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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 1,603 records · Page 89
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Self-Inhibition Phenomena in Cu 3 Pt Oxidation by CO 2

Here, this study investigates the oxidation behavior of Cu 3 Pt(100) in CO 2 using a combination of ambient-pressure X-ray photoelectron spectroscopy, mass spectroscopy, and density functional theory modeling. Our in situ measurements reveal the simultaneous oxidation and reduction of Cu 2 O due to the opposing effects of atomic oxygen and CO generated from dissociative CO 2 adsorption, leading to a dynamic equilibrium state of simultaneously occurring redox reactions. Complementary atomistic calculations elucidate the inhibitory effects of subsurface Pt enrichment and the counteracting roles of CO 2 and CO in surface oxidation and reduction. These results provide mechanistic insights into the dissociative pathway of CO 2 molecules and dynamic evolution of surface composition and reactivity of Cu-based alloy catalysts in CO 2 -rich environments, with broader implications for tuning gas–surface reactions by manipulating gas reactants or solid surface composition.

36 MATERIALS SCIENCE↗
DOE OSTI2019

First-Principles Calculation of Water p K a Using the Newly Developed SCAN Functional

Acid/base chemistry is an intriguing topic that still constitutes a challenge for computational chemistry. While estimating the acid dissociation constant (or pK a ) could shed light on many chemistry processes, especially in the fields of biochemistry and geochemistry, evaluating the relative stability between protonated and nonprotonated species is often very difficult. Indeed, a prerequisite for calculating the pK a of any molecule is an accurate description of the energetics of water dissociation. In this study, we applied constrained molecular dynamics simulations, a noncanonical sampling technique, to investigate the water deprotonation process by selecting the OH distance as the reaction coordinate. The calculation is based on density functional theory and the newly developed SCAN functional, which has shown excellent performance in describing water structure. This first benchmark of SCAN on a chemical reaction shows that this functional accurately models the energetics of proton transfer reactions in an aqueous environment. After taking Coulomb long-range corrections and nuclear quantum effects into account, the estimated water pK a is only 1.0 pK a unit different from the target experimental value. Our results show that the combination of SCAN and constrained MD successfully reproduces the chemistry of water and constitutes a good framework for calculating the free energy of chemical reactions of interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Dry Reforming of Methane on Single-Site Ni/MgO Catalysts: Importance of Site Confinement

Single-site catalysts (SSCs) have drawn considerable attention, because of their superior behaviors in catalysis. However, the origin of promoting the effect of a single site is not well understood. Here in this paper, we take the single-atom Ni1/Mg(100) and single-site Ni4/Mg(100) catalysts as a case study to elucidate their behaviors under the complex dry reforming of methane (DRM, CO 2 + CH 4 → 2CO + 2H 2 ) reaction by combining theoretical modeling (density functional theory and kinetic Monte Carlo simulation) and experimental studies. The synergy between single Ni atom and MgO is found to improve the binding property of MgO; yet, it is not enough to dissociate CO 2 and CH 4 . It can be achieved by the single-site Ni 4 /MgO(100) catalyst, enabling the formations of CO, H 2 , and H 2 O under the DRM conditions. During this process, coking, as observed for bulklike Ni particles, is eliminated. By confining the reaction to occur at the isolated Ni sites in the SSC, the Ni 4 /MgO(100) catalyst is able to balance the CO 2 and CH 4 activations, which is identified as the key for tuning the DRM activity and selectivity of Ni/MgO catalysts. The theory-identified promotion introduced by increasing the size of MgO-supported Ni clusters from Ni 1 to Ni 4 and the MgO-introduced site confinement of single-site catalysts are verified by corresponding experimental studies, highlighting the essential roles of confined sites in tuning the performance of SSCs during complex catalytic processes.

