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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Light-Promoted C(sp 3 )–C(sp 3 ) Reductive Elimination from Dialkyl NiII Complexes

Ni-catalyzed cross-coupling is a powerful strategy to forge C(sp 3 )–C(sp 3 ) bonds. Typically, to do so requires overcoming a challenging C–C bond-forming reductive elimination, often enabled by the intermediacy of highly oxidized Ni species or outer-sphere processes. While direct C(sp 3 )–C(sp 3 ) reductive elimination from the Ni II base oxidation state is normally thermally inaccessible, light-activation provides an avenue to affect such transformations. Here, we investigate the mechanism of light-induced C(sp 3 )–C(sp 3 ) bond formation from dialkyl bipyridine Ni II complexes through a variety of organometallic, spectroscopic, and computational studies. Wavelength-dependent quantum yields, ligand electronics–reactivity relationships, excited-state lifetimes, computed barriers, and product distributions from crossover studies support a photolysis/radical rebound mechanism. Furthermore, this reactivity paradigm complements existing strategies in the literature to promote reductive elimination from Ni II , such as the use of destabilizing, sterically hindered ligands and reduction of electron density at Ni through the binding of electron-deficient olefins. Hence, we envision that light-induced reductive elimination may enable the development of challenging C(sp 3 )–C(sp 3 ) couplings.

Alkyls↗
DOE OSTI2025

Potential Cost Reduction in New Nuclear Deployments Based on Recent AP1000 Experience

The completion of Vogtle Units 3 and 4, despite significant cost and schedule overruns, a major bankruptcy, and a pandemic, demonstrates that the U.S. nuclear industry can still develop new supply chains, train a highly skilled workforce, and build large nuclear power plants. Vogtle, being a first-of-a-kind (FOAK) plant, faced overruns, but FOAK overruns can decrease with more deployments through a combination of design standardization and modularization, transferring and implementing lessons learned between consecutive projects, and innovation. This report quantifies the potential cost and schedule reductions in future AP1000 plants in the US and identifies the barriers in achieving those reductions. It starts with a summary and analysis of the cost and construction timeline data for AP1000 plants that started construction in the United States (Vogtle) and China. Motivated by the steep schedule reductions from the first to second series of AP1000 plants in China, a cost reduction model was developed to quantify potential reductions for future AP1000 builds in the US. Results show that within about 3 more builds, AP1000s can become economically attractive in large markets in the U.S., without leveraging the Investment Tax Credit (ITC) or Production Tax Credit (PTC), and much sooner if these tax credits are available. Importantly the financial risks for future AP1000 builds in the US might be much smaller than observed in the FOAK plants. The study also identifies various barriers for future builds including the availability of a supply chain and a skilled workforce, and emphasizes the importance of making investments to gather and implement lessons learned between consecutive projects.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

Solid State Reduction Driven Synthesis of Mn Containing Multi-principal Component Alloys

In recent years, high entropy alloys (HEAs), also known as multi-principal component alloys (MPCAs) have emerged as a new and exciting class of materials. This paper reports on the solid state reduction synthesis of a series of CoFeNiMn-based MPCA compositions, starting from a mixture of the corresponding oxides. One of the aims of the study was to test whether the degree of reduction of MnO, a highly stable oxide, could be enhanced by tailoring the alloy composition. Specifically, the influence of Ni content was studied because Ni exhibits a significant negative enthalpy of mixing with Mn. High purity precursor powders of Co(OH) 2 , Fe 2 O 3 , MnO 2 , and NiO were milled and mixed using standard ceramic processing methods. Here, the nominal sample compositions (assuming complete oxide reduction) were (CoFeMn) x Ni (1-x) , for x = 0, 0.083, 0.166, and 0.25. The oxide samples were subjected to a series of isothermal reduction anneals in flowing 3 pct H 2 –Ar at 1100 °C. The resulting microstructures were characterized using scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD). The composition of the resulting MPCAs was determined quantitatively using wavelength dispersive spectroscopy (WDS) in the electron microprobe. The study revealed that for each of the initial oxide compositions studied, it was possible to achieve an MPCA with ~ 25 at. pct Mn. These results were found to be consistent with the predictions of a thermodynamic model whereby a negative enthalpy of mixing (ΔH mix ), combined with a contribution from configurational entropy, can offset a positive free energy of reduction (ΔG red ). The incorporation of vibrational entropy into first principles calculations was found to have a significant effect on the predicted crystal structure of the MPCAs.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Scaled melter testing of alternative reductants for Low-Activity Waste vitrification: Melter feed properties and processing behavior

