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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 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Removal of Homogeneous Broadening from 1 H-Detected Multidimensional Solid-State NMR Spectra

1 H-detected magic-angle spinning (MAS) NMR experiments have revolutionized the NMR studies of biological and inorganic solids by providing unparalleled sensitivity and resolution. Despite these gains, homogeneous broadening, originating from the incomplete removal of homonuclear dipolar interactions under fast MAS, remains highly prevalent and limits the achievable resolution. In direct analogy to super-resolution microscopy methods, we show that resolution beyond that currently achievable by fast MAS alone can be obtained by experiment-driven deconvolution. Following the acquisition of a single 2D NMR spectrum to measure the frequency-dependent homogeneous lineshapes, any number of 1 H-detected spectra can be enhanced in resolution, yielding comparable spectra as obtained with twice the MAS frequency. In conclusion, the versatility of this approach is demonstrated in the enhancement of single- and double-quantum homonuclear correlation spectra, in addition to heteronuclear correlation spectra acquired on a surface organometallic complex and the protein GB1.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Homogeneous and Heterogeneous (Fex, Cr1-x)(OH)3 Precipitation: Implications for Cr Sequestration

The formation of (Fe, Cr)(OH)3 nanoparticles determines the fate of aqueous Cr in many aquatic environments. Using small angle X-ray scattering, precipitation rates of (Fe, Cr)(OH)3 nanoparticles in solution and on quartz were quantified from 0.1 mM Fe(III) solutions containing 0 – 0.25 mM Cr(III) at pH = 3.7 ± 0.2. Concentration ratio of aqueous Cr(III)/Fe(III) controlled the chemical composition (x) of (Fex, Cr1-x)(OH)3 precipitates, solutions’ supersaturation with respect to precipitates, and the surface charge of quartz. Therefore, aqueous Cr(III)/Fe(III) ratio affected homogeneous (in solution) and heterogeneous (on quartz) precipitation rates of (Fex, Cr1-x)(OH)3 through different mechanisms. The sequestration mechanisms of Cr(III) in precipitates were also investigated. In solutions with high aqueous Cr(III)/Fe(III) ratios, surface enrichment of Cr(III) on the precipitates occurred, resulting in slower particle growth in solution. From solutions with 0 – 0.1 mM Cr(III), the particles on quartz grew from 2 to 4 nm within 1 h. Interestingly, from solution with 0.25 mM Cr(III), particles of two distinct sizes (2 and 6 nm) formed on quartz, and their sizes remained unchanged throughout the reaction. Our study provided new insights on homogeneous and heterogeneous precipitation of (Fex, Cr1-x)(OH)3 nanoparticles, which can help determine the fate of Cr in aquatic environments.

GISAXS↗
DOE OSTI2017

Homogeneous Nucleation of Ice in Transiently-Heated, Supercooled Liquid Water Films

e have investigated the nucleation and growth of crystalline ice in 0.24 µm thick, supercooled water films deposited on Pt(111) at cryogenic temperatures. The films were heated with ~10 ns infrared laser pulses, which produced typical heating and cooling rates of ~109 – 1010 K/s. The crystallization of these water films was monitored with infrared spectroscopy. The experimental conditions were chosen such that ice nucleation at the water/metal interface was suppressed and nucleation at the water/vacuum interfaces did not affect the observations. Since the water films were flat, their internal pressure was not raised due to curvature effects. Therefore, the experiments were sensitive to the homogeneous ice nucleation rate in the temperature range from ~210 K to 225 K. The experiments show that the maximum for the homogeneous ice nucleation rate versus temperature, Jmax, needs to be = 1026 m-3s-1 and is likely to be ~1029±2 m-3s-1. We argue that such large nucleation rates are consistent with experiments on hyperquenched glassy water, which typically have crystalline fractions of ~1% or more.

