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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 883 records · Page 49
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Optical detection of alcohols with a Cu($\tiny{I}$)HETPHEN complex by reversible aldehyde to hemiacetal conversion

A heteroleptic copper(I) bis(phenanthroline) complex with aldehyde groups at the 4,7 positions of the phenanthroline ligand was synthesized. Here, the complex is responsive to alcohol, resulting in a distinct colour change caused by the facile reaction of the aldehyde group with alcohol, forming a hemiacetal product. The aldehyde species can be regenerated after heating the intermediate at 80 °C for 10 minutes, demonstrating the reusability of the complex for alcohol detection. This work presents a new strategy for applying transition metal complexes in small molecule sensing by installing functional groups in the secondary coordination sphere which reversibly react with analytes.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Spin dynamics of [1,2- 13 C 2 ]pyruvate hyperpolarization by parahydrogen in reversible exchange at micro Tesla fields

Hyperpolarization of 13 C-pyruvate via Signal Amplification By Reversible Exchange (SABRE) is an important recent discovery because of both the relative simplicity of hyperpolarization and the central biological relevance of pyruvate as a biomolecular probe for in vitro or in vivo studies. Here, we analyze the [1,2- 13 C 2 ]pyruvate-SABRE spin system and its field dependence theoretically and experimentally. We provide first-principles analysis of the governing 4-spin dihydride- 13 C 2 Hamiltonian and numerical spin dynamics simulations of the 7-spin dihydride- 13 C 2 –CH 3 system. Furthermore, the analytical and the numerical results are compared to matching systematic experiments. With these methods we unravel the observed spin state mixing of singlet states and triplet states at microTesla fields and we also analyze the dynamics during transfer from micro-Tesla field to high field for detection to understand the resulting spectra from the [1,2- 13 C 2 ]pyruvate-SABRE system.

13C pyruvate↗
DOE OSTI2023

In situ studies of reversible solid–gas reactions of ethylene responsive silver pyrazolates

Solid–gas reactions and in situ powder X-ray diffraction investigations of trinuclear silver complexes {[3,4,5-(CF 3 ) 3 Pz]Ag} 3 and {[4-Br-3,5-(CF 3 ) 2 Pz]Ag} 3 supported by highly fluorinated pyrazolates reveal that they undergo intricate ethylene-triggered structural transformations in the solid-state producing dinuclear silver–ethylene adducts. Despite the complexity, the chemistry is reversible producing precursor trimers with the loss of ethylene. Less reactive {[3,5-(CF 3 ) 2 Pz]Ag} 3 under ethylene pressure and low-temperature conditions stops at an unusual silver–ethylene complex in the trinuclear state, which could serve as a model for intermediates likely present in more common trimer–dimer reorganizations described above. Complete structural data of three novel silver–ethylene complexes are presented together with a thorough computational analysis of the mechanism.

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

Reversible Cl/Cl - redox in a spinel Mn 3 O 4 electrode

A unique prospect of using halides as charge carriers is the possibility of the halides undergoing anodic redox behaviors when serving as charge carriers for the charge-neutrality compensation of electrodes. However, the anodic conversion of halides to neutral halogen species has often been irreversible at room temperature due to the emergence of diatomic halogen gaseous products. Here, we report that chloride ions can be reversibly converted to near-neutral atomic chlorine species in the Mn 3 O 4 electrode at room temperature in a highly concentrated chloride-based aqueous electrolyte. Notably, the Zn 2+ cations inserted in the first discharge and trapped in the Mn 3 O 4 structure create an environment to stabilize the converted chlorine atoms within the structure. Characterization results suggest that the Cl/Cl - redox is responsible for the observed large capacity, as the oxidation state of Mn barely changes upon charging. Computation results corroborate that the converted chlorine species exist as polychloride monoanions, e.g., [Cl 3 ] - and [Cl 5 ] - , inside the Zn 2+ -trapped Mn 3 O 4 , and the presence of polychloride species is confirmed experimentally. Our results point to the halogen plating inside electrode lattices as a new charge-storage mechanism.