This study examines the use of boron nitride (BN) and coke dust as alternative reductants for low-activity waste vitrification in scaled melter systems, intended to enhance operational flexibility at the Hanford Waste Treatment and Immobilization Plant. The baseline reductant, sucrose, while widely considered advantageous for glass production rates, produces challenging off gas emissions during processing. Early crucible-scale testing indicated that BN and coke effectively control foaming and glass redox, while significantly reducing acetonitrile emissions. Both real tank waste and simulant waste melter feeds were tested with BN and coke in this study. Rheological properties for melter feeds with both reductants were within operational limits, although the particle size of coke should be controlled and sufficient agitation is necessary to ensure smooth operations. While promising for handling and reduction of emissions, both simulant melter feeds demonstrated lower average glass production rates in the simulant melter system compared with sucrose. In the radioactive system, the rates were more comparable to previously measured low activity waste feeds on the order of 1285 kg m 2 day −1 for BN and 1671 kg m −2 day −1 for coke. Further scale-up testing is required to interpret the processing rates in the context of the full scale melter systems and evaluate the cost-benefit impact of these reductants on efficiency and sustainability.

Rigby, Jessica C. [Pacific Northwest National Labo↗
DOE OSTI2024

Sustained bacterial N 2 O reduction at acidic pH

Nitrous oxide (N 2 O) is a climate-active gas with emissions predicted to increase due to agricultural intensification. Microbial reduction of N 2 O to dinitrogen (N 2 ) is the major consumption process but microbial N 2 O reduction under acidic conditions is considered negligible, albeit strongly acidic soils harbor nosZ genes encoding N 2 O reductase. Here, we study a co-culture derived from acidic tropical forest soil that reduces N 2 O at pH 4.5. The co-culture exhibits bimodal growth with a Serratia sp. fermenting pyruvate followed by hydrogenotrophic N 2 O reduction by a Desulfosporosinus sp. Integrated omics and physiological characterization revealed interspecies nutritional interactions, with the pyruvate fermenting Serratia sp. supplying amino acids as essential growth factors to the N 2 O-reducing Desulfosporosinus sp. Thus, we demonstrate growth-linked N 2 O reduction between pH 4.5 and 6, highlighting microbial N 2 O reduction potential in acidic soils.

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

Four-electron oxidation and one-electron reduction of the bis(terphenylthiolate) U( II ) complex, U(SAr iPr6 ) 2 [Ar iPr6 = C 6 H 3 -2,6-(C 6 H 2 -2,4,6- i Pr 3 ) 2 ]

Here, the utility of the sterically bulky terphenylthiolate ligand, (SAr iPr6 ) 1− in expanding uranium reductive chemistry has been explored. Reduction of U(SAr iPr6 ) 2 I forms the U(II) complex, U(SAr iPr6 ) 2 , in which the metal is protected by the flanking arene rings of the ligand, but they move out of the way to accommodate the four electron reduction of PhN=NPh to form the U(VI) bis(imido) product U(SAr iPr6 ) 2 (=NPh) 2 (THF) 2 . Here, the KC 8 reduction of U(SAr iPr6 ) 2 generates a more reduced complex, KU(μ-SAr iPr6 ) 2 , initially identified by a −2.55 V vs. Fc + /Fc electrochemical reduction event in THF.

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

The Effects of Compounded Model Size Reductions on Adversarial Robustness

Recent advances in Edge AI and Tiny Machine Learning (TinyML) have enabled the deployment of machine learning models on resource-constrained environments. However, deploying these models on edge devices, such as micro-controllers, requires significant model footprint reduction through a variety of techniques such as quantization, pruning, and clustering. While these optimization methods offer considerable advantages, they potentially introduce AI-related security vulnerabilities, particularly concerning model robustness with respect to adversarial AI attacks. Prior research has extensively examined the impact of quantization on adversarial robustness; however, the effects of alternative reduction techniques and their combinations remain understudied. This paper investigates the impact of model size reduction techniques on adversarial robustness, when applied individually and combined. We utilized Fast Gradient Sign Method (FGSM) and Projected Gradient Descent (PGD) attacks to generate adversarial perturbations for both training and testing data, and then evaluated the models' accuracy under adversarial training conditions. Our findings revealed that reduction techniques generally diminished robustness; although, combining techniques was not found to make robustness any worse than when applied individually. Moreover, specific techniques can potentially enhance resistance to small size perturbations. This research provides insights into the trade-offs between model size reduction and security, establishing a foundation for future investigations into improving adversarial training techniques and methodologies for maintaining robustness while preserving memory footprint benefits.