Xu, Yuntao↗
DOE OSTI2023

Heterogenization of Homogeneous Ruthenium(II) Catalysts for Carbon-Neutral Dehydrogenation of Polyalcohols

Liquid organic hydrogen carrier (LOHC) systems are an excellent alternative to pressurized gas and liquid hydrogen storage technologies due to their high volumetric storage capacities and straightforward adaptation to existing infrastructure. Homogeneous catalysts are promising for the selective and reversible release of hydrogen from LOHC. However, separation from product mixtures and recycling inhibit their use, particularly when comprised of costly low-abundance elements, motivating the development of heterogeneous versions that are more easily recovered and reused. Here, we describe two methods for the heterogenization of molecular Ru catalysts that efficiently dehydrogenate the polyalcohol LOHCs ethylene glycol (EG) and 1,2-propanediol (1,2-PDO). The heterogeneous versions of these catalysts maintain catalytic activity for hydrogen production comparable to the homogeneous complexes, with up to 81% conversion and 99% selectivity. Further, DFT modeling indicates mechanistic similarities for the dehydrogenations of EG and 1,2-PDO, with the rate-limiting steps associated with protonation of the Ru–H bond to form H 2 and the alkoxide species coordinated to Ru(II), followed by β-hydride elimination to regenerate the Ru–H bond. Overall, the data suggest these heterogenized molecular catalysts have potential for practical use in polyalcohol-based LOHC systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Scaling Relations in Homogeneous Catalysis: Analyzing the Buchwald–Hartwig Amination Reaction

Scaling relations are widely used to study surface reactions. However, the exploration of its utility in homogeneous catalysis is currently far less reported. In this work, we have investigated the transferability of the concept of scaling relations to a homogeneous catalysis reaction known as the Buchwald–Hartwig amination (BHA) reaction. The reaction of PhBr with MeNH 2 using 37 different Pd–L complexes (L = phosphine ligand) is studied, and scaling relations are established among the reaction intermediates and transition states. Using the scaling relations, we construct volcano plots, which is the plot of the log(rate) vs the descriptor intermediate energy. The insights from the volcano plots agree well with the experimental trends from the literature and give direction toward better catalyst design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Is It Homogeneous or Heterogeneous Catalysis Derived from [RhCp*Cl2]2? In Operando-XAFS, Kinetic and Crucial Kinetic Poisoning Evidence for Subnanometer Rh4 Cluster-Based Benzene Hydrogenation Catalysis

Determining the true, kinetically dominant catalytically active species, in the classic benzene hydrogenation system pioneered by Maitlis and co-workers 34 years ago starting with [RhCp*Cl2]2 (Cp* = [{eta}5-C5(CH3)5]), has proven to be one of the most challenging case studies in the quest to distinguish single-metal-based 'homogeneous' from polymetallic, 'heterogeneous' catalysis. The reason, this study will show, is the previous failure to use the proper combination of (i) operando spectroscopy to determine the dominant form(s) of the precatalyst's mass under catalysis (i.e., operating) conditions, plus then and crucially also (ii) the previous lack of the necessary kinetic studies, catalysis being a 'wholly kinetic phenomenon' as J. Halpern long ago noted. An important contribution from this study will be to reveal the power of quantitiative kinetic poisoning experiments for distinguishing single-metal, or in this case subnanometer Rh4 cluster-based catalysis from larger, polymetallic Rh(0)n nanoparticle catalysis, at least under favorable conditions. The combined operando-XAFS (X-ray absorption fine structure) spectroscopy and kinetic evidences provide a compelling case for Rh4-based, with average stoichiometry 'Rh4Cp*2.4Cl4Hc', benzene hydrogenation catalysis in 2-propanol with added Et3N and at 100 C and 50 atm initial H2 pressure. The results also reveal, however, that if even ca. 1.4% of the total soluble Rh(0)n had formed nanoparticles, then those Rh(0)n nanoparticles would have been able to account for all the observed benzene hydrogenation catalytic rate (using commercial, ca. 2 nm, polyethyleneglycol-dodecylether hydrosol stabilized Rh(0)n nanoparticles as a model system). The results 'especially the poisoning methodology developed and employed' are of significant, broader interest since determining the nature of the true catalyst continues to be a central, often vexing issue in any and all catalytic reactions. The results are also of fundamental interest in that they add to a growing body of evidence indicating that certain, appropriately ligated, coordinatively unsaturated, subnanometer M4 transition-metal clusters can be relatively robust catalysts. Also demonstrated herein is that Rh4 clusters are poisoned by Hg(0), demonstrating for the first time that the classic Hg(0) poisoning test of 'homogeneous' vs 'heterogeneous'catalysts cannot distinguish Rh4-based subnanometer catalysts from Rh(0)n nanoparticle catalysts, at least for the present examples of these two specific, Rh-based catalysts.