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

Surface-Plasmon-Mediated Gradient Force Enhancement and Mechanical State Transitions of Graphene Sheets

Graphene, a two-dimensional material possessing extraordinary properties in electronics as well as mechanics, provides a great platform for various optoelectronic and opto-mechanical devices. Here in this article, we theoretically study the optical gradient force arising from the coupling of surface plasmon modes on parallel graphene sheets, which can be several orders stronger than that between regular dielectric waveguides. Furthermore, with an energy functional optimization model, possible force-induced deformation of graphene sheets is calculated. We show that the significantly enhanced optical gradient force may lead to mechanical state transitions of graphene sheets, which are accompanied by abrupt changes in reflection and transmission spectra of the system. Our demonstrations illustrate the potential for a broader graphene-related applications such as force sensors and actuators.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Evidence for a Solid-Electrolyte Inductive Effect in the Superionic Conductor Li 10 Ge 1– x Sn x P 2 S 12

Strategies to enhance ionic conductivities in solid electrolytes typically focus on the effects of modifying their crystal structures or of tuning mobile-ion stoichiometries. A less-explored approach is to modulate the chemical bonding interactions within a material to promote fast lithium-ion diffusion. Recently, the idea of a solid-electrolyte inductive effect has been proposed, whereby changes in bonding within the solid-electrolyte host framework modify the potential energy landscape for the mobile ions, resulting in an enhanced ionic conductivity. Direct evidence for a solid-electrolyte inductive effect, however, is lacking—in part because of the challenge of quantifying changes in local bonding interactions within a solid-electrolyte host framework. Here, we consider the evidence for a solid-electrolyte inductive effect in the archetypal superionic lithium-ion conductor Li 10 Ge 1–x Sn x P 2 S 12 . Substituting Ge for Sn weakens the {Ge,Sn}–S bonding interactions and increases the charge density associated with the S 2– ions. This charge redistribution modifies the Li + substructure causing Li + ions to bind more strongly to the host framework S 2– anions, which in turn modulates the Li + ion potential energy surface, increasing local barriers for Li + ion diffusion. Each of these effects is consistent with the predictions of the solid-electrolyte inductive effect model. Density functional theory calculations predict that this inductive effect occurs even in the absence of changes to the host framework geometry due to Ge → Sn substitution. These results provide direct evidence in support of a measurable solid–electrolyte inductive effect and demonstrate its application as a practical strategy for tuning ionic conductivities in superionic lithium-ion conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Confinement of Iodine Molecules into Triple-Helical Chains within Robust Metal–Organic Frameworks

During nuclear waste disposal process, radioactive iodine as a fission product can be released. The widespread implementation of sustainable nuclear energy thus requires the development of efficient iodine stores that have simultaneously high capacity, stability and more importantly, storage density (and hence minimized system volume). Here, we report high I 2 adsorption in a series of robust porous metal–organic materials, MFM-300(M) (M = Al, Sc, Fe, In). MFM-300(Sc) exhibits fully reversible I 2 uptake of 1.54 g g –1 , and its structure remains completely unperturbed upon inclusion/removal of I 2 . Direct observation and quantification of the adsorption, binding domains and dynamics of guest I 2 molecules within these hosts have been achieved using XPS, TGA-MS, high resolution synchrotron X-ray diffraction, pair distribution function analysis, Raman, terahertz and neutron spectroscopy, coupled with density functional theory modeling. These complementary techniques reveal a comprehensive understanding of the host–I 2 and I 2 –I 2 binding interactions at a molecular level. The initial binding site of I 2 in MFM-300(Sc), I 2 I , is located near the bridging hydroxyl group of the [ScO 4 (OH) 2 ] moiety [I 2 I ···H–O = 2.263(9) Å] with an occupancy of 0.268. I 2 II is located interstitially between two phenyl rings of neighboring ligand molecules [I 2 II ···phenyl ring = 3.378(9) and 4.228(5) Å]. I 2 II is 4.565(2) Å from the hydroxyl group with an occupancy of 0.208. Significantly, at high I 2 loading an unprecedented self-aggregation of I 2 molecules into triple-helical chains within the confined nanovoids has been observed at crystallographic resolution, leading to a highly efficient packing of I 2 molecules with an exceptional I 2 storage density of 3.08 g cm –3 in MFM-300(Sc).