Austria, Phillipe [ORNL] (ORCID:0000000236223973)↗
DOE OSTI2025

Kinetic Model of Photochemical Nitrogen Reduction [SWR-25-97]

The code in this repository was used to model the kinetics of photochemical nitrogen reduction. Each directory represents a manuscript. The directory titled Dahl_CRPS_2025 contains the code used to fit the kinetic models presented in the manuscript titled, "Pre-steady-state kinetics of nanocrystal:molybdenum nitrogenase biohybrids reveals hole-scavenging efficiency is critical to achieving N2 reduction" by Peter J. Dahl, Lauren M. Pellows, Zhi-Yong Yang, Lance C. Seefeldt, John W. Peters, Gordana Dukovic, David W. Mulder, and Paul W. King. Molybdenum (Mo) nitrogenase is a two-component enzyme complex that catalyzes the reduction of dinitrogen to ammonia and protons to hydrogen gas. We have shown that electrons for dinitrogen reduction can be delivered photochemically to the catalytic MoFe protein component by CdS nanocrystals. In this study, we used electron paramagnetic resonance spectroscopy to measure the transient populations of catalytic intermediates. We fit the populations with a pre-steady-state kinetic model which allowed us to distinguish between productive and non-productive reaction pathways and extract the rate constants for the reaction. Our results demonstrated that the rate of catalytic electron delivery into MoFe protein increased with the concentration of sacrificial electron donor. This enabled electron delivery to exceed the rate of hydride protonation, a relaxation pathway which competes with N2 binding. Thus, managing the balance between electron transfer and hole transfer reactions is required to achieve a kinetic regime that favors N2 reduction.

Dahl, Peter [National Renewable Energy Laboratory ↗
DOE OSTI2025

Compact Absorber Technology Leads to Significant Reduction in the Cost of Point Source CO 2 Capture

The size of columns in traditional absorption-based processes for CO 2 capture contributes significantly to the overall capital cost. A demonstrated method to reduce the cost of point source CO 2 capture, focusing on reducing the absorber height by increasing the liquid-to-gas reaction contact area and decreasing the CO 2 diffusion resistance without increasing gas-side pressure drop is presented along with techno-economic analysis results. Bench-scale tests on the unique Compact Absorber showed overall CO 2 mass transfer enhancement of varying degrees compared to a traditional packed column for similar process conditions, demonstrating that a 60+% reduction in size of a typical post-combustion absorber with a packing height of 70-100 ft and total height of 150-180 ft can be achieved. The techno-economic analysis showed significant cost reductions when the Compact Absorber is combined with other transformative aspects of the University of Kentucky Institute for Decarbonization and Energy Advancement point source CO 2 capture process compared to the U.S. Department of Energy National Energy Technology Laboratory pertinent reference case for pulverized coal plants with CO 2 capture. Here, a levelized cost of electricity excluding CO 2 transportation and storage of $\$95.6$/MWh was estimated, which is a 9% reduction, with a total capital cost contribution of $45/MWh, which is a 12% reduction. Additionally, a breakeven CO 2 sales price also referred to as the cost of CO 2 capture, of $36.70/tonne was estimated when the UK hindered primary amine solvent is used, which is a 20% reduction compared to the reference case.

CO2 capture↗
DOE OSTI2024

Evaluation of the Turbine Integrated Mortality Reduction (TIMR SM ) Technology as a Smart Curtailment Approach (Final Summary Report)