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

Precise Synthesis of 4.75 V-Tolerant LiCoO 2 with Homogeneous Delithiation and Reduced Internal Strain

The rapid advancements in 3C electronic devices necessitate an increase in the charge cutoff voltage of LiCoO 2 to unlock a higher energy density that surpasses the currently available levels. However, the structural devastation and electrochemical decay of LiCoO 2 are significantly exacerbated, particularly at ≥4.5 V, due to the stress concentration caused by more severe lattice expansion and shrinkage, coupled with heterogeneous Li + intercalation/deintercalation reactions. Herein, employing the molten-salt synthesis technique, we propose a universal morphology-shaping strategy to attain bulk reaction homogeneity and reduce internal strains, even at extremely high charge voltages. The newly designed flattened polygon prismlike LiCoO 2 (P-LCO) particle, featuring a regular symmetrical arrangement along the c-axis, demonstrates a more homogeneous Li + extraction/insertion reaction, which results in a restrained transformation to detrimental O1 phase and reduced variation in lattice volume throughout the (de)lithiation processes. This benefits the mitigation of the local stress accumulation misfit dislocations and particle cracking, ultimately maintaining the mechanical stability of the cathode. Consequently, P-LCO is capable of breaking the voltage ceiling and exhibits exceptional long-term cycling capability at an ultrahigh voltage of 4.75 V. In conclusion, this work offers a brand-new perspective for the rational design of cathode morphology to address capacity deterioration caused by inhomogeneous delithiation and internal strain, thus inspiring the development of high-energy-density cathodes with improved durability.

36 MATERIALS SCIENCE↗
DOE OSTI2010

Impact of heterogeneous ice nuclei on homogeneous freezing events in cirrus clouds

The influence of initial heterogeneous nucleation on subsequent homogeneous nucleation events in cirrus clouds is investigated using a box model which includes the explicit impact of aerosols on the nucleation of ice crystals and sedimentation. Different effects are discussed, namely the impact of external mixtures of heterogeneous ice nuclei and the influence of size-dependent freezing thresholds. Several idealized experiments are carried out, which show that the treatment of external mixtures of ice nuclei can strongly change later homogeneous nucleation events (i.e., the ice crystal number densities) in different matters. The use of size-dependent freezing thresholds can also change the cloud prop erties when compared to more simple parameterizations. This size effect is most important for large IN concentrations. Based upon these findings, recommendations for future modeling and measurement efforts are presented.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Perturbation of Tropical Stratospheric Ozone Through Homogeneous and Heterogeneous Chemistry Due To Pinatubo

Abstract The Pinatubo eruption in 1991 injected 10–20 Tg SO 2 into the stratosphere, which formed sulfate aerosols through oxidation. Our modeling results show that volcanic heating significantly perturbs the heterogeneous and homogeneous chemistry including NO x and HO x catalytic cycles in the tropical stratosphere. The simulated tropical chemical ozone tendency is positive at 20 mb while negative at 10 mb in the tropics. The simulated ozone chemical tendency is of the same magnitude as the dynamical ozone tendency caused by the accelerated tropical upwelling, but with the opposite sign. Our study finds that the tropical ozone chemical tendency due to homogeneous chemistry becomes more important than heterogeneous chemistry 3 months after eruption. Sensitivity simulations further suggest that the tropical ozone tendency through heterogeneous chemistry is saturated when the injected amount exceeds 2 Tg.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Tuning hydrogenation chemistry of Pd-based heterogeneous catalysts by introducing homogeneous-like ligands

Abstract Noble metals have been extensively employed in a variety of hydrotreating catalyst systems for their featured functionality of hydrogen activation but may also bring side reactions such as undesired deep hydrogenation. It is crucial to develop a viable approach to selectively inhibit side reactions while preserving beneficial functionalities. Herein, we present modifying Pd with alkenyl-type ligands that forms homogeneous-like Pd-alkene metallacycle structure on the heterogeneous Pd catalyst to achieve the selective hydrogenolysis and hydrogenation. Particularly, a doped alkenyl-type carbon ligand on Pd-Fe catalyst is demonstrated to donate electrons to Pd, creating an electron-rich environment that elongates the distance and weakens the electronic interaction between Pd and unsaturated C of the reactants/products to control the hydrogenation chemistry. Moreover, high H 2 activation capability is maintained over Pd and the activated H is transferred to Fe to facilitate C-O bond cleavage or directly participate in the reaction on Pd. The modified Pd-Fe catalyst displays comparable C-O bond cleavage rate but much higher selectivity (>90%) than the bare Pd-Fe (<50%) in hydrotreating of diphenyl ether (DPE, modelling the strongest C-O linkage in lignin) and enhanced ethene selectivity (>90%) in acetylene hydrogenation. This work sheds light on the controlled synthesis of selective hydrotreating catalysts via mimicking homogeneous analogues.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Evaluation of CdZnTeSe as a high-quality gamma-ray spectroscopic material with better compositional homogeneity and reduced defects