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

Li–Mn–O Li-rich cation disordered rock-salt cathode materials do not undergo reversible oxygen redox during cycling

An in-depth study of “Li 4 Mn 2 O 5 ”, a nanocomposite of Li 2 O and Li 4-x Mn 2 O 5 with a disordered rock salt structure (LMO), was conducted to determine the origins of the observed anomalously high charge and discharge capacity in lithium cells, which can exceed 350 mA h g -1 . Using soft and hard X-ray absorption spectroscopy (XAS), mapping of resonant inelastic X-ray scattering (mRIXS), and X-ray Raman spectroscopy (XRS), it was determined that electrochemical decomposition of Li 2 O upon charge and reduction of Mn to below 3+ during discharge is responsible for the capacities that are observed, with no evidence of contributions from reversible oxygen redox. Here, the over-reduction is exacerbated when charging limits of 4.5–4.8 V are used due to side reactions between electrolytic solution and the highly oxidized active material. These side reactions result in dissolution of Mn at room temperature and release of oxygen and other gases during initial cycles, which, in turn, cause rapid capacity fading. This is accompanied by evolution of the voltage profile upon cycling towards one that resembles that of manganese oxide spinels. The cycling behavior can be improved somewhat by reducing the upper voltage limit, although this results in a diminishment of the discharge capacities below 200 mA h g -1 . By adding various amounts of spinel LiMn 2 O 4 during synthesis, it was possible to produce LMOs with rock salt structures having significantly improved cycling behavior but still having capacities in excess of 250 mA h g -1 . An optimized modified material also exhibits better rate capability and much less gas evolution during initial cycles than the unmodified LMO. Interestingly, as-made modified materials generally exhibited lower than expected average Mn oxidation states attributable to oxygen loss during the synthesis process, as well as higher capacities than expected based on their manganese contents. The oxygen loss during processing may reduce the activity of the remaining oxygen and account for the lower reactivity of the spinel-modified material.

25 ENERGY STORAGE↗
DOE OSTI2025

Reversible enzyme-catalysed NAD + /NADH electrochemistry

The formate dehydrogenase subcomplex FdsBG from Cupriavidus necator has been electrochemically activated to reversibly interconvert NAD + /NADH and provide unique insight to its kinetics and reactivity.

Giang, Peter D. [School of Chemistry and Molecular↗
DOE OSTI2018

Observation of trapped-electron-mode microturbulence in reversed field pinch plasmas

Density fluctuations in the large-density-gradient region of improved confinement Madison Symmetric Torus reversed field pinch (RFP) plasmas exhibit multiple features that are characteristic of the trapped-electron mode (TEM). Core transport in conventional RFP plasmas is governed by magnetic stochasticity stemming from multiple long-wavelength tearing modes. Using inductive current profile control, these tearing modes are reduced, and global confinement is increased to that expected for comparable tokamak plasmas. Under these conditions, new short-wavelength fluctuations distinct from global tearing modes appear in the spectrum at a frequency of f ~ 50 kHz, which have normalized perpendicular wave numbers k ⊥ ρ s ≲0.2 and propagate in the electron diamagnetic drift direction. They exhibit a critical-gradient threshold, and the fluctuation amplitude increases with the local electron density gradient. These characteristics are consistent with predictions from gyrokinetic analysis using the Gene code, including increased TEM turbulence and transport from the interaction of remnant tearing magnetic fluctuations and zonal flow.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Fast ion transport in the quasi-single helical reversed-field pinch

