids indicated that further speedups factors of 5-10 are obtainable. The implementation of PCE in INVERSE is not in a form that users can easily access. With regard to (ii), solving the inverse problem using a predictive modeling paradigm, the most significant accomplishment of this project were the derivation and implementation of adjoint-based second derivatives in neutron and photon transport theory. There are two codes that compute these derivatives. SENSPG computes them for uncollided gamma rays and SENSMG computes them for neutron leakage. SENSMG is open-source code available on github. Other significant accomplishments included a stand-alone code, MULTI-PRED, that implements the predictive modeling paradigm, along with a detailed manual. The code was implemented in the existing INVERSE code for inverse problems, but a head-to-head comparison of inverse methods was not achieved. We also derived and implemented the capability to compute sensitivities for multiplicity measurements into the SENSMG code, and this capability was used in a data assimilation application, but it was not used for solving inverse problems. With regard to (iii), developing benchmarks to demonstrate the importance of high-order sensitivity and uncertainty analysis, the most significant accomplishment of this project were two test problems that showed how important second-order sensitivities are.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2022

Demonstration and Evaluation of the Human-Technology Integration Function Allocation Methodology

There is an imminent need for the existing nuclear power plants to reduce their operating and maintenance (O&M) costs to remain economically viable. Digital technology, including automation, provides a significant opportunity for the existing nuclear power plant fleet to transform the way in which work is accomplished, reducing O&M costs, and allowing the fleet to remain economically competitive. One notable opportunity to significantly reduce O&M costs pertains to modifications to the plant equipment and main control room (MCR). Existing instrumentation and control (I&C) technologies in the MCR are highly analog, costly to operate and maintain, and demand a high cognitive and physical workload from plant staff (i.e., operators). Digitalizing the MCR has a range of broad economic benefits, including improved plant performance and reduced manual work. Further, digital I&C systems can fundamentally change the way in which plant staff operate the plant; this is the concept of operation. Human-technology integration is important to ensure that impacts to the concept of operation are done in a way that account for capabilities of people and technology. Human-technology integration employs human factors engineering (HFE) methods and principles to maximize the benefits of digital technology, reducing human error, improving overall decision-making and usability. The U.S. Department of Energy Light Water Reactor Sustainability Program is applying human-technology integration research to ensure digital technologies are safe, reliable, and efficient. This paper documents the demonstration of the human-technology guidance developed by the Light Water Reactor Sustainability Program from a first-of-a-kind digital I&C upgrade, specifically addressing function analysis and allocation for a new digital I&C system that included changes in automation levels. The program’s specific approach is included in this work, following lessons learned. This document serves as a resource for industry to follow in applying human-technology integration and HFE to digital modifications, specific to function analysis and allocation. The lessons learned should be considered in the planning and execution of HFE activities that support such digital modifications.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2023

Tensile behavior of diffusion bonded AA6061 - AA6061 with variation in cooling method

Hot isostatically pressed AA6061 cladding is an important structural component of the high performance, Zr-laminated U-10Mo monolithic fuel system for the application in research and test reactors. In this study, the mechanical behavior of two diffusion bonded aluminum alloy, AA6061, was examined using tensile testing. Solid-to-solid diffusion bonding between two pieces of AA6061 was performed by isothermal annealing at 560 °C for 1.5 h, and diffusion couples were subsequently cooled via three different cooling methods: furnace cooling, air cooling, and water quenching. Dog-bone shaped tensile specimens, with 10 mm in gauge length (with diffusion bonded interface in the middle), and 1.5 × 1.5 mm 2 gauge cross-sections, were fabricated from the diffusion bonded AA6061 by electro-discharge machining. Yield strength (% EL at failure) of furnace cooled, air cooled and water quenched tensile specimens determined was 82 ~ 89 MPa (10 ~ 30%), 112 ~ 116 MPa (10 ~ 14%), and 149 ~ 164 MPa (10 ~ 17%), respectively. This variation in mechanical behavior was examined with cooling-rate dependent, concentrated precipitation of Mg 2 Si at the diffusion bonded interface, with due respect for mechanical properties of the AA6061 alloy that inherently vary as a function of cooling rate from 560 °C. Finite element analysis using ABAQUS was employed to augment experimental findings with the appropriate microstructural constituents and alloy properties. Results suggest that the strength is dominated by matrix/bulk properties of AA6061, while ductility is strongly influenced by the cooling method dependent presence of Mg 2 Si precipitates at the interface.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2023