X- and gamma-ray detectors have broad applications ranging from medical imaging to security, non-proliferation, high-energy physics and astrophysics. Detectors with high energy resolution, e.g. less than 1.5% resolution at 662 keV at room temperature, are critically important in most uses. The efficacy of adding selenium to the cadmium zinc telluride (CdZnTe) matrix for radiation detector applications has been studied. In this paper, the growth of a new quaternary compound Cd 0.9 Zn 0.1 Te 0.98 Se 0.02 by the Traveling Heater Method (THM) is reported. The crystals possess a very high compositional homogeneity with less extended defects, such as secondary phases and sub-grain boundary networks. Virtual Frisch-grid detectors fabricated from as-grown ingots revealed ~0.87-1.5% energy resolution for 662-keV gamma rays. The superior material quality with a very low density of defects and very high compositional homogeneity heightens the likelihood that Cd 0.9 Zn 0.1 Te 0.98 Se 0.02 will be the next generation room-temperature detector material.

36 MATERIALS SCIENCE↗
DOE OSTI2021

The homogenous alternative to biomineralization: Zn- and Mn-rich materials enable sharp organismal “tools” that reduce force requirements

We measured hardness, modulus of elasticity, and, for the first time, loss tangent, energy of fracture, abrasion resistance, and impact resistance of zinc- and manganese-enriched materials from fangs, stings and other “tools” of an ant, spider, scorpion and nereid worm. The mechanical properties of the Zn- and Mn-materials tended to cluster together between plain and biomineralized “tool” materials, with the hardness reaching, and most abrasion resistance values exceeding, those of calcified salmon teeth and crab claws. Atom probe tomography indicated that Zn was distributed homogeneously on a nanometer scale and likely bound as individual atoms to more than ¼ of the protein residues in ant mandibular teeth. This homogeneity appears to enable sharper, more precisely sculpted “tools” than materials with biomineral inclusions do, and also eliminates interfaces with the inclusions that could be susceptible to fracture. Based on contact mechanics and simplified models, we hypothesize that, relative to plain materials, the higher elastic modulus, hardness and abrasion resistance minimize temporary or permanent tool blunting, resulting in a roughly 2/3 reduction in the force, energy, and muscle mass required to initiate puncture of stiff materials, and even greater force reductions when the cumulative effects of abrasion are considered. We suggest that the sharpness-related force reductions lead to significant energy savings, and can also enable organisms, especially smaller ones, to puncture, cut, and grasp objects that would not be accessible with plain or biomineralized “tools”.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Physical Justification for Negative Remanent Magnetization in Homogeneous Nanoparticles

The phenomenon of negative remanent magnetization (NRM) has been observed experimentally in a number of heterogeneous magnetic systems and has been considered anomalous. The existence of NRM in homogenous magnetic materials is still in debate, mainly due to the lack of compelling support from experimental data and a convincing theoretical explanation for its thermodynamic validation. Here we resolve the long-existing controversy by presenting experimental evidence and physical justification that NRM is real in a prototype homogeneous ferromagnetic nanoparticle, an europium sulfide nanoparticle. We provide novel insights into major and minor hysteresis behavior that illuminate the true nature of the observed inverted hysteresis and validate its thermodynamic permissibility and, for the first time, present counterintuitive magnetic aftereffect behavior that is consistent with the mechanism of magnetization reversal, possessing unique capability to identify NRM. The origin and conditions of NRM are explained quantitatively via a wasp-waist model, in combination of energy calculations.