The reversed-field pinch (RFP) can spontaneously transition from an axisymmetric magnetic topology to a 3D-helical geometry. Investigations on fast ion transport associated with energetic particle driven Alfvén instabilities, tearing mode induced stochasticity, and neoclassical effects have been performed on the Madison Symmetric Torus. STELLGAP produced shear-Alfvén continua seeded with V3FIT 3D-equilibrium reconstructions describe the response of Alfvénic bursting activity as a direct consequence of the equilibrium change on the fast ion resonance. Furthermore, far infrared interferometry resolved electron density perturbations associated with the bursts provide a spatial measurement of the mode structure and support the reconstructions. The bursts produce no global resonant fast ion transport; however, their disappearance at a high core-resonant amplitude implies other transport mechanisms at play. Additionally, neutral particle analysis and neutron signals suggest fast ion losses at sufficient core tearing mode strength, supporting the lack of Alfvénic activity. The guiding-center code ORBIT corroborates rapid fast ion loss times in the helical state largely as a consequence of remnant tearing modes. Additionally, ORBIT simulations demonstrate little neoclassical enhancement of particle transport. While superbanana orbits may exist, the growth in the core-resonant fast ion island and the associated secondary mode overlap govern the largest transport process, leading to robust fast ion losses in the 3D-RFP.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Global simulation of ion temperature gradient instabilities in a field-reversed configuration

We investigate the global properties of drift waves in the beam driven field-reversed configuration (FRC), the C2-U device, in which the central FRC and its scrape-off layer (SOL) plasma are connected with the formation sections and divertors. The ion temperature gradient modes are globally connected and unstable across these regions, while they are linearly stable inside the FRC separatrix. The unstable global drift waves in the SOL show an axially varying structure that is less intense near the central FRC region and the mirror throat areas, while being more robust in the bad curvature formation exit areas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Persistent and reversible electrostatic control of doping in graphene/hexagonal boron nitride heterostructures

Since its first application as a substrate for graphene field effect transistors (FETs), hexagonal boron nitride (hBN) has become a prominent component in two-dimensional (2D) material devices. In addition, hBN has been shown to host defects that can be manipulated to change the electronic properties of adjacent 2D materials. Despite the wide use of such defect manipulations, no focused efforts have been made to further the understanding of defect excitations and their influence in graphene/hBN FETs. In this study, we explore the effect of high electric fields (~10 V/nm) on graphene/hBN FETs and find that persistent and reversible shifts in graphene's charge neutrality point (CNP) occur. By increasing the applied electric field and temperature of our device, we find that this CNP shift is enhanced. With this insight, we propose a mechanism that explains these observations based on Poole–Frenkel emissions from defects in hBN. Finally, we show that such an effect may be suppressed by using graphite as a backgate, thus preventing unintended changes in the electrical properties of graphene/hBN FETs.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Reversible oxidation and reduction of gold-supported iron oxide islands at room temperature

Monolayer iron oxides grown on metal substrates have widely been used as model systems in heterogeneous catalysis. By means of ambient-pressure scanning tunneling microscopy (AP-STM), we studied the in situ oxidation and reduction of FeO(111) grown on Au(111) by oxygen (O 2 ) and carbon monoxide (CO), respectively. Oxygen dislocation lines present on FeO islands are highly active for O 2 dissociation. X-ray photoelectron spectroscopy measurements distinctly reveal the reversible oxidation and reduction of FeO islands after sequential exposure to O 2 and CO. Here, our AP-STM results show that excess O atoms can be further incorporated on dislocation lines and react with CO, whereas the CO is not strong enough to reduce the FeO supported on Au(111) that is essential to retain the activity of oxygen dislocation lines.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Time reversal symmetry breaking and odd viscosity in active fluids: Green–Kubo and NEMD results

Active fluids, which are driven at the microscale by non-conservative forces, are known to exhibit novel transport phenomena due to the breaking of time reversal symmetry. Recently, Epstein and Mandadapu [arXiv:1907.10041 (2019)] obtained Green-Kubo relations for the full set of viscous coefficients governing isotropic chiral active fluids, including the so-called odd viscosity, invoking Onsager's regression hypothesis for the decay of fluctuations in active non-equilibrium steady states. In this Communication, we test these Green-Kubo relations using molecular dynamics simulations of a canonical model system consisting of actively torqued dumbbells. We find the resulting odd and shear viscosity values from the Green-Kubo relations to be in good agreement with values measured independently through non-equilibrium molecular dynamics flow simulations. This provides a test of the Green-Kubo relations and lends support to the application of the Onsager regression hypothesis in relation to viscous behaviors of active matter systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