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

Spectroscopic evidence for a type II Weyl semimetallic state in MoTe 2

In a type I Dirac or Weyl semimetal, the low-energy states are squeezed to a single point in momentum space when the chemical potential μ is tuned precisely to the Dirac/Weyl point. Recently, a type II Weyl semimetal was predicted to exist, where the Weyl states connect hole and electron bands, separated by an indirect gap. This leads to unusual energy states, where hole and electron pockets touch at the Weyl point. Here we present the discovery of a type II topological Weyl semimetal state in pure MoTe 2 , where two sets of Weyl points ( W ± 2 , W ± 3 ) exist at the touching points of electron and hole pockets and are located at different binding energies above E F . Using angle-resolved photoemission spectroscopy, modelling, density functional theory and calculations of Berry curvature, we identify the Weyl points and demonstrate that they are connected by different sets of Fermi arcs for each of the two surface terminations. We also find new surface ‘track states’ that form closed loops and are unique to type II Weyl semimetals. Lastly, this material provides an exciting, new platform to study the properties of Weyl fermions.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes

The introduction of sp 3 defects into single-walled carbon nanotubes through covalent functionalization can generate new light-emitting states and thus dramatically expand their optical functionality. This may open up routes to enhanced imaging, photon upconversion, and room-temperature single-photon emission at telecom wavelengths. However, a significant challenge in harnessing this potential is that the nominally simple reaction chemistry of nanotube functionalization introduces a broad diversity of emitting states. Precisely defining a narrow band of emission energies necessitates constraining these states, which requires extreme selectivity in molecular binding configuration on the nanotube surface. We show that such selectivity can be obtained through aryl functionalization of so-called ‘zigzag’ nanotube structures to achieve a threefold narrowing in emission bandwidth. Accompanying density functional theory modelling reveals that, because of the associated structural symmetry, the defect states become degenerate, thus limiting emission energies to a single narrow band. Finally, we show that this behaviour can only result from a predominant selectivity for ortho binding configurations of the aryl groups on the nanotube lattice.

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

Stable single-site organonickel catalyst preferentially hydrogenolyses branched polyolefin C–C bonds

Current methods of processing accumulated polyolefin waste typically require harsh conditions, precious metals or high metal loadings to achieve appreciable activities. Here, in this work, we examined supported, single-site organonickel catalysts for polyolefin upcycling. Chemisorption of Ni(COD) 2 (COD, 1,5-cyclooctadiene) onto Brønsted acidic sulfated alumina (AlS) yields a highly electrophilic Ni(I) precatalyst, AlS/Ni(COD) 2 , which is converted under H 2 to the active AlS/Ni II H catalyst. This single-site system exhibits unique hydrogenolysis selectivity that favours cleaving branched polyolefin C–C linkages, enabling the hydrogenolytic separation of polyethylene and isotactic polypropylene (iPP) mixtures. Moreover, AlS/Ni II H remains highly selective and active for hydrogenolysis of iPP admixed with polyvinyl chloride, and the spent catalyst can be repeatedly regenerated by AlEt3 treatment. Experimental mechanistic analysis and density functional theory modelling reveal a turnover-limiting C–C scission pathway featuring β-alkyl transfer and strong olefin binding. These results highlight the potential of nickel-based systems for the selective upcycling of complex plastic waste streams.

green chemistry↗
DOE OSTI2023

Grazing-incidence diffraction reveals cellulose and pectin organization in hydrated plant primary cell wall

Abstract The primary cell wall is highly hydrated in its native state, yet many structural studies have been conducted on dried samples. Here, we use grazing-incidence wide-angle X-ray scattering (GIWAXS) with a humidity chamber, which enhances scattering and the signal-to-noise ratio while keeping outer onion epidermal peels hydrated, to examine cell wall properties. GIWAXS of hydrated and dried onion reveals that the cellulose ( $$110/1\overline{1}0$$ 110 / 1 1 ¯ 0 ) lattice spacing decreases slightly upon drying, while the (200) lattice parameters are unchanged. Additionally, the ( $$110/1\overline{1}0$$ 110 / 1 1 ¯ 0 ) diffraction intensity increases relative to (200). Density functional theory models of hydrated and dry cellulose microfibrils corroborate changes in crystalline properties upon drying. GIWAXS also reveals a peak that we attribute to pectin chain aggregation. We speculate that dehydration perturbs the hydrogen bonding network within cellulose crystals and collapses the pectin network without affecting the lateral distribution of pectin chain aggregates.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2014

