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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 163 records · Page 9

Coupling Amorphization and Compositional Optimization of Ternary Metal Phosphides toward High-Performance Electrocatalytic Hydrogen Production

Amorphous materials, with abundant active sites and unique electronic configurations, have the potential to outperform their crystalline counterparts in high-performance catalysis for clean energy. However, their synthesis and compositional optimization remain underexplored due to the strict conditions required for their formation. Here, in this study, we report the synthesis of ternary platinum-nickel-phosphorus (PtNiP) amorphous nanoparticles (ANPs) within milliseconds by flash Joule heating, which features ultrafast cooling that enables the vitrification of metal precursors. Through compositional optimization, the Gibbs free energy of hydrogen adsorption for Pt 4 Ni 4 P 1 ANPs is optimized at 0.02 eV, an almost ideal value, even surpassing that of the benchmark metallic platinum catalyst. As a result, the PtNiP ANPs exhibited superior activity in electrocatalytic hydrogen evolution in acid electrolyte (η 10 ∼ 14 mV, Tafel slope ∼ 18 mV dec –1 , and mass activity 5× higher than state-of-the-art Pt/C). Life-cycle assessment and technoeconomic analysis suggest that, compared to existing processes, our approach enables notable reductions in greenhouse gas emission, energy consumption, and production cost for practical electrolyzer catalyst manufacturing.

36 MATERIALS SCIENCE↗

Photoredox Catalysis with Spin Magnetic Field Effects: A Scheme for Chiral Resolution

Quantities that break both mirror symmetry and time-reversal symmetry, such as the orbital angular momentum, are known to connect molecular chirality with an applied magnetic field. This concept has led to observations such as magneto-chiral dichroism and chirality-induced spin selectivity (CISS). However, being small, these effects often require additional amplification procedures such as flow chemistry to achieve bulk enantioseparation. In this work, we demonstrate how the magnetic field effect on photogenerated radical pairs, which also breaks time-reversal symmetry, can be harnessed for enantiopurification. Fundamental to this process is the collective decay of the singlet and triplet radical-pair states made possible by an applied magnetic field. Because opposite enantiomers exhibit spin-orbit coupling matrix elements of opposite signs, the singlet and triplet decay channels interfere constructively in one enantiomer. Meanwhile, molecules of the other enantiomer are funnelled into the first enantiomer through excited-state chirality inversion, achieving (dynamic kinetic) chiral resolution. Using an axially chiral binaphthyl derivative and a borane photosensitizer as prototype, we predict an appreciable enantiomeric excess (e.e.) of 90% to be possible at steady state, attained within hundreds of milliseconds when irradiated by a laser. Importantly, our analytical results showcase regimes of perfect enantioselectivity (100% e.e.), accessible by further chemical optimization of the photosensitizer for which general strategies are discussed. Altogether, this work illustrates a so-far untapped but powerful control knob for photoredox catalysis based on spin chemistry principles.

Magnetic properties↗

Combined Optical and Radio-Frequency Perspectives on a Hybrid Cloud-To-Ground Lightning Flash Observed by the FORTE Satellite

In this work, we use the coincident optical and radio-frequency (RF) measurements taken by the Fast On-orbit Recording of Transient Events (FORTE) satellite to shed light on common optical signatures recorded by NASA and NOAA lightning imagers during Cloud-to-Ground (CG) lightning. We build flash cluster data for FORTE using the same techniques as the NASA/NOAA instruments to document the optical/RF evolution of an oceanic hybrid -CG flash. The flash began with strong Very High Frequency (VHF)-band emission from a Narrow Bipolar Event (NBE) that initiated a period of normal bilevel intracloud (IC) activity in two vertical layers (8 and 12 km) that lasted for 490 ms. VHF waveforms show step leader activity ahead of the return stroke. All impulsive VHF sources after the stroke come from the lower (8 km) layer. K-changes are noted following the return stroke, but no subsequent strokes are detected. The optical flash began 136 ms after the NBE RF pulse. Twenty-two of the 33 optical groups were dim and occurred during the in-cloud phase of the flash. This activity included both isolated pulses and sustained periods of illumination over tens of milliseconds. Initial cloud pulses accounted for 23% of the total optical radiance from the flash. Illumination during the return stroke contributed 58% of the total radiance, and the K-changes and cloud pulses after the stroke supplied the remaining 19%. These results highlight the benefit of having RF alongside optical lightning measurements for clarifying signatures in the optical data and providing information on their physical origins.