Comparative study of two Saccharomyces cerevisiae strains with kinetic models at genome-scale

The parameterization of kinetic models requires measurement of fluxes and/or metabolite levels for a base strain and a few genetic perturbations thereof. Unlike stoichiometric models that are mostly invariant to the specific strain, it remains unclear whether kinetic models constructed for different strains of the same species have similar or significantly different kinetic parameters. This important question underpins the applicability range and prediction limits of kinetic reconstructions. To this end, herein we parameterize two separate large-scale kinetic models using K-FIT with genome-wide coverage corresponding to two distinct strains of Saccharomyces cerevisiae: CEN.PK 113-7D strain (model k-sacce306-CENPK), and growth-deficient BY4741 (isogenic to S288c; model k-sacce306-BY4741). The metabolic network for each model contains 306 reactions, 230 metabolites, and 119 substrate-level regulatory interactions. The two models (for CEN.PK and BY4741) recapitulate, within one standard deviation, 77% and 75% of the fitted dataset fluxes, respectively, determined by 13 C metabolic flux analysis for wild-type and eight single-gene knockout mutants of each strain. Strain-specific kinetic parameterization results indicate that key enzymes in the TCA cycle, glycolysis, and arginine and proline metabolism drive the metabolic differences between these two strains of S. cerevisiae. Our results suggest that although kinetic models cannot be readily used across strains as stoichiometric models, they can capture species-specific information through the kinetic parameterization process.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Voltage and Temperature Limits of Advanced Electrolytes for Lithium-Metal Batteries

Several advanced electrolytes (mainly ether-based) have recently demonstrated excellent electrochemical performance in high energy density lithium (Li)-metal batteries. However, the safety of these ether-based electrolytes is still unknown. This work evaluates the thermal stability of these new formulations to understand their safety limits of operation in comparison to carbonate electrolytes typically used in Li-ion batteries. Electrolyte stability is assessed in conjunction with LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode and Li-metal anode at ultra-high voltages (≤ 4.8 V) and temperatures (≤ 300°C) to trigger thermal runaway, where onset and extent of heat release are monitored via isothermal microcalorimetry and differential scanning calorimetry Most ether-based electrolytes show improved thermal resilience over commercial carbonate formulations when heated up to 300°C. The thermal behavior in presence of charged cathode and Li-metal suggests that the new electrolytes may be better at stabilizing active material surfaces than carbonate electrolytes. Although extreme voltages severely destabilize the ether-based formulations, prompting thermal runaway, a phosphate based localized high concentration electrolyte exhibits superior stability over commercial carbonate electrolytes at all tested temperatures (32°C, 45°C, and 60°C). Although thermal analysis during the first charge process (as adopted in this preliminary study) may be insufficient to conclude the long-term advantages of these electrolytes, a more stable electrolyte identified under extreme voltage and temperature conditions will provide valuable guidance for the safety of future electrolyte designs.

25 ENERGY STORAGE↗
DOE OSTI2025

Multifunctional Polar 2D Lead Iodide Perovskites Exhibiting Persistent Spin Texture

Ferroelectric Rashba semiconductors are a rare class of multifunctional materials promising for spin–orbitronics due to the possibility of electrically switchable spin textures. Hybrid organic–inorganic metal halide perovskites offer exceptional tunability that can be harnessed to target noncentrosymmetry; however, the complex interactions between organic and inorganic components are not rationally understood. Here, we use an asymmetric spacer cation with a strong molecular dipole moment (2-fluorobenzylammonium, 2FBZ) and increase the intrinsic quantum well thickness to n > 1 to synthesize three new polar 2D lead iodide perovskites (2FBZ) 2 (A) n-1 Pb n I 3n+1 with A = methylammonium (MA) or formamidinium (FA) and n = 2, 3. Single-crystal structure analysis reveals the C 2v symmetry of these crystal structures and substantial structural distortions, which enable Rashba and Dresselhaus band splitting and persistent spin texture, confirmed by DFT calculations. Measurements of the resulting symmetry-dependent properties, such as second harmonic generation, switchable photovoltaic effect, ferroelectric polarization, and low temperature photoluminescence show switchable ferroelectric semiconducting properties. Furthermore, these results introduce a general chemical design strategy toward polar symmetry by exploiting the complex interplay between asymmetric spacer cations and A-site cations in quasi-2D (n > 1) halide perovskites to realize new classes of multifunctional materials for future spin–orbitronic applications.

Cations↗