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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 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Rhodium Single–Atom Catalysts on Titania for Reverse Water Gas Shift Reaction Explored by First Principles Mechanistic Analysis and Compared to Nanoclusters

The thermocatalytic reduction of CO2 by H2 often proceeds via two competing reaction mechanisms—the reverse water gas shift reaction (rWGSR, CO2 + H2 ⇌ CO + H2O) and methanation (CO2 + 4H2 ⇌ CH4 + 2H2O). Atomically dispersed Rh1 catalysts on TiO2 show high selectivity toward the rWGSR compared with larger Rh nanoclusters, but the origin of this size-dependent selectivity has not been fully explained. Here we report density functional theory (DFT) calculations and microkinetic simulations that clarify the Rh1 active sites and rWGSR pathway on anatase TiO2(101), as well as the high rWGSR selectivity of Rh1 compared with supported Rhx (x = 2–8 atoms) nanoclusters. DFT-computed formation energies, vibrational frequency analysis, and microkinetic modeling suggest three plausible active sites: Rh1 on titania (Rh1/TiO2(101)), Rh1 with a nearby hydroxyl group (Rh1OH/TiO2(101)), and Rh1 near an oxygen vacancy at a three-fold coordinated site (Rh1 near O3cvac). Predicted turnover frequencies and apparent activation barriers for Rh1 indicate a faster reaction involving CO2 dissociation assisted by a support oxygen vacancy via Rh1 near O3cvac, as well as slower reactions involving Rh1OH/TiO2(101) or Rh1/TiO2(101) through a COOH intermediate. Furthermore, these Rh1 sites are selective toward CO rather than CH4 because of the weak adsorption of CO, large barrier for C-O bond dissociation, and the lack of nearby metal sites for H2 dissociation, in contrast to Rhx nanoclusters, including Rh2 dimers.

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

Photocatalytic Hydrogen Evolution by a De Novo Designed Metalloprotein that Undergoes Ni–Mediated Oligomerization Shift

De novo metalloprotein design involves the construction of proteins guided by specific repeat patterns of polar and apolar residues, which, upon self-assembly, provide a suitable environment to bind metals and produce artificial metalloenzymes. While a wide range of functionalities have been realized in de novo designed metalloproteins, the functional repertoire of such constructs towards alternative energy-relevant catalysis is currently limited. Here we show the application of de novo approach to design a functional H 2 evolving protein. The design involved the assembly of an amphiphilic peptide featuring cysteines at tandem a/d sites of each helix. Intriguingly, upon Ni II addition, the oligomers shift from a major trimeric assembly to a mix of dimers and trimers. The metalloprotein produced H 2 photocatalytically with a bell-shape pH dependence, having a maximum activity at pH 5.5. Transient absorption spectroscopy is used to determine the timescales of electron transfer as a function of pH. Selective outer sphere mutations are made to probe how the local environment tunes activity. Finally, a preferential enhancement of activity is observed via steric modulation above the Ni II site, towards the N-termini, compared to below the Ni II site towards the C-termini.

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

Shifting institutional culture to develop climate solutions with Open Science

To address our climate emergency, “we must rapidly, radically reshape society”—Johnson & Wilkinson, All We Can Save. In science, reshaping requires formidable technical (cloud, coding, reproducibility) and cultural shifts (mindsets, hybrid collaboration, inclusion). We are a group of cross-government and academic scientists that are exploring better ways of working and not being too entrenched in our bureaucracies to do better science, support colleagues, and change the culture at our organizations. We share much-needed success stories and action for what we can all do to reshape science as part of the Open Science movement and 2023 Year of Open Science.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Warming of alpine tundra enhances belowground production and shifts community towards resource acquisition traits

Abstract Climate warming is expected to stimulate plant growth in high‐elevation and high‐latitude ecosystems, significantly increasing aboveground net primary production (ANPP). However, the effects of simultaneous changes in temperature, snowmelt timing, and summer water availability on total net primary production (NPP)—and elucidation of both above‐ and belowground responses—remain an important area in need of further study. In particular, measures of belowground net primary productivity (BNPP) are required to understand whether ANPP changes reflect changes in allocation or are indicative of a whole plant NPP response. Further, plant functional traits provide a key way to scale from the individual plant to the community level and provide insight into drivers of NPP responses to environmental change. We used infrared heaters to warm an alpine plant community at Niwot Ridge, Colorado, and applied supplemental water to compensate for soil water loss induced by warming. We measured ANPP, BNPP, and leaf and root functional traits across treatments after 5 yr of continuous warming. Community‐level ANPP and total NPP (ANPP + BNPP) did not respond to heating or watering, but BNPP increased in response to heating. Heating decreased community‐level leaf dry matter content and increased total root length, indicating a shift in strategy from resource conservation to acquisition in response to warming. Water use efficiency (WUE) decreased with heating, suggesting alleviation of moisture constraints that may have enabled the plant community to increase productivity. Heating may have decreased WUE by melting snow earlier and creating more days early in the growing season with adequate soil moisture, but stimulated dry mass investment in roots as soils dried down later in the growing season. Overall, this study highlights how ANPP and BNPP responses to climate change can diverge, and encourages a closer examination of belowground processes, especially in alpine systems, where the majority of NPP occurs belowground.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Spatial Bayesian models project shifts in suitable habitat for Pacific Northwest tree species under climate change

Abstract We developed spatial Bayesian hierarchical models to assess potential climate change impacts on suitable habitat for five important tree species in the Pacific northwestern United States (California, Oregon, and Washington). Individual‐species models were fit with presence–absence data from forest inventory field plots and spatial relationships were specified through a conditional autoregressive model. This modeling approach allowed us to visualize uncertainty in response curves, map current and future prediction uncertainty, and provide interval estimates for change. Upward elevational or northward latitudinal shifts in climatically suitable habitat were projected for all species. Climate change impacts were the most damaging for noble fir ( Abies procera ), for which 79%–100% of the current range was projected to become climatically unsuitable by the 2080s. Although coastal Douglas‐fir ( Pseudotsuga menziesii var. menziesii ) has been projected by others to gain habitat in Canada, within our study area we projected a net loss of climatically suitable habitat (ca. 8000–31,400 km 2 ) under three of four future climate scenarios. A net loss in habitat was also projected for Oregon white oak ( Quercus garryana ) under three of four scenarios, with 40%–60% of the current range becoming unsuitable. Although there was no net loss of habitat for forest land blue oak under any scenario, other factors like competition may inhibit blue oak ( Quercus douglasii ) and white oak from occupying areas projected to increase in climatic suitability. Additionally, between 13% and 32% of blue oak's current range was projected to become unsuitable; some of these areas aligned with dieback following the 2012–2015 California drought, which our data set predates. Unlike the other four species, we projected a 17%–25% increase in climatically suitable habitat for California black oak ( Quercus kelloggii ), although 1%–20% of the current range was still projected to become unsuitable. Our findings indicate that, although some species will face more pressure in tracking climatically suitable habitat than others, climate change will impact the location of suitable habitat for many species.

Kralicek, Karin↗
DOE OSTI2020

HIV-1 transmitted drug resistance surveillance: shifting trends in study design and prevalence estimates

HIV-1 transmitted drug resistance (TDR) prevalence increased during the initial years of the antiretroviral therapy (ART) global scale-up. Few studies have examined recent trends in TDR prevalence using published genetic sequences and described the characteristics of ART-naïve persons from whom these published sequences have been obtained. We identified 125 studies published between 2014 and 2019 for which HIV-1 reverse transcriptase (RT) with or without protease from ≥50 ART-naïve adult persons were submitted to the GenBank sequence database. The population characteristics and TDR prevalence were compared to those in 122 studies published in the preceding five years between 2009 and 2013. TDR prevalence was analysed using median study-level and person-level data. The 2009 to 2013 and 2014 to 2019 studies reported sequence data from 32,866 and 41,724 ART-naïve persons respectively. Studies from the low- and middle-income country (LMIC) regions in sub-Saharan Africa, South/Southeast Asia and Latin America/Caribbean accounted for approximately two-thirds of the studies during each period. Between the two periods, the proportion of studies from sub-Saharan Africa and from South/Southeast Asia countries other than China decreased from 43% to 32% and the proportion of studies performed at sentinel sites for recent HIV-1 infection decreased from 33% to 22%. Between 2014 and 2019, median study-level TDR prevalence was 4.1% in South/Southeast Asia, 6.0% in sub-Saharan Africa, 9.1% in Latin America/Caribbean, 8.5% in Europe and 14.2% in North America. In the person-level analysis, there was an increase in overall, NNRTI and two-class NRTI/NNRTI resistance in sub-Saharan Africa; an increase in NNRTI resistance in Latin America/Caribbean, and an increase in overall, NNRTI and PI resistance in North America. Overall, NNRTI and dual NRTI/NNRTI-associated TDR prevalence was significantly higher in sub-Saharan Africa studies published between 2014 and 2019 compared with those published between 2009 and 2013. The decreasing proportion of studies from the hardest hit LMIC regions and the shift away from sentinel sites for recent infection suggests that global TDR surveillance efforts and publication of findings require renewed emphasis.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Multinuclear 1 H/ 13 C/ 15 N chemical shift assignment of therapeutic octreotide acetate performed at natural abundance

Abstract Octreotide acetate, the active pharmaceutical ingredient in the long‐acting release (LAR) drug product Sandostatin®, is a cyclic octapeptide that mimics the naturally occurring somatostatin peptide hormone. Modern NMR can be a robust analytical method to identify and quantify octreotide molecules. Previous 1 H chemical shift assignments were mostly performed in organic solvents, and no assignments for heteronuclear 13 C, 15 N, and aromatic 1 H nuclei are available. Here, using state‐of‐the‐art 1D and 2D homo‐ and heteronuclear NMR experiments, octreotide was fully assigned, including water exchangeable amide protons, in aqueous buffer except for 13 CO and 15 NH of F1, 15 NH of C2, and 15 NζHζof K5 that were not observed because of water exchange or conformational exchange. The solution NMR spectra were then directly compared with 1D 1 H/ 13 C/ 15 N solid‐state NMR (SSNMR) spectra showing the potential applicability of 13 C/ 15 N SSNMR for octreotide drug product characterization.

Chemistry↗
DOE OSTI2024

Fermionic shift symmetries in (anti) de Sitter space

We study extended shift symmetries that arise for fermionic fields on anti-de Sitter (AdS) space and de Sitter (dS) space for particular values of the mass relative to the curvature scale. We classify these symmetries for general mixed-symmetry fermionic fields in arbitrary dimension and describe how fields with these symmetries arise as the decoupled longitudinal modes of massive fermions as they approach partially massless points. For the particular case of AdS 4 , we look for non-trivial Lie superalgebras that can underly interacting theories that involve these fields. We study from this perspective the minimal such theory, the Akulov-Volkov theory on AdS 4 , which is a non-linear theory of a spin-1/2 Goldstino field that describes the spontaneous breaking of $\mathcal{N}$ = 1 supersymmetry on AdS 4 down to the isometries of AdS 4 . We show how to write the nonlinear supersymmetry transformation for this theory using the fermionic ambient space formalism. We also study the Lie superalgebras of candidate multi-field examples and rule out the existence of a supersymmetric special galileon on AdS 4 .

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2022

On the implications of positive W mass shift

We investigate the phenomenological implications of the recent W mass measurement by the CDF collaboration, which exhibits tension with the standard model (SM) electroweak fit. Performing the fit to the electroweak observables within the SM effective field theory, we find that the new physics that contributes either to the determination of the electroweak vacuum expectation value, or to the oblique parameters, can improve the agreement with data. The best description is obtained from a fit where flavor universality is not required in the new physics operators, with 2 to 3 σ indications for several nonzero Wilson coefficients. We point out that top partners with order TeV masses could lead to the observed shift in the W mass.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Robust late twenty-first century shift in the regional monsoons in RegCM-CORDEX simulations

Abstract We use an unprecedented ensemble of regional climate model (RCM) projections over seven regional CORDEX domains to provide, for the first time, an RCM-based global view of monsoon changes at various levels of increased greenhouse gas (GHG) forcing. All regional simulations are conducted using RegCM4 at a 25 km horizontal grid spacing using lateral and lower boundary forcing from three General Circulation Models (GCMs), which are part of the fifth phase of the Coupled Model Inter-comparison Project (CMIP5). Each simulation covers the period from 1970 through 2100 under two Representative Concentration Pathways (RCP2.6 and RCP8.5). Regional climate simulations exhibit high fidelity in capturing key characteristics of precipitation and atmospheric dynamics across monsoon regions in the historical period. In the future period, regional monsoons exhibit a spatially robust delay in the monsoon onset, an increase in seasonality, and a reduction in the rainy season length at higher levels of radiative forcing. All regions with substantial delays in the monsoon onset exhibit a decrease in pre-monsoon precipitation, indicating a strong connection between pre-monsoon drying and a shift in the monsoon onset. The weakening of latent heat driven atmospheric warming during the pre-monsoon period delays the overturning of atmospheric subsidence in the monsoon regions, which defers their transitioning into deep convective states. Monsoon changes under the RCP2.6 scenario are mostly within the baseline variability.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Quantifying and visualizing the microscopic degrees of freedom of grain boundaries in the Wigner–Seitz cell of the displacement-shift-complete lattice

Here we introduce a grain boundary (GB) translation vector, t ws , to describe and quantify the domain of the microscopic degrees of freedom of GBs. It has long been recognized that for fixed macroscopic degrees of freedom of a GB there exists a large multiplicity of states characterized by different relative grain translations. More recently another degree of freedom, [n], the number of GB atoms, has emerged and is now recognized as an equally important component of GB structural multiplicity. In this work, we show that all GB microstates can be uniquely characterized by their value of t ws , which is located within the Wigner–Seitz (WS) cell of the Displacement-Shift-Complete lattice (DSCL) of the GB. The GB translation vector captures information about both the translation state and the number of GB atoms. We show that the density of GB microstates inside the WS cell of the DSCL is not uniform and can form clusters that correspond to different GB phases. Further, the vectors connecting the centers of the clusters correspond to the Burgers vectors of GB phase junctions, which can be predicted without building the junctions. Using t ws , we quantify GB excess shear and argue that it is defined up to a DSCL vector, which has implications for thermodynamic equilibrium conditions. Additionally, this work generalizes the definition of the number of GB atoms [n] to asymmetric boundaries.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Efficient continuous Energy-Multigroup hybrid depletion scheme using the Shift Monte Carlo code. Part I: Energy condensation sensitivity analysis

Monte Carlo (MC) codes coupled to depletion solvers are increasingly used to provide high fidelity fuel cycle modeling capabilities. Here, these coupled depletion-MC tools produce accurate results in general but can experience nonphysical spatial oscillations when time steps are large or when a system’s dominance ratio approaches unity. Two substepping techniques have been developed previously to remedy and dampen these spatial oscillations without needing to reduce step sizes. The first approach relied on higher-order techniques to account for spectral changes within steps (extrapolation and interpolation techniques). The second approach used the first order perturbation (FOP) theory to account for the change in the one-group spatial flux distribution within steps. This paper develops a hybrid depletion methodology which, in a way, combines how the flux is handled in both substepping techniques. Specifically, the multigroup (MG) MC Shift code is used to update the flux distribution within steps rather than a one-group FOP solver. A fully reflected pincell is investigated, which is not spatially dependent in the MG representation. Thus, the analysis in this paper is an initial demonstration of hybrid depletion. An upcoming companion paper will focus on how the hybrid depletion dampens spatial oscillations. The hybrid depletion approach is verified to be consistent with previous constant extrapolation depletion (CED) methods. This paper finds that the hybrid CED exhibits some error in the eigenvalue and one group constants within macro steps. To address this discrepancy, a simple interpolation scheme (CELI) is investigated. This work found that CELI sufficiently addresses the discrepancy in spectrum for macro steps up to 100 days. Overall, this work demonstrates that the hybrid depletion method can significantly reduce the number of high fidelity MC executions in a MC-coupled depletion with an acceptable eigenvalue error.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2020

A reduced-order shifted boundary method for parametrized incompressible Navier–Stokes equations

Here, we investigate a projection-based reduced order model of the steady incompressible Navier–Stokes equations for moderate Reynolds numbers. In particular, we construct an “embedded” reduced basis space, by applying proper orthogonal decomposition to the Shifted Boundary Method, a high-fidelity embedded method recently developed. We focus on the geometrical parametrization through level-set geometries, using a fixed Cartesian background geometry and the associated mesh. This approach avoids both remeshing and the development of a reference domain formulation, as typically done in fitted mesh finite element formulations. Two-dimensional computational examples for one and three parameter dimensions are presented to validate the convergence and the efficacy of the proposed approach.

"embedded" basis↗
DOE OSTI2021

Current research in low temperature proton exchange membrane-based electrolysis and a necessary shift in focus

While hydrogen has limited use in energy markets today, significant growth is possible in grid storage and as an energy carrier in other sectors. Along with lower electricity prices, further hydrogen cost reduction can enable electrochemical water splitting, particularly as the use of intermittent, renewable power sources increases and the quantity and duration of storage requirements limit electrical storage options. With the improved viability of large-scale hydrogen production, research in low temperature electrolysis has dramatically increased. The overwhelming majority of research efforts within proton exchange membrane-based systems has focused on catalyst development, although a smaller set have developed transport layers as well. As proton exchange membrane-based electrolysis shifts into higher technology readiness levels, however, there is a growing need for work optimizing materials integration, developing component-specific and device-level accelerated stress tests, and addressing manufacturing considerations. These areas directly impact electrolyzer performance, durability, and cost, and are critical to advancing hydrogen’s value and electrochemical water splitting.

08 HYDROGEN↗
DOE OSTI2023

Lithium promotion of Pt/m-ZrO 2 catalysts for low temperature water-gas shift

Low temperature water-gas shift (LTS) is an important reaction occurring in a fuel processor for producing and purifying hydrogen. Platinum supported on m-ZrO 2 belongs to a family of catalysts consisting of metal nanoparticles and an active partially reducible oxide, with the catalysis proposed to occur at the boundary between metal particles and the support. In this investigation, increasing the loading of lithium dopant increased the LTS rate up to 0.54 wt % lithium, where conversion was 2.4 times that of the unpromoted catalyst at 260°C. Further increases in lithium loading up to 1.5 wt % decreased the rate, although it remained higher than that of the unpromoted catalyst. Infrared spectroscopy and CO 2 temperature programmed desorption experiments showed three effects with increasing lithium loading: (1) lithium promoter weakened the C–H bond of formate, the proposed rate limiting step of the interfacial surface formate mechanism; (2) high levels of lithium suppressed the platinum site capacity required for hydrogen transfer; and (3) high levels of lithium increased catalyst basicity. Aspects (2) and (3) tended to inhibit desorption of product CO 2 , an acidic molecule the removal of which is metal-catalyzed. XANES and XPS experiments revealed that electron transfer to enrich Pt nanoparticles is unlikely the root cause of C–H bond weakening in formate. However, other electronic effects (e.g., electrostatic effects or molecular rearrangement due to enhanced basicity) were not ruled out.

08 HYDROGEN↗
DOE OSTI2021

Proton-detected solid-state NMR spectroscopy of spin-1/2 nuclei with large chemical shift anisotropy

Constant-time (CT) dipolar heteronuclear multiple quantum coherence (D-HMQC) has previously been demonstrated as a method for proton detection of high-resolution wideline NMR spectra of spin-1/2 nuclei with large chemical shift anisotropy (CSA). However, 1 H transverse relaxation and t 1 -noise often reduce the sensitivity of D-HMQC experiments, preventing the theoretical gains in sensitivity provided by 1 H detection from being realized. In this paper, we demonstrate a series of improved pulse sequences for 1 H detection of spin-1/2 nuclei under fast MAS, with 195 Pt SSNMR experiments on cisplatin as an example. First, a t 1 -incrementation protocol for D-HMQC dubbed Arbitrary Indirect Dwell (AID) is demonstrated. AID allows the use of arbitrary, rotor asynchronous t 1 -increments, but removes the constant time period from CT D-HMQC, resulting in improved sensitivity by reducing transverse relaxation losses. Next, we show that short high-power adiabatic pulses (SHAPs), which efficiently invert broad MAS sideband manifolds, can be effectively incorporated into 1 H detected symmetry-based resonance echo double resonance (S-REDOR) and t 1 -noise eliminated (TONE) D-HMQC experiments. The S-REDOR experiments with SHAPs provide approximately double the dipolar dephasing, as compared to experiments with rectangular inversion pulses. We lastly show that sensitivity and resolution can be further enhanced with the use of swept excitation pulses as well as adiabatic magic angle turning (aMAT).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Enhanced backscatter and unsaturated blue wavelength shifts in F-doped fused silica optical fibers exposed to extreme neutron radiation damage

Amorphous fused silica (a-SiO 2 ) optical fibers, with and without inscribed Bragg gratings, were interrogated using infrared (~1550 nm) optical backscatter reflectometry during ~25 days of intense neutron irradiation to a fast (energy > 0.1 MeV) neutron fluence of ~10 21 n/cm 2 , or ~1.5 atomic displacements per atom. The reflected light amplitudes in Ge-doped core telecommunications fiber dropped below detection limits (>15 dB attenuation) within 3 days of irradiation (~10 20 fast n/cm 2 ). Here, amplitudes from a pure silica core, F-doped silica cladding fiber reached equilibrium levels ~1.5–2 dB higher than pre-irradiation values, whereas Bragg gratings inscribed in the same fiber using a femtosecond laser (point-by-point method) suffered > 45 dB attenuation. Blue wavelength shifts were initially consistent with previous radiation-induced compaction models but increased linearly with increasing neutron fluence (no evidence of saturation) beyond 10 20 n/cm 2 and exceeded 0.6%, which corresponds to >1,000 °C drift if used to measure temperature changes.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Irradiation-induced shift in the thermodynamic stability of phases and the self-healing effect in transformative high entropy alloys

Here, this work investigated Fe 40 Mn 20 Cr 15 Co 20 Si 5 high entropy alloy (CS-HEA), which exhibits transformation induced plasticity (TRIP) from γ-fcc → ε-hcp, as a probable candidate for nuclear applications. CS-HEA is an extensively-explored, low stacking fault energy alloy with superior strength, ductility, fatigue resistance, and corrosion resistance. This study delved into the effect of irradiation on the shift in thermodynamic stability of the phases and thus radiation tolerance. The evolution of phases, lattice parameters, and transformation volume, V γ→ε , were evaluated from X-ray diffraction experiments along with the mechanical response from nanoindentation. The alloy exhibited a recently-proposed novel self-healing mechanism possible due to the TRIP effect to minimize irradiation damage by restraining the γ-fcc → ε-hcp transformation via thermal aid; this self-healing mechanism was confirmed by transmission electron microscopy. The results were corroborated by a negative change in V γ→ε and a low |V γ→ε |, which is an important criterion for recovery of parent γ-fcc phase. Thus, this alloy was deemed a good radiation-tolerant candidate for nuclear application.

36 MATERIALS SCIENCE↗