54 ENVIRONMENTAL SCIENCES↗

Insights Into Lightning K‐Leader Initiation and Development From Three Dimensional Broadband Interferometric Observations

Abstract We report detailed observations of K‐leaders and the activity between them with the three‐dimensional Broadband Interferometric Mapping and Polarization system (BIMAP‐3D) at Los Alamos National Laboratory. It is found that K‐leaders have a general propagation trend of initial acceleration and then gradual deceleration, and the corresponding very high frequency (VHF) radiation power is exponentially correlated with the leader speed. Based on the 3D development and simultaneous electric field change measurement, some simple K‐leaders can be modeled with time‐evolving point charges at the propagating leader tip and at the stationary origin. We found that the charge magnitude increases during the initial acceleration stage and stays relatively constant for the rest of the development. K‐leaders are observed to interact with other branches; the branches affect the leader's propagation speed, and may affect the charge transfer. After the occurrence of a K‐leader, VHF emissions are quenched for several milliseconds. VHF sources then reappear in an impulsive and scattered manner as “twinkling,” and these sources are found not uniquely on the so‐called needles, but also on the main channel. These twinkling sources start near the apparent positive leader tip, and extend back toward the direction of the flash origin at about 10 5 m/s, while the apparent positive tip continues to extend forward at about 10 4 m/s. The twinkling extending toward the direction of flash origin appears to initiate the following K‐leader, although it may be interrupted by a K‐leader along a different branch, or simply die out without more K‐leader activity.

54 ENVIRONMENTAL SCIENCES↗

Ultracompact 3D microfluidics for time-resolved structural biology

To advance microfluidic integration, we present the use of two-photon additive manufacturing to fold 2D channel layouts into compact free-form 3D fluidic circuits with nanometer precision. We demonstrate this technique by tailoring microfluidic nozzles and mixers for time-resolved structural biology at X-ray free-electron lasers (XFELs). We achieve submicron jets with speeds exceeding 160 ms -1 , which allows for the use of megahertz XFEL repetition rates. By integrating an additional orifice, we implement a low consumption flow-focusing nozzle, which is validated by solving a hemoglobin structure. Also, aberration-free in operando X-ray microtomography is introduced to study efficient equivolumetric millisecond mixing in channels with 3D features integrated into the nozzle. Such devices can be printed in minutes by locally adjusting print resolution during fabrication. This technology has the potential to permit ultracompact devices and performance improvements through 3D flow optimization in all fields of microfluidic engineering.

3-D reconstruction↗

Polymerization and editing modes of a high-fidelity DNA polymerase are linked by a well-defined path

Proofreading by replicative DNA polymerases is a fundamental mechanism ensuring DNA replication fidelity. In proofreading, mis-incorporated nucleotides are excised through the 3'-5' exonuclease activity of the DNA polymerase holoenzyme. The exonuclease site is distal from the polymerization site, imposing stringent structural and kinetic requirements for efficient primer strand transfer. Yet, the molecular mechanism of this transfer is not known. Here we employ molecular simulations using recent cryo-EM structures and biochemical analyses to delineate an optimal free energy path connecting the polymerization and exonuclease states of E. coli replicative DNA polymerase Pol III. We identify structures for all intermediates, in which the transitioning primer strand is stabilized by conserved Pol III residues along the fingers, thumb and exonuclease domains. We demonstrate switching kinetics on a tens of milliseconds timescale and unveil a complete pol-to-exo switching mechanism, validated by targeted mutational experiments.

59 BASIC BIOLOGICAL SCIENCES↗

A multi-step nucleation process determines the kinetics of prion-like domain phase separation

Compartmentalization by liquid-liquid phase separation (LLPS) has emerged as a ubiquitous mechanism underlying the organization of biomolecules in space and time. Here, we combine rapid-mixing time-resolved small-angle X-ray scattering (SAXS) approaches to characterize the assembly kinetics of a prototypical prion-like domain with equilibrium techniques that characterize its phase boundaries and the size distribution of clusters prior to phase separation. We find two kinetic regimes on the micro- to millisecond timescale that are distinguished by the size distribution of clusters. At the nanoscale, small complexes are formed with low affinity. After initial unfavorable complex assembly, additional monomers are added with higher affinity. At the mesoscale, assembly resembles classical homogeneous nucleation. Careful multi-pronged characterization is required for the understanding of condensate assembly mechanisms and will promote understanding of how the kinetics of biological phase separation is encoded in biomolecules.

59 BASIC BIOLOGICAL SCIENCES↗

Urban mining by flash Joule heating

Abstract Precious metal recovery from electronic waste, termed urban mining, is important for a circular economy. Present methods for urban mining, mainly smelting and leaching, suffer from lengthy purification processes and negative environmental impacts. Here, a solvent-free and sustainable process by flash Joule heating is disclosed to recover precious metals and remove hazardous heavy metals in electronic waste within one second. The sample temperature ramps to ~3400 K in milliseconds by the ultrafast electrical thermal process. Such a high temperature enables the evaporative separation of precious metals from the supporting matrices, with the recovery yields >80% for Rh, Pd, Ag, and >60% for Au. The heavy metals in electronic waste, some of which are highly toxic including Cr, As, Cd, Hg, and Pb, are also removed, leaving a final waste with minimal metal content, acceptable even for agriculture soil levels. Urban mining by flash Joule heating would be 80× to 500× less energy consumptive than using traditional smelting furnaces for metal-component recovery and more environmentally friendly.

01 COAL, LIGNITE, AND PEAT↗

Long-lived electronic spin qubits in single-walled carbon nanotubes

Abstract Electron spins in solid-state systems offer the promise of spin-based information processing devices. Single-walled carbon nanotubes (SWCNTs), an all-carbon one-dimensional material whose spin-free environment and weak spin-orbit coupling promise long spin coherence times, offer a diverse degree of freedom for extended range of functionality not available to bulk systems. A key requirement limiting spin qubit implementation in SWCNTs is disciplined confinement of isolated spins. Here, we report the creation of highly confined electron spins in SWCNTs via a bottom-up approach. The record long coherence time of 8.2 µs and spin-lattice relaxation time of 13 ms of these electronic spin qubits allow demonstration of quantum control operation manifested as Rabi oscillation. Investigation of the decoherence mechanism reveals an intrinsic coherence time of tens of milliseconds. These findings evident that combining molecular approaches with inorganic crystalline systems provides a powerful route for reproducible and scalable quantum materials suitable for qubit applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Heterogeneity in M. tuberculosis β-lactamase inhibition by Sulbactam

Abstract For decades, researchers have elucidated essential enzymatic functions on the atomic length scale by tracing atomic positions in real-time. Our work builds on possibilities unleashed by mix-and-inject serial crystallography (MISC) at X-ray free electron laser facilities. In this approach, enzymatic reactions are triggered by mixing substrate or ligand solutions with enzyme microcrystals. Here, we report in atomic detail (between 2.2 and 2.7 Å resolution) by room-temperature, time-resolved crystallography with millisecond time-resolution (with timepoints between 3 ms and 700 ms) how the Mycobacterium tuberculosis enzyme BlaC is inhibited by sulbactam (SUB). Our results reveal ligand binding heterogeneity, ligand gating, cooperativity, induced fit, and conformational selection all from the same set of MISC data, detailing how SUB approaches the catalytic clefts and binds to the enzyme noncovalently before reacting to a trans- enamine. This was made possible in part by the application of singular value decomposition to the MISC data using a program that remains functional even if unit cell parameters change up to 3 Å during the reaction.

74 ATOMIC AND MOLECULAR PHYSICS↗

Flash healing of laser-induced graphene

The advancement of laser-induced graphene (LIG) technology has streamlined the fabrications of flexible graphene devices. However, the ultrafast kinetics triggered by laser irradiation generates intrinsic amorphous characteristics, leading to high resistivity and compromised performance in electronic devices. Healing graphene defects in specific patterns is technologically challenging by conventional methods. Herein, we report the rapid rectification of LIG’s topological defects by flash Joule heating in milliseconds (referred to as F-LIG), whilst preserving its overall structure and porosity. The F-LIG exhibits a decreased I D /I G ratio from 0.84 – 0.33 and increased crystalline domain from Raman analysis, coupled with a 5-fold surge in conductivity. Pair distribution function and atomic-resolution imaging delineate a broader-range order of F-LIG with a shorter C-C bond of 1.425 Å. The improved crystallinity and conductivity of F-LIG with excellent flexibility enables its utilization in high-performance soft electronics and low-voltage disinfections. Notably, our F-LIG/polydimethylsiloxane strain sensor exhibits a gauge factor of 129.3 within 10% strain, which outperforms pristine LIG by 800%, showcasing significant potential for human-machine interfaces.