Remarkable NO oxidation on single supported platinum atoms

Our first-principles density functional theoretical modeling suggests that NO oxidation is feasible on fully oxidized single θ-alumina-supported platinum atoms via a modified Langmuir-Hinshelwood pathway. This is in contrast to the known decrease in NO oxidation activity of supported platinum with decreasing Pt particle size believed to be due to increased platinum oxidation. In order to validate our theoretical study, we evaluated single θ-Al 2 O 3 -supported platinum atoms and found them to exhibit remarkable NO oxidation activity. A comparison of turnover frequencies (TOF) of single supported Pt atoms with those of platinum particles for NO oxidation shows that single supported Pt atoms are as active as fully formed platinum particles. The overall picture of NO oxidation on supported Pt is that NO oxidation activity decreases with decreasing Pt particle size but accelerates when Pt is present only as single atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Assembly of three-dimensional binary superlattices from multi-flavored particles

Binary superlattices constructed from nano- or micron-sized colloidal particles have a wide variety of applications, including the design of advanced materials. Self-assembly of such crystals from their constituent colloids can be achieved in practice by, among other means, the functionalization of colloid surfaces with single-stranded DNA sequences. However, when driven by DNA, this assembly is traditionally premised on the pairwise interaction between a single DNA sequence and its complement, and often relies on particle size asymmetry to entropically control the crystalline arrangement of its constituents. The recently proposed “multi-flavoring” motif for DNA functionalization, wherein multiple distinct strands of DNA are grafted in different ratios to different colloids, can be used to experimentally realize a binary mixture in which all pairwise interactions are independently controllable. Here we use various computational methods, including molecular dynamics and Wang–Landau Monte Carlo simulations, to study a multi-flavored binary system of micron-sized DNA-functionalized particles modeled implicitly by Fermi–Jagla pairwise interactions. We show how self-assembly of such systems can be controlled in a purely enthalpic manner, and by tuning only the interactions between like particles, demonstrate assembly into various morphologies. Although polymorphism is present over a wide range of pairwise interaction strengths, we show that careful selection of interactions can lead to the generation of pure compositionally ordered crystals. Additionally, we show how the crystal composition changes with the like-pair interaction strengths, and how the solution stoichiometry affects the assembled structures.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Observing the three-dimensional dynamics of supported metal complexes

Dynamics are intricately linked with activity and selectivity when it comes to catalysis, as noted for instance in the enzymatic principles of induced fit and allostery, and yet the range of motions heterogeneous catalytic sites are able to undergo is poorly understood. Solid-state nuclear magnetic resonance (NMR) spectroscopy is perhaps the only tool capable of probing the rapid conformational dynamics found in heterogeneous catalysts but has historically been restricted by its low sensitivity, limiting the detail with which structures can be resolved. In this work, we apply solid-state NMR and dynamic nuclear polarization, in combination with density functional theory modeling, to reveal the high-resolution structure and motional freedom of a scandium supported complex in three dimensions. The results are contrasted with the study of the analogous homoleptic complex in the crystalline state, highlighting the impacts that surface structure may have on the dynamics of supported complexes.

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

Modeling and Simulation of Ternary Pumped Storage Hydropower for Power System Studies

As the deployment of wind and solar energy increases in the United States, energy storage (ES) will play an important role in future electric power grids. To help manage the variability from high penetration levels of renewable generation, ES can provide promising power/energy demand to coordinate with renewables generation, as a virtual power plant (VPP). There is an industry need for the capability in power system studies to model ternary pumped storage hydropower (T-PSH) that offers increased system benefits. This paper presents a comprehensive vendor-neutral dynamic model of T-PSH in GE's commercial software positive sequence load flow (PSLF). A new governor model is developed with detailed gate valve modeling and a shared-penstock function. Specifically, this model is designed to simulate the seamless transition among three operation modes: generation mode, pumping mode, and hydraulic short-circuit mode. The developed T-PSH model has been tested and validated on a 10-bus test system. A comparison study of T-PSH to conventional pumped storage hydropower has also been conducted on the Western Interconnection system.