CONDENSED-MATTER PHYSICS↗
DOE OSTI2023

Homogeneous versus MOF-supported catalysis: a direct comparison of catalytic hydroboration with Ni tripodal P 3 E (E = Si, Ge) complexes

The MOF material NU-1000 was employed to host Ni tripodal complexes prepared from new organometallic precursors [HNi(κ 4 (E,P,P,P)-E(o-C 6 H 4 CH 2 PPh 2 ) 3 ], E = Si (Ni-1), Ge (Ni-2). The new heterogeneous catalytic materials, Ni-1@NU-1000 and Ni-2@NU-1000, show the advantages of both homogeneous and heterogeneous catalysts. Finally, they catalyze the hydroboration of aldehydes and ketones more efficiently than the homogeneous Ni-1 and Ni-2, under aerobic conditions and show recyclability.

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

On the use of NMR distance measurements for assessing surface site homogeneity

The past few decades have seen tremendous growth in the area of single-site heterogeneous catalysis, which aims to combine the best aspects of homogeneous and heterogeneous catalysis, namely molecular-level site control and ease of separation/recycling. Despite this, we still do not have a means of assessing site homogeneity and whether the produced catalyst is indeed a “single-site”. Recent developments have enabled the use of NMR-based distance measurements to determine the conformations and configurations of surface sites, leading to the question whether such measurements can be used to distinguish materials containing either single or multiple surface sites with otherwise indistinguishable NMR properties. Here, we describe a Monte Carlo-based multi-structure search algorithm and its application to the determination of multi-site structures from supported metal complexes. The sensitivity of REDOR data to the existence of multiple sites is assessed using synthetic data and prior literature examples are revisited to determine whether the single-site approximation was indeed appropriate. We lastly apply this new methodology to differentiate the configurations of zirconocene complexes grafted onto alumina supports that were thermally treated at different temperatures.

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

Stabilizing homogeneous CaMn6Sn6via oscillatory crystal growth: structural complexity in a kagome metal

CaMn6Sn6 is a member of the large family of Mn-based kagome metals derived by filling voids of the prototypical CoSn structure. We observed Ca-deficiency and structural complexity, with approximately 10% deficiency of calcium relative to the ideal 166 stoichiometry. These features are common in related Ca-based materials. We find that growth conditions stabilize different phases with varying Curie temperatures. Diffraction and magnetization measurements reveal that conventional growth profiles yield inhomogeneity both within and between crystals in a given batch, whereas an oscillatory temperature profile promotes homogeneous crystals that adopt a superstructure beyond the parent hexagonal structure type. We present the physical properties of crystals grown using the oscillatory approach. The crystals are highly conductive, with a c-axis residual resistivity ratio ρ(300 K)/ρ(2 K) exceeding 100 and a positive, linear magnetoresistance at base temperature. Magnetically, the crystals are quite similar to MgMn6Sn6, with easy-plane ferromagnetic behavior and a Curie temperature of TC ≈ 237 K. These results highlight the critical role of growth conditions in stabilizing homogeneous crystals of complex phases such as Ca0.9Mn6Sn6. The oscillatory growth approach provides an effective route for accessing the intrinsic properties of this complex material and may be broadly useful for the growth of related kagome systems.

May, Andrew [ORNL] (ORCID:0000000307778539)↗
DOE OSTI2010

A plasma needle for generating homogeneous discharge in atmospheric pressure air

Homogeneous discharge in air is often considered to be the ultimate low-temperature atmospheric pressure plasmas for industrial applications. In this paper, we present a method whereby stable homogeneous discharge in open air can be generated by a simple plasma needle. The discharge mechanism is discussed based on the spatially resolved light emission waveforms from the plasma. Optical emission spectroscopy is used to determine electron energy and rotational temperature, and results indicate that both electron energy and rotational temperature increase with increasing the applied voltage. The results are analyzed qualitatively based on the discharge mechanism.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2010

Some scenarios with non-homogeneous Higgs vacuum

The standard Higgs mechanism employed in the Standard Model (SM) for electroweak symmetry breaking, relies on a homogenous Higgs vacuum expectation value (v.e.v.), i.e. a vacuum that does not depend on the position or the time coordinates. However, other non-homogeneous structures could also be considered, either at long or short distances. For instance, spatial variations of the Higgs v.e.v. on cosmological scales, would induce variations of the fundamental constants, and are severely constrained. Other possibilities, such as a discrete microscopic structure of the Higgs vacuum, or a confined Higgs mechanism associated with a strongly interacting Higgs sector, could be tested and give some light on the electroweak-scale contributions to the cosmological constant.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