36 MATERIALS SCIENCE↗

Recycling polyolefin plastic waste at short contact times via rapid joule heating

Abstract The chemical deconstruction of polyolefins to fuels, lubricants, and waxes offers a promising strategy for mitigating their accumulation in landfills and the environment. Yet, achieving true recyclability of polyolefins into C 2 -C 4 monomers with high yields, low energy demand, and low carbon dioxide emissions under realistic polymer-to-catalyst ratios remains elusive. Here, we demonstrate a single-step electrified approach utilizing Rapid Joule Heating over an H-ZSM-5 catalyst to efficiently deconstruct polyolefin plastic waste into light olefins (C 2 -C 4 ) in milliseconds, with high productivity at much higher polymer-to-catalyst ratio than prior work. The catalyst is essential in producing a narrow distribution of light olefins. Pulsed operation and steam co-feeding enable highly selective deconstruction (product fraction of >90% towards C 2 -C 4 hydrocarbons) with minimal catalyst deactivation compared to Continuous Joule Heating. This laboratory-scale approach demonstrates effective deconstruction of real-life waste materials, resilience to additives and impurities, and versatility for circular polyolefin plastic waste management.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nondestructive flash cathode recycling

Effective recycling of end-of-life Li-ion batteries (LIBs) is essential due to continuous accumulation of battery waste and gradual depletion of battery metal resources. The present closed-loop solutions include destructive conversion to metal compounds, by destroying the entire three-dimensional morphology of the cathode through continuous thermal treatment or harsh wet extraction methods, and direct regeneration by lithium replenishment. Here, we report a solvent- and water-free flash Joule heating (FJH) method combined with magnetic separation to restore fresh cathodes from waste cathodes, followed by solid-state relithiation. The entire process is called flash recycling. This FJH method exhibits the merits of milliseconds of duration and high battery metal recovery yields of ~98%. After FJH, the cathodes reveal intact core structures with hierarchical features, implying the feasibility of their reconstituting into new cathodes. Relithiated cathodes are further used in LIBs, and show good electrochemical performance, comparable to new commercial counterparts. Life-cycle-analysis highlights that flash recycling has higher environmental and economic benefits over traditional destructive recycling processes.

25 ENERGY STORAGE↗

Spin switchable optical phenomena in Rashba band structures through intersystem crossing in momentum space in solution-processing 2D-superlattice perovskite film

Spin-switchable phenomena are a critical element for the development of spintronic and chiroptic devices. Herein we combine a 2D-superlattice perovskite (4,4-DFPD2PbI4) film with a ferromagnetic cobalt (Co) layer to form a multiferroic perovskite/Co interface, and demonstrate spin-switchable circularly polarized luminescence (CPL) between right-handed σ+ and left-handed σ− polarizations. When the ferromagnetic spins of Co at the Co/perovskite interface are altered between positive and negative magnetic field directions, the CPL from the 2D-superlattice perovskite switches from σ+ to σ− polarization. The magnetic field effects present a unique method to confirm that CPL is generated by the circular-orbital momentum of light-emitting excitons within Rashba band structures, eliminating artifacts involving structural birefringence. Our polarized neutron reflectometry measurements confirm a super long-range spin-orbit interaction occurring in the 2D-superlattice perovskite films. The temperature dependence of spin-switchable phenomenon indicates an extraordinarily long orbital polarization lifetime, reaching microseconds at room temperature and milliseconds at 5 K.

36 MATERIALS SCIENCE↗

Non-Markovian relaxation spectroscopy of fluxonium qubits

Recent studies have shown that parasitic two-level systems (TLS) in superconducting qubits, which are a leading source of decoherence, can have relaxation times longer than the qubits themselves. However, the standard techniques used to characterize qubit relaxation is only valid for measuring T 1 under the Born-Markov approximation and could mask environmental memory effects in practice. Here, we introduce two-timescale relaxometry, a technique to probe the qubit and environment relaxation simultaneously and efficiently. We apply it to high-coherence fluxonium qubits over a frequency range of 0.1-0.4 GHz, and reveal a discrete spectrum of TLS with millisecond lifetimes. Our analysis of the spectrum is consistent with a random distribution of TLS in the aluminum oxide tunnel barrier of the Josephson junction chain of the fluxonium, with a spectral and volumetric density and average electric dipole similar to previous TLS studies at much higher frequencies. Our study suggests that investigating and mitigating TLS in the junction chain is crucial to the development of various types of noise-protected qubits in circuit QED.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Machine learning pipeline for denoising low signal-to-noise ratio and out-of-distribution transmission electron microscopy datasets

High-resolution transmission electron microscopy (HRTEM) is crucial for observing material’s structural and morphological evolution at Angstrom scales, but the electron beam can alter these processes. Devices such as CMOS-based direct-electron detectors operating in electron-counting mode can be utilized to substantially reduce the electron dosage. However, the resulting images often lead to a low signal-to-noise ratio, which requires frame integration that sacrifices temporal resolution. Several machine learning (ML) models have been recently developed to successfully denoise HRTEM images. Yet, these models are often computationally expensive, and their inference speeds on GPUs are outpaced by the imaging speed of advanced detectors, precluding in situ analysis. Furthermore, the performance of these denoising models on datasets with imaging conditions that deviate from the training datasets has not been evaluated. To mitigate these gaps, we propose a new self-supervised ML denoising pipeline specifically designed for time-series HRTEM images. This pipeline integrates a blind-spot convolution neural network with pre-processing and post-processing steps, including drift correction and low-pass filtering. Results demonstrate that our model outperforms various other ML and non-ML denoising methods in noise reduction and contrast enhancement, leading to improved visual clarity of atomic features. Additionally, the model is drastically faster than U-Net-based ML models and demonstrates excellent out-of-distribution generalization. The model’s computational inference speed is in the order of milliseconds per image, rendering it suitable for application in in-situ HRTEM experiments.

36 MATERIALS SCIENCE↗

Photonic curing of solution-deposited ZrO 2 dielectric on PEN: a path towards high-throughput processing of oxide electronics

High-throughput manufacturing of oxide electronics will enable new applications ranging from large-area displays to flexible medical devices and low-cost solar panels. However, high quality oxide films from solution-based precursors typically require 20 minutes or more of thermal annealing at high temperature (> 250 °C) for each layer, severely limiting both the throughput and substrate choice. Here, we report high speed photonic curing of ZrO 2 dielectric thin films on flexible plastic substrates. The curing and patterning processes can be achieved simultaneously by using shadow mask patterning or adjusting conditions to convert oxide only on top of underlying metal contacts, i.e. self-aligned patterning. Metal-insulator-metal capacitors using two layers of ZrO 2 films photonically cured in just 100 seconds per layer show non-dispersive capacitance-frequency behavior from 10 2 to 10 6 Hz, high areal capacitance of 200 nF/cm 2 and low dissipation factor of 0.03 at 10 5 Hz, leakage current density of ~ 10 -7 A/cm 2 at an applied field of 2 MV/cm, and a breakdown field of nearly 8 MV/cm. Using an upgraded tool, similar dielectric properties are achieved in as short as 100 milliseconds using a single pulse of light, revealing a pathway to oxide film processing beyond 30 m/min.

14 SOLAR ENERGY↗

Symmetry-mediated quantum coherence of W 5+ spins in an oxygen-deficient double perovskite

Elucidating the factors limiting quantum coherence in real materials is essential to the development of quantum technologies. Here we report a strategic approach to determine the effect of lattice dynamics on spin coherence lifetimes using oxygen deficient double perovskites as host materials. In addition to obtaining millisecond T 1 spin-lattice lifetimes at T ~ 10 K, measurable quantum superpositions were observed up to room temperature. We determine that T 2 enhancement in Sr 2 CaWO 6-δ over previously studied Ba 2 CaWO 6-δ is caused by a dynamically-driven increase in effective site symmetry around the dominant paramagnetic site, assigned as W 5+ via electron paramagnetic resonance spectroscopy. Further, a combination of experimental and computational techniques enabled quantification of the relative strength of spin-phonon coupling of each phonon mode. This analysis demonstrates the effect of thermodynamics and site symmetry on the spin lifetimes of W 5+ paramagnetic defects, an important step in the process of reducing decoherence to produce longer-lived qubits.

36 MATERIALS SCIENCE↗