13 HYDRO ENERGY↗
DOE OSTI2012

Propagation characteristics of a Gaussian laser beam in plasma with modulated collision frequency

The propagation characteristics of a Gaussian laser beam in cold plasma with the electron collision frequency modulated by laser intensity are presented. The nonlinear dynamics of the ponderomotive force, which induce nonlinear self-focusing as opposed to spatial diffraction, are considered. The effective dielectric function of the Drude model and complex eikonal function are adopted in deriving coupled differential equations of the varying laser beam parameters. In the framework of ponderomotive nonlinearity, the frequency of electron collision in plasmas, which is proportional to the spatial electron density, is strongly interrelated with the laser beam propagation characteristics. Hence, the propagation properties of the laser beam and the modulated electron collision frequency distribution in plasma were studied and explained in depth. Employing this self-consistent method, the obtained simulation results approach practical conditions, which is of significance to the study of laser-plasma interactions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

Communication: Quantum molecular dynamics simulation of liquid para-hydrogen by nuclear and electron wave packet approach

Liquid para-hydrogen (p-H{sub 2}) is a typical quantum liquid which exhibits strong nuclear quantum effects (NQEs) and thus anomalous static and dynamic properties. We propose a real-time simulation method of wave packet (WP) molecular dynamics (MD) based on non-empirical intra- and inter-molecular interactions of non-spherical hydrogen molecules, and apply it to condensed-phase p-H{sub 2}. The NQEs, such as WP delocalization and zero-point energy, are taken into account without perturbative expansion of prepared model potential functions but with explicit interactions between nuclear and electron WPs. The developed MD simulation for 100 ps with 1200 hydrogen molecules is realized at feasible computational cost, by which basic experimental properties of p-H{sub 2} liquid such as radial distribution functions, self-diffusion coefficients, and shear viscosities are all well reproduced.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

A multiclass vehicular dynamic traffic flow model for main roads and dedicated lanes/roads of multimodal transport network

We present in this paper a model of vehicular traffic flow for a multimodal transportation road network. We introduce the notion of class of vehicles to refer to vehicles of different transport modes. Our model describes the traffic on highways (which may contain several lanes) and network transit for pubic transportation. The model is drafted with Eulerian and Lagrangian coordinates and uses a Logit model to describe the traffic assignment of our multiclass vehicular flow description on shared roads. The paper also discusses traffic streams on dedicated lanes for specific class of vehicles with event-based traffic laws. An Euler-Lagrangian-remap scheme is introduced to numerically approximate the model’s flow equations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Effect of surface fields on the dynamic resistance of planar HgCdTe mid-wavelength infrared photodiodes

This work investigates the effect of surface fields on the dynamic resistance of a planar HgCdTe mid-wavelength infrared photodiode from both theoretical and experimental aspects, considering a gated n-on-p diode with the surface potential of its p-region modulated. Theoretical models of the surface leakage current are developed, where the surface tunnelling current in the case of accumulation is expressed by modifying the formulation of bulk tunnelling currents, and the surface channel current for strong inversion is simulated with a transmission line method. Experimental data from the fabricated devices show a flat-band voltage of V{sub FB}=−5.7 V by capacitance-voltage measurement, and then the physical parameters for bulk properties are determined from the resistance-voltage characteristics of the diode working at a flat-band gate voltage. With proper values of the modeling parameters such as surface trap density and channel electron mobility, the theoretical R{sub 0}A product and corresponding dark current calculated from the proposed model as functions of the gate voltage V{sub g} demonstrate good consistency with the measured values. The R{sub 0}A product remarkably degenerates when V{sub g} is far below or above V{sub FB} because of the surface tunnelling current or channel current, respectively; and it attains the maximum value of 5.7×10{sup 7} Ω · cm{sup 2} around the transition between surface depletion and weak inversion when V{sub g}≈−4 V, which might result from reduced generation-recombination current.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