Wind energy is a crucial technology for achieving net-zero emissions by 2050. However, the growth and deployment of wind energy in North America have led to the deaths of many bat species due to operating wind turbines. Hundreds of thousands of bats are estimated to die at wind turbines annually in North America. Operational minimization, which includes feathering turbine blades and curtailment, has been documented to reduce bat fatality effectively. Curtailment refers to altering turbine operation based on wind speed, time of year, temperature, sensors, and activity models. However, when turbines are curtailed, they do not generate power, resulting in energy loss and revenue for wind energy facilities. The Electric Power Research Institute (EPRI) funded the development of Turbine Integrated Mortality Reduction (TIM SM ) Technology, which curtails turbine operation when bats are detected. The initial TIMR system research showed promising results, with an 85% reduction in overall bat fatalities and a 91% reduction for the little brown bat. However, these results were based on a single site during one fall season, and it was unclear if similar results could be replicated at other wind energy facilities. This research aimed to validate the TIMR system results from the prior field study at a second site in the U.S., estimate the power production and reduction in bat mortality at turbines with installed TIMR systems relative to blanket curtailment and fully operational turbines, test the TIMR system in two calendar years and during the summer and fall periods, and evaluate the operational and commercial characteristics of the TIMR system for potential wind industry adoption. The study was conducted at a 500.9-MW wind energy facility in southeast Adair County, Iowa. Three experimental treatments were involved in this randomized block design study: TIMR, Curtailment at 5.0 m/s, and Normal Operation. In 2021, three treatments were used at 18 turbines, expanding to four treatments across 36 turbines in 2022. The TIMR system worked as designed throughout the entire study; however, because of unexpected wind turbine operational challenges in 2021, there was not sufficient sample size to evaluate the treatment differences. In 2022, there were significant differences in fatality levels between treatment types and normal operating turbines. Curtailment at 5.0 m/s reduced fatalities by 30.8% compared to normal operations, and TIMR decreased fatalities by 48.6% compared to normal operations. Two different methods were used to evaluate the differences in energy loss for each treatment. The TIMR system resulted in 1.3% to 1.6 % annual energy loss in 2021 and 1.0% to 1.2 % in 2022. The Curtailment at 5.0 m/s resulted in 0.6% to 0.8 % annual energy loss in 2021 and 0.5% to 0.6 % in 2022. The project achieved all the stated objectives and demonstrated that TIMR is an effective technology that balances bat fatality reduction with energy generation. The results will support the deployment of TIMR and other acoustic sensor-based technologies. The research provides valuable insights into the impact of different treatments on fatality rates and energy outputs, contributing to the ongoing efforts to mitigate the environmental impact of wind energy.

17 WIND ENERGY↗
NASA NTRS1975

Compliant wall-turbulent skin-friction reduction research

Previous compliant-wall experiments successful in reducing skin-friction drag probably have had a (unplanned) membrane resonance at a favorable frequency, amplitude, wave shape, length, and speed. The most probable drag reduction mechanism involves a direct coupling between the fluid and the moving wall when the wall natural resonance frequencies are near the fundamental turbulent burst frequency. Local skin-friction reductions of 61% were measured with mylar/PVC plastisol compliant surfaces. These reductions were observed only at certain flow conditions, indicating that changing tunnel total temperature may have altered the substrate dynamic modulus, damping, and coupled mylar tension. Apparently, the coupled membrane/substrate must be excited in compatible narrow-band natural frequency modes. An accelerated effort is required to develop practical durable compliant surfaces optimized for maximum drag reduction. Application of compliant walls to other transportation modes appears feasible with liquid flows offering the greatest skin-friction drag reduction potential.

Fischer, M. C.↗
NASA NTRS1978

Reduction of aircraft gas turbine engine pollutant emissions

To accomplish simultaneous reduction of unburned hydrocarbons, carbon monoxide, and oxides of nitrogen, required major modifications to the combustor. The modification most commonly used was a staged combustion technique. While these designs are more complicated than production combustors, no insurmountable operational difficulties were encountered in either high pressure rig or engine tests which could not be resolved with additional normal development. The emission reduction results indicate that reductions in unburned hydrocarbons were sufficient to satisfy both near and far-termed EPA requirements. Although substantial reductions were observed, the success in achieving the CO and NOx standards was mixed and depended heavily on the engine/engine cycle on which it was employed. Technology for near term CO reduction was satisfactory or marginally satisfactory. Considerable doubt exists if this technology will satisfy all far-term requirements.

Diehl, L. A.↗
NASA NTRS1979

Bosch - An alternate CO2 reduction technology

The Bosch process is the most promising CO2 reduction concept for future prolonged space missions. The paper presents the design of a three-person-capacity preprototype B-CRS (Bosch-based CO2 Reduction Subsystem). It is sized to reduce 3.0 kg/d CO2 generated by the crew and to supply the product water to an O2 generation subsystem to obtain O2. The design supports future development of the B-CRS as an alternative CO2 reduction subsystem to the Sabatier-based process presently under test at NASA. The discussion covers the Bosch CO2 reduction concept, process and hardware description, performance parameters, design specifications, subsystem schematic and operation, mechanical subsystem summary, control/monitor instrumentation, and subsystem packaging. A B-CRS with a proven technological base is an attractive CO2 reduction subsystem that eliminates overboard venting.

Heppner, D. B.↗
NASA NTRS1980

Structural parameters that influence the noise reduction characteristics of typical general aviation materials

Effect of panel curvature and oblique angle of sound incidence on noise reduction characteristics of an aluminum panel are experimentally investigated. Panel curvature results show significant increase in stiffness with comparable decrease of sound transmission through the panel in the frequency region below the panel/cavity resonance frequency. Noise reduction data have been achieved for aluminum panels with clamped, bonded and riveted edge conditions. These edge conditions are shown to influence noise reduction characteristics of aluminum panels. Experimentally measured noise reduction characteristics of flat aluminum panels with uniaxial and biaxial in-plane stresses are presented and discussed. Results indicate important improvement in noise reduction of these panels in the frequency range below the fundamental panel/cavity resonance frequency.

Roskam, J.↗
NASA NTRS1985

Airfoil large-eddy breakup devices for turbulent drag reduction

Large-eddy breakup devices were tested in a turbulent boundary layer at a momentum thickness Reynolds number of 7400. The drag reducing characteristics of thin, tapered plates, NACA 0009, and NACA 4409 airfoil shapes were determined and compared with lower Reynolds number data obtained with thin elements. The results indicate that at the higher Reynolds numbers of the present tests the thin, tapered plates in a tandem arrangement produced large downstream skin-friction reductions (maximum 0/40 percent/), and gave net drag reductions at least as large as for lower Reynolds numbers. Tandem NACA 0009 airfoils, which were approximately 10 times thicker than the thin plates, gave similar results with a maximum downstream skin-friction reduction of 0(30 percent) and a net drag reduction of 7 percent. The device drag for this shape was determined to be near laminar skin friction. The NACA 4409 airfoils suffered large regions of separated flow and produced no net drag reduction.

Anders, J. B.↗
NASA NTRS1987

Noise reduction for model counterrotation propeller at cruise by reducing aft-propeller diameter

The forward propeller of a model counterrotation propeller was tested with its original aft propeller and with a reduced diameter aft propeller. Noise reductions with the reduced diameter aft propeller were measured at simulated cruise conditions. Reductions were as large as 7.5 dB for the aft-propeller passing tone and 15 dB in the harmonics at specific angles. The interaction tones, mostly the first, were reduced probably because the reduced-diameter aft-propeller blades no longer interacted with the forward propeller tip vortex. The total noise (sum of primary and interaction noise) at each harmonic was significantly reduced. The chief noise reduction at each harmonic came from reduced aft-propeller-alone noise, with the interaction tones contributing little to the totals at cruise. Total cruise noise reductions were as much as 3 dB at given angles for the blade passing tone and 10 dB for some of the harmonics. These reductions would measurably improve the fuselage interior noise levels and represent a definite cruise noise benefit from using a reduced diameter aft propeller.

Dittmar, James H.↗
NASA NTRS1987

Turbulent drag reduction research at NASA Langley - Progress and plans

Prospective research efforts planned at NASA-Langley in view of results obtained to date in passive turbulent drag reduction experiments are discussed. It has been established that conventional flow-aligned riblets are effective even in the presence of a degree of flow inclination and pressure gradients, and at transonic speeds. No increase in net drag reduction is expected from nonconventional riblet geometries. Large eddy breakup devices promise drag reductions in the 8-15 percent range. Heat transfer-augmentation, noise-reduction, turboprop/fuselage interaction noise reduction, are other advantages expected from this line of research.

Wilkinson, S. P.↗
NASA NTRS1988

Grammians and model reduction in limited time and frequency intervals

In this paper the controllability and observability grammians in limited time and frequency intervals are studied, and used for model reduction. In balanced and modal coordinates a near-optimal reduction procedure is developed, yielding the reduction error (norm of the difference between the output of the original system and the reduced model) almost minimal. Several examples are given to illustrate the concept for model reduction of continuous- and discrete-time systems, stable and unstable systems, in limited tim or/and frequency interval. Finally, the model reduction of a flexible truss structure is presented.

Gawronski, Wodek↗