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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 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Reducing Internal Resistance in Activated Carbon Supercapacitors via Exfoliated Coal-Derived Graphene Additive

Low equivalent series resistance (ESR) is critical for high-rate energy storage devices (e.g., supercapacitors), and graphene is a promising additive for reducing ESR in carbon-based supercapacitor electrodes. However, graphene can be costly and difficult to produce at scale. This study investigates the addition of graphene, produced through electrochemical exfoliation of domestic coal-derived graphite, in activated carbon-based supercapacitors. The coal-derived graphene was incorporated at varying weight loadings and tested in symmetric supercapacitors with aqueous electrolytes. ESR was evaluated using both direct current internal resistance (DCIR) and electrochemical impedance spectroscopy (EIS) measurements. DCIR measurements revealed ESR reductions of ∼34%, ∼18%, and ∼21% at 3, 5, and 10 wt % loadings, respectively, compared to the baseline (0 wt %) of ∼0.54 Ω. These results were further confirmed by EIS measurements. Correspondingly, power density increased by ∼52%, ∼27%, and ∼35% at 3, 5, and 10 wt % loadings relative to the baseline (∼29 kW/kg). Additionally, the electrodes exhibited moderate increases in specific capacitance and energy density, along with stable cycling performance (capacitance retention above 85% after 100,000 cycles) and capacitive behavior (α = 0.95−0.97), suggesting favorable charge transfer kinetics. These findings highlight the potential of exfoliated coal-derived graphene as an effective additive for supercapacitor electrodes.

capacitors↗
DOE OSTI2020

Silver Adsorption on Calcium Niobate(001) Nanosheets: Calorimetric Energies That Explain Sinter-Resistant Support

Metal nanoparticles deposited on oxide supports are essential to many technologies, including catalysts, fuel cells and electronics. Therefore, understanding the chemical bonding strength between metal nanoparticles and oxide surfaces is of great interest. The adsorption energetics, adhesion energy and adsorbate structure of Ag on dehydrated HCa 2 Nb 3 O 10 (001) nanosheets at 300 K have been studied using metal adsorption calorimetry and surface spectroscopies. These dehydrated (“dh”) calcium niobate nanosheets “(dh-HCa 2 Nb 3 O 10 (001))” have stoichiometry Ca 4 Nb 6 O 19 . They impart unusual stability to metal nanoparticles when used as catalyst supports and are easy-to-prepare by Langmuir-Blodgett (LB) techniques, highly ordered, and essentially single-crystal surfaces of mixed oxides with a huge ratio of terrace to edge sites. Below monolayer coverage, Ag grows on dh-HCa 2 Nb 3 O 10 (001) as 2D islands of thickness ~2 layers. The differential heat of Ag adsorption is initially ~303 kJ/mol, increasing slowly to ~338 kJ/mol by 0.8 ML. At higher coverages, Ag atoms mainly add on top of these 2D islands, growing 3D nanoparticles of increasing thickness, as the heat decreases asymptotically towards silver’s heat of sublimation (285 kJ/mol). The adhesion energy of Ag(s) to this Ca niobate surface is estimated to be 4.33 J/m 2 , larger than on any oxide surface previously measured. This explains the sinter resistance reported for metal nanoparticles on this support. Electron transfer from Ag into the calcium niobate is also measured. Furthermore, these results demonstrate an easy way to do singlecrystal-type surface science studies - and especially thermochemical measurements - on the complex surfaces of mixed oxides: using LB-deposited perovskite nanosheets and ultrahigh vacuum annealing in O 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Modulating the Molecular Geometry and Solution Self-Assembly of Amphiphilic Polypeptoid Block Copolymers by Side Chain Branching Pattern

Solution self-assembly of coil-crystalline diblock copolypeptoids has attracted increasing attention due to its capability to form hierarchical nanostructures with tailorable morphologies and functionalities. While the N-substituent (or side chain) structures are known to affect the crystallization of polypeptoids, their roles in dictating the hierarchical solution self-assembly of diblock copolypeptoids are not fully understood. Herein, we designed and synthesized two types of diblock copolypeptoids, i.e., poly(N-methylglycine)-b-poly(N-octylglycine) (PNMG-b-PNOG) and poly(N-methylglycine)-b-poly(N-2-ethyl-1-hexylglycine) (PNMG-b-PNEHG), to investigate the influence of N-substituent structure on the crystalline packing and hierarchical self-assembly of diblock copolypeptoids in methanol. With a linear aliphatic N-substituent, the PNOG blocks pack into a highly ordered crystalline structure with a board-like molecular geometry, resulting in the self-assembly of PNMG-b-PNOG molecules into a hierarchical microflower morphology composed of radially arranged nanoribbon subunits. By contrast, the PNEHG blocks bearing bulky branched aliphatic N-substituents are rod-like and prefer to stack into a columnar hexagonal liquid crystalline mesophase, which drives PNMG-b-PNEHG molecules to self-assemble into symmetrical hexagonal nanosheets in solution. A combination of time-dependent small/wide-angle X-ray scattering and microscopic imaging analysis further revealed the self-assembly mechanisms for the formation of these microflowers and hexagonal nanosheets. These results highlight the significant impact of the N-substituent architecture (i.e., linear versus branched) on the supramolecular self-assembly of diblock copolypeptoids in solution, which can serve as an effective strategy to tune the geometry and hierarchical structure of polypeptoid-based nanomaterials.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2021

Revealing the Dynamics and Roles of Iron Incorporation in Nickel Hydroxide Water Oxidation Catalysts

We report the surface of an electrocatalyst undergoes dynamic chemical and structural transformations under electro-chemical operating conditions. There is a dynamic exchange of metal cations between the electrocatalyst and electrolyte. Understanding how iron in the electrolyte gets incorporated in the nickel hydroxide electrocatalyst is critical for pinpointing the roles of Fe during water oxidation. Here, we report that iron incorporation and oxygen evolution reaction (OER) are highly coupled, especially at high working potentials. The iron incorporation rate is much higher at OER potentials than that at the OER dormant state (low potentials). At OER potentials, iron incorporation favors electrochemically more reactive edge sites, as visualized by synchrotron X-ray fluorescence microscopy. Using X-ray absorption spectroscopy and density functional theory calculations, we show that Fe incorporation can suppress the oxidation of Ni and enhance the Ni reducibility, leading to improved OER catalytic activity. Our findings provide a holistic approach to understanding and tailoring Fe incorporation dynamics across the electrocatalyst-electrolyte interface, thus controlling catalytic processes.

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

EELS Studies of Cerium Electrolyte Reveal Substantial Solute Concentration Effects in Graphene Liquid Cells

Graphene liquid cell transmission electron microscopy is a powerful technique to visualize nanoscale dynamics and transformations at atomic resolution. However, the solution in liquid cells is known to be affected by radiolysis, and the stochastic formation of graphene liquid cells raises questions about the solution chemistry in individual pockets. In this study, electron energy loss spectroscopy (EELS) was used to evaluate a model encapsulated solution, aqueous CeCl 3 . First, the ratio between the O K-edge and Ce M-edge was used to approximate the concentration of cerium salt in the graphene liquid cell. It was determined that the ratio between oxygen and cerium was orders of magnitude lower than what is expected for a dilute solution, indicating that the encapsulated solution is highly concentrated. To probe how this affects the chemistry within graphene liquid cells, the oxidation of Ce 3+ was measured using time-resolved parallel EELS. Here, it was determined that Ce 3+ oxidizes faster under high electron fluxes, but reaches the same steady-state Ce 4+ concentration regardless of flux. The time-resolved concentration profiles enabled direct comparison to radiolysis models, which indicate rate constants and g-values of certain molecular species are substantially different in the highly concentrated environment. Finally, electron flux-dependent gold nanocrystal etching trajectories showed that gold nanocrystals etch faster at higher electron fluxes, correlating well with the Ce 3+ oxidation kinetics. Understanding the effects of the highly concentrated solution in graphene liquid cells will provide new insight on previous studies and may open up opportunities to systematically study systems in highly concentrated solutions at high resolution.

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

Platinum Graphene Catalytic Condenser for Millisecond Programmable Metal Surfaces

Accelerating catalytic chemistry and tuning surface reactions require precise control of the electron density of metal atoms. In this work, nanoclusters of platinum were supported on a graphene sheet within a catalytic condenser device that facilitated electron or hole accumulation in the platinum active sites with negative or positive applied potential, respectively. The catalytic condenser was fabricated by depositing on top of a p-type Si wafer an amorphous HfO 2 dielectric (70 nm), on which was placed the active layer of 2–4 nm platinum nanoclusters on graphene. A potential of ±6 V applied to the Pt/graphene layer relative to the silicon electrode moved electrons into or out of the active sites of Pt, attaining charge densities more than 1% of an electron or hole per surface Pt atom. At a level of charge condensation of ±10% of an electron per surface atom, the binding energy of carbon monoxide to a Pt(111) surface was computed via density functional theory to change 24 kJ mol –1 (0.25 eV), which was consistent with the range of carbon monoxide binding energies determined from temperature-programmed desorption (ΔBE CO of 20 ± 1 kJ mol –1 or 0.19 eV) and equilibrium surface coverage measurements (ΔBE CO of 14 ± 1 kJ mol –1 or 0.14 eV). Impedance spectroscopy indicated that Pt/graphene condensers with potentials oscillating at 3000 Hz exhibited negligible loss in capacitance and charge accumulation, enabling programmable surface conditions at amplitudes and frequencies necessary to achieve catalytic resonance.

Inorganic carbon compounds↗
DOE OSTI2023

Geometric Transformations Afforded by Rotational Freedom in Aramid Amphiphile Nanostructures

Molecular self-assembly in water leads to nanostructure geometries that can be tuned owing to the highly dynamic nature of amphiphiles. There is growing interest in strongly interacting amphiphiles with suppressed dynamics, as they exhibit ultrastability in extreme environments. However, such amphiphiles tend to assume a limited range of geometries upon self-assembly due to the specific spatial packing induced by their strong intermolecular interactions. To overcome this limitation while maintaining structural robustness, we incorporate rotational freedom into the aramid amphiphile molecular design by introducing a diacetylene moiety between two aramid units, resulting in diacetylene aramid amphiphiles (D-AAs). This design strategy enables rotations along the carbon–carbon sp hybridized bonds of an otherwise fixed aramid domain. We show that varying concentrations and equilibration temperatures of D-AA in water lead to self-assembly into four different nanoribbon geometries: short, extended, helical, and twisted nanoribbons, all while maintaining robust structure with thermodynamic stability. In conclusion, we use advanced microscopy, X-ray scattering, spectroscopic techniques, and two-dimensional (2D) NMR to understand the relationship between conformational freedom within strongly interacting amphiphiles and their self-assembly pathways.

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

Twisto-Electrochemical Activity Volcanoes in Trilayer Graphene

In this work, we develop a twist-dependent electrochemical activity map, combining a low-energy continuum electronic structure model with modified Marcus–Hush–Chidsey kinetics in trilayer graphene. We identify a counterintuitive rate enhancement region spanning the magic angle curve and incommensurate twists in the system geometry. We find a broad activity peak with a ruthenium hexamine redox couple in regions corresponding to both magic angles and incommensurate angles, a result qualitatively distinct from the twisted bilayer case. Flat bands and incommensurability offer new avenues for reaction rate enhancements in electrochemical transformations.

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

Mo Atom Rearrangement Drives Layer-Dependent Reactivity in Two-Dimensional MoS 2

Two-dimensional (2D) materials offer a valuable platform for manipulating and studying chemical reactions at the atomic level, owing to the ease of controlling their microscopic structure at the nanometer scale. While extensive research has been conducted on the structure-dependent chemical activity of 2D materials, the influence of structural transformation during the reaction has remained largely unexplored. In this work, we report the layer-dependent chemical reactivity of MoS 2 during a nitridation atomic substitution reaction and attribute it to the rearrangement of Mo atoms. Our results show that the chemical reactivity of MoS 2 decreases as the number of layers is reduced in the few-layer regime. In particular, monolayer MoS 2 exhibits significantly lower reactivity compared with its few-layer and multilayer counterparts. Atomic-resolution transmission electron microscopy (TEM) reveals that MoN nanonetworks form as reaction products from monolayer and bilayer MoS 2 , with the continuity of the MoN crystals increasing with layer number, consistent with the local conductivity mapping data. The layer-dependent reactivity is attributed to the relative stability of the hypothetically formed MoN phase, which retains the number of Mo atomic layers present in the precursor. Specifically, the low chemical reactivity of monolayer MoS 2 is attributed to the high energy cost associated with Mo atom diffusion and migration necessary to form multilayer Mo lattices in the thermodynamically stable MoN phase. In conclusion, this study underscores the critical role of lattice rearrangement in governing chemical reactivity and highlights the potential of 2D materials as versatile platforms for advancing the understanding of materials chemistry at the atomic scale.

Chemical reactivity↗
DOE OSTI2025

Modulation of the Electronic and Vibrational Landscape in Lead Organic Chalcogenides

Metal organic chalcogenides (MOCs) are an emerging class of two-dimensional (2D) materials featuring tunable band gaps and strong light-matter interactions with great potential for optical and polaritonic applications. Lead organic chalcogenides (LOCