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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Weakening the N–H Bonds of NH 3 Ligands: Triple Hydrogen-Atom Abstraction to Form a Chromium(V) Nitride

Weakening and cleaving N-H bonds is crucial for improving molecular ammonia oxidation catalysts. In this work, we report the synthesis and hydrogen atom abstraction chemistry of bis(ammonia) Cr porphyrin complexes Cr(TPP)(NH 3 ) 2 and Cr(TMP)(NH 3 ) 2 (TPP = 5,10,15,20-tetraphenyl-meso-porphyrin and TMP = 5,10,15,20-tetramesityl-meso-porphyrin) using bulky aryloxyl radicals. The triple hydrogen atom abstraction reaction results in the formation of Cr V (por)(≡N), with the nitride deriving from ammonia, as indicated by UV-Vis and FT-IR spectroscopy, and a single crystal structural determination of Cr(TPP)(≡N). Subsequent oxidation of this chromium(V)-nitrido complex results in the formation of Cr III (por), with scission of the Cr≡N bond. A computational analysis illustrates the progression from Cr II to Cr V and evaluates the energetics of abstracting hydrogen atoms from Cr II -NH 3 to generate Cr V ≡N. The formation and isolation of Cr V (por)(≡N) illustrates the stability of these species and the need to chemically activate the nitride moiety for atom transfer or N-N coupling reactivity.

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

Water Weakening of Calcium Oxide

Chemomechanical processes such as water weakening can control the permeability and deformation of rocks and manmade materials. Here, atomistic modeling and nanomechanical experiments were used to identify molecular origins of chemomechanical effects in calcium oxide (CaO) and its effect on observed elastic, plastic, and brittle deformation. Classical molecular dynamics simulations with the bond order-based reactive force-field ReaxFF were used to assess brittle fracture. In the presence of water, CaO fractured earlier and more often during quasi-static loading, with a calculated reduction in fracture toughness of ~80% associated with changes in the stress distribution around the crack tip. Experimentally, elastic and plastic deformation of CaO surfaces exposed to water was assessed experimentally using in situ liquid nanoindentation. Nanoindentation showed that following exposure to water, the contact hardness decreased by 1–2 orders of magnitude and decreased the modulus by 2–3 orders of magnitude due to surface hydroxylation. Furthermore, the strong chemomechanical effects on the mechanical processes in CaO suggests that minerals with similar structures may exhibit comparable effects, influencing the stability of cements and geomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Coordination-Induced N–H Bond Weakening in a Molybdenum Pyrrolidine Complex: Isotopic Labeling Provides Insight into the Pathway for H 2 Evolution

The synthesis and characterization of a cationic molybdenum pyrrolidine complex is described that exhibits significant coordination-induced N–H bond weakening. Here, the N–H bond dissociation free energy (BDFE) of the coordinated pyrrolidine in [( Ph Tpy)(PPh 2 Me) 2 Mo(NH(pyrr))][BArF 24 ] ([1-NH(pyrr)] + ; PhTpy = 4'-Ph-2,2',6',2''-terpyridine, NH(pyrr) = pyrrolidine, ArF 24 = [C 6 H 3 -3,5-(CF 3 ) 2 ] 4 ) was determined to be between 41–51 kcal mol -1 by thermochemical analysis and supported by a density functional theory (DFT) computed value of 48 kcal mol -1 . The complex [1-NH(pyrr)] + underwent proton-coupled electron transfer (PCET) to 2,4,6-tri-tert-butylphenoxyl radical, as well as spontaneous H 2 evolution upon gentle heating to furnish the corresponding molybdenum pyrrolidide complex, [( Ph Tpy)(PPh 2 Me) 2 Mo(N(pyrr))][BArF 24 ] ([1-N(pyrr)] + ). Thermolysis of the deuterated isotopolog, [1-ND(pyrr)] + still produced H 2 with concomitant incorporation of the isotopic label into the pyrrolidide ligand in the product [(1-N(pyrr-d n )] + (n = 0–2), consistent with an H 2 evolution pathway involving intramolecular H–H bond formation followed by an intermolecular product-forming PCET step. These observations provide context for understanding H 2 evolution in the nonclassical ammine complex [( Ph Tpy)(PPh 2 Me) 2 Mo(NH 3 )][BArF 24 ] ([1-NH 3 ] + ) and are supported by DFT-computed reaction thermochemistry. Overall, these studies offer rare insight into the H 2 formation pathway in nonclassical amine complexes with N–H BDFEs below the thermodynamic threshold for H 2 evolution and inform the development of well-defined, thermody-namically potent PCET reagents.

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

Warm Phase of AMV Damps ENSO Through Weakened Thermocline Feedback

Abstract Interactions between ocean basins affect El Niño–Southern Oscillation (ENSO), altering its impacts on society. Here, we explore the effect of Atlantic Multidecadal Variability (AMV) on ENSO behavior using idealized experiments performed with the NCAR‐CESM1 model. Comparing warm (AMV+) to cold (AMV−) AMV conditions, we find that ENSO sea surface temperature (SST) anomalies are reduced by ∼10% and ENSO precipitation anomalies are shifted to the west during El Niño and east during La Niña. Using the Bjerknes stability index, we attribute the reduction in ENSO variability to a weakened thermocline feedback in boreal autumn. In AMV+, the Walker circulation and trade winds strengthen over the tropical Pacific, increasing the background zonal SST gradient. The background changes shift ENSO anomalies westwards, with wind stress anomalies more confined to the west. We suggest the changes in ENSO‐wind stress decrease the strength of the thermocline feedback in the east, eventually reducing ENSO growth rate.

Trascasa‐Castro, Paloma↗
DOE OSTI2023

Entrainment Makes Pollution More Likely to Weaken Deep Convective Updrafts Than Invigorate Them

Are the results of aerosol invigoration studies that neglect entrainment valid for diluted deep convective clouds? We address this question by applying an entraining parcel model to soundings from tropical and midlatitude convective environments, wherein pollution is assumed to increase parcel condensate retention. Invigoration of 5%–10% and <2% is possible in undiluted tropical and midlatitude parcels respectively when freezing is rapid. This occurs because the positive buoyancy contribution from freezing is larger than the negative buoyancy contribution from condensate loading, leading to positive net condensate contribution to buoyancy. However, aerosol-induced weakening is more likely when realistic entrainment rates occur because water losses from entrainment more substantially reduce the latent heating relative to the loading contribution. This leads to larger net negative buoyancy contribution from condensates in polluted than in clean entraining parcels. Our results demonstrate that accounting for entrainment is critical in conceptual models of aerosol indirect effects in deep convection.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Time‐Dependent Weakening of Granite at Hydrothermal Conditions

Abstract The evolution of a fault's frictional strength during the interseismic period is a critical component of the earthquake cycle, yet there have been relatively few studies that examine the time‐dependent evolution of strength at conditions representative of seismogenic depths. Using a simulated fault in Westerly granite, we examined how frictional strength evolves under hydrothermal conditions up to 250°C during slide‐hold‐slide experiments. At temperatures ≤100°C, frictional strength generally increases with hold duration but, at 200 and 250°C, an initial increase in strength transitions to rapid time‐dependent weakening for holds longer than 14 hr. Forward modeling of long hold periods at 250°C using the rate and state friction constitutive equations requires a second, strongly negative, state variable with a long evolution distance. This implies that significant hydrothermal alteration is occurring at 250°C, consistent with microstructural observations of dissolution and secondary mineral precipitation.

Geology↗
DOE OSTI2024

Why Does Atmospheric Radiative Heating Weaken Midlatitude Cyclones?

Abstract Recent work has indicated that atmospheric radiative heating reduces the kinetic energy of large‐scale eddies in the midlatitudes. However, a physical mechanism that connects radiation to the midlatitude eddy kinetic energy is still uncertain. Using a high‐resolution general circulation model we perform an experiment in which the radiative cooling profile at each model time step is overwritten with the climatological mean, computed from a control simulation. This approach separates the mean and transient effects of radiative heating on the extratropical circulation. We find that, when radiative heating is fixed, the globally‐averaged eddy kinetic energy is enhanced by ∼6%. We show that thermal radiation dampens temperature anomalies near the surface and tropopause in low‐pressure systems, destroying eddy available potential energy and eddy kinetic energy. We identify this as a possible mechanism by which atmospheric radiative heating weakens midlatitude cyclones.

Mischell, Eric↗
DOE OSTI2026

Examining the Robustness of Weakened Orographic Influence on Precipitation in Downscaled Climate Projections Over the Western US

Assessing local climate change impacts often requires downscaling coarse global climate model (GCM) output to finer resolution. Two main approaches exist: dynamical downscaling using high-resolution regional climate models, and statistical downscaling based on historical relationships between large-scale and local variables. In a recent analysis of five dynamically downscaled simulations over the western United States, Koszuta et al. (2024, https://doi.org/10.1029/2023gl107298) found that warming weakens orographic influence on winter precipitation, damping increases on windward slopes and amplifying them in rain-shadowed regions. Here we show that this effect is robust across seasons and multiple dynamically downscaled ensembles, and is more pronounced at higher model resolutions. However, it is absent in projections from a widely used statistical model (LOCA2), even when trained on high-resolution future simulations (LOCA2-Hybrid). This highlights a key limitation of many statistical downscaling methods: their preservation of parent GCM trends, which usually fail to capture emergent changes in orographic precipitation patterns.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Stratospheric aerosol injection can weaken the carbon dioxide greenhouse effect

Abstract Stratospheric aerosol injection is a proposed method for offsetting greenhouse gas-induced warming by introducing scattering aerosols into the lower stratosphere to reflect sunlight. Here we explore a potentially more efficient alternative: weakening the Earth’s greenhouse effect by deploying absorptive aerosols in the upper stratosphere (~10 hPa). These aerosols warm the carbon dioxide emission level—where outgoing longwave radiation is most sensitive to temperature—thereby enhancing top-of-atmosphere infrared emission without altering atmospheric carbon dioxide concentrations. Idealized climate model simulations indicate that this approach can reduce global temperatures an order of magnitude more efficiently per unit aerosol mass than conventional scattering-based interventions. Although based on simplified model experiments lacking interactive aerosol processes and operational constraints, our results identify a distinct physical mechanism for climate intervention, arguing for further research into the impacts—especially potential unintended side effects—of injecting absorptive aerosols into the upper stratosphere as an alternative solar radiation management strategy.

Environmental Sciences & Ecology↗
DOE OSTI2025

Scalable, biologically sourced depolymerizable polydienes with intrinsically weakened carbon–carbon bonds

Currently, there are few examples of circularly recyclable polymers with all-carbon backbones, probably owing to the challenge of using selective C–C bond cleavage to efficiently produce monomers in recycling processes. Furthermore, here we demonstrate a series of biologically sourced polymuconate polymers synthesized via simple free-radical polymerization that exhibit intrinsically weakened C–C bonds and controlled chemical recycling to monomers. Modifying the side chains and copolymerization ratios allows a wide range of mechanical property tuning, achieving performances comparable to those of commercial plastics such as polystyrene, polymethyl methacrylate and polybutadiene. Techno-economic analysis and life cycle assessment for production at a scale of 100 kilotons per year show that the materials are currently slightly more expensive and environmentally intensive compared with conventional rubbers. However, use of recycled materials via depolymerization can greatly decrease the cost and environmental impacts of polymuconate production (for example, down to US$1.59 per kilogram) to outperform its commercial counterparts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Hyperconjugation-controlled molecular conformation weakens lithium-ion solvation and stabilizes lithium metal anodes

Tuning the solvation structure of lithium ions via electrolyte engineering has proven effective for lithium metal (Li) anodes. Further advancement that bypasses the trial-and-error practice relies on the establishment of molecular design principles. Expanding the scope of our previous work on solvent fluorination, we report here an alternative design principle for non-fluorinated solvents, which potentially have reduced cost, environmental impact, and toxicity. By studying non-fluorinated ethers systematically, we found that the short-chain acetals favor the [gauche, gauche] molecular conformation due to hyperconjugation, which leads to weakened monodentate coordination with Li + . The dimethoxymethane electrolyte showed fast activation to >99% coulombic efficiency (CE) and high ionic conductivity of 8.03 mS cm -1 . The electrolyte performance was demonstrated in anode-free Cu$∥$LFP pouch cells at current densities up to 4 mA cm -2 (70 to 100 cycles) and thin-Li$∥$high-loading-LFP coin cells (200–300 cycles). Overall, we demonstrated and rationalized the improvement in Li metal cyclability by the acetal structure compared to ethylene glycol ethers. We expect further improvement in performance by tuning the acetal structure.

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

Heterobimetallic multi-site concerted proton electron transfer (MS-CPET) promotes coordination-induced O–H bond weakening

Coordination-induced bond weakening of X–H bonds (X = O, N, C) has been observed in a number of low-valent transition metal compounds. However, the impact of an appended electron reservoir on the bond dissociation free energy of the O–H bond (BDFE O–H ) of a substrate bound to a d 0 metal is poorly understood. To gain insight into the ability of separated deprotonation and oxidation sites to decrease the BDFE O–H during proton-coupled electron transfer (PCET) reactions, a bimetallic system in which the sites of proton and electron loss are two distinct metal sites is described. Herein, the interconversion of tris(phosphinoamide) Zr/Co complexes HO–Zr(MesNP i Pr 2 ) 3 CoCN t Bu and O$≡$Zr(MesNP i Pr 2 ) 3 CoCN t Bu via hydrogen atom addition/abstraction was studied. Since the Zr center remains in the d 0 Zr IV state throughout these transformations, the electron transfer process is mediated by the appended redox-active Co 0/I center. A series of open-circuit potential (OCP) measurements on the HO–Zr(MesNP i Pr 2 ) 3 CoCN t Bu and O$≡$Zr(MesNP i Pr 2 ) 3 CoCN t Bu complexes was performed, from which the BDFE O–H was found to be 64 ± 1 kcal mol −1 . The BDFE O–H value was further verified through a series of stoichiometric H atom transfer reactions, stoichiometric protonation/deprotonation reactions, and computational studies.

Chemistry↗
DOE OSTI2024

Nitrogen Deposition Weakens Soil Carbon Control of Nitrogen Dynamics Across the Contiguous United States

ABSTRACT Anthropogenic nitrogen (N) deposition is unequally distributed across space and time, with inputs to terrestrial ecosystems impacted by industry regulations and variations in human activity. Soil carbon (C) content normally controls the fraction of mineralized N that is nitrified ( ƒ nitrified ), affecting N bioavailability for plants and microbes. However, it is unknown whether N deposition has modified the relationships among soil C, net N mineralization, and net nitrification. To test whether N deposition alters the relationship between soil C and net N transformations, we collected soils from coniferous and deciduous forests, grasslands, and residential yards in 14 regions across the contiguous United States that vary in N deposition rates. We quantified rates of net nitrification and N mineralization, soil chemistry (soil C, N, and pH), and microbial biomass and function (as beta‐glucosidase (BG) and N ‐acetylglucosaminidase (NAG) activity) across these regions. Following expectations, soil C was a driver of ƒ nitrified across regions, whereby increasing soil C resulted in a decline in net nitrification and ƒ nitrified . The ƒ nitrified value increased with lower microbial enzymatic investment in N acquisition (increasing BG:NAG ratio) and lower active microbial biomass, providing some evidence that heterotrophic microbial N demand controls the ammonium pool for nitrifiers. However, higher total N deposition increased ƒ nitrified , including for high soil C sites predicted to have low ƒ nitrified , which decreased the role of soil C as a predictor of ƒ nitrified . Notably, the drop in contemporary atmospheric N deposition rates during the 2020 COVID‐19 pandemic did not weaken the effect of N deposition on relationships between soil C and ƒ nitrified . Our results suggest that N deposition can disrupt the relationship between soil C and net N transformations, with this change potentially explained by weaker microbial competition for N. Therefore, past N inputs and soil C should be used together to predict N dynamics across terrestrial ecosystems.

Nieland, Matthew A. [Stockbridge School of Agricul↗
DOE OSTI2023

Carbon cycle extremes accelerate weakening of the land carbon sink in the late 21st century

Increasing surface temperature could lead to enhanced evaporation, reduced soil moisture availability, and more frequent droughts and heat waves. The spatiotemporal co-occurrence of such effects further drives extreme anomalies in vegetation productivity and net land carbon storage. However, the impacts of climate change on extremes in net biospheric production (NBP) over longer time periods are unknown. Using the percentile threshold on the probability distribution curve of NBP anomalies, we computed negative and positive extremes in NBP. Here we show that due to climate warming, about 88% of global regions will experience a larger magnitude of negative NBP extremes than positive NBP extremes toward the end of 2100, which accelerate the weakening of the land carbon sink. Our analysis indicates the frequency of negative extremes associated with declines in biospheric productivity was larger than positive extremes, especially in the tropics. While the overall impact of warming at high latitudes is expected to increase plant productivity and carbon uptake, high-temperature anomalies increasingly induce negative NBP extremes toward the end of the 21st century. Using regression analysis, we found soil moisture anomalies to be the most dominant individual driver of NBP extremes. The compound effect of hotness, dryness, and fire caused extremes at more than 50% of the total grid cells. The larger proportion of negative NBP extremes raises a concern about whether the Earth is capable of increasing vegetation production with a growing human population and rising demand for plant material for food, fiber, fuel, and building materials. The increasing proportion of negative NBP extremes highlights the consequences not only of reduction in total carbon uptake capacity but also of conversion of land to a carbon source.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Lithium-ion hopping weakens thermal stability of LiPF 6 carbonate electrolytes

Lithium hexafluorophosphate (LiPF 6 )-based carbonate electrolytes are widely used in commercial lithium-ion batteries (LIBs), but their thermal instability limits the cycle life and safety of LIBs at elevated temperatures. Few studies have yielded insight into the initial PF 6 — decomposition reaction that promotes thermal instability of LiPF6-based electrolytes. Here, we find that lithium-ion hopping assisted by the overall reorientational motion of propylene carbonate molecules facilitates PF 6 — decomposition at elevated temperatures in 1 M LiPF 6 /propylene carbonate electrolyte. Further, we demonstrate that urea additives, by preventing lithium-ion hopping, suppress the initial LiPF 6 decomposition reaction and enhance the thermal stability of the electrolyte. LIB cell tests with LiNi 0.6 Mn 0.2 Co 0.2 O 2 ||Li 4 Ti 5 O 12 show improved LIB performance at elevated temperatures with the thermally stabilized electrolyte. This study provides key insights into the design of thermally stable LiPF 6 -based carbonate electrolytes for improving the cycle life, calendar life, and safety of LIBs in elevated-temperature applications.

25 ENERGY STORAGE↗
DOE OSTI2026

Coordination-Induced Weakening of N–H Bonds Driven by Bimetallic Cooperativity in Zr/Co Compounds

The bond dissociation free energy (BDFE) of the element-hydrogen bonds of protic substrates have been found to decrease upon metal coordination. Herein, an early/late heterobimetallic complex is used to examine the impact on the BDFE N−H when the substrate binding site and the redox-active site are two different metals that are spatially separated. A tris- (phosphinoamide) framework is used to link a d 0 ZrIV center with an accessible substrate binding site to a coordinatively saturated redox-active Co center, which serves as an appended electron reservoir. A series of aniline, amido, and imido Zr/Co model compounds were synthesized starting from the Zr IV /Co −I aniline adduct PhH 2 N−Zr(MesNP i Pr 2 ) 3 CoCN t Bu (2). 2,4,6-tristert- butylphenoxyl radical ( t Bu 3 ArO • ) was used to abstract one or two H atoms and produce the amido and imido complexes PhHNZr( MesNP i Pr 2 ) 3 CoCN t Bu (3) and PhN≡Zr(MesNP i Pr 2 ) 3 CoCNtBu (4), respectively. Using open-circuit potential measurements, the BDFE N−H within 2 and 3 were determined to be 37 kcal/mol (2) and 55 kcal/mol (3). Cyclic voltammetry measurements were conducted to determine the Co I/0 and Co 0/−I redox potentials. The pK a s were then estimated using the Bordwell equation to provide further insight into the thermochemical aspects of the observed proton coupled electron transfer (PCET) reactions.

Bond dissociation free energy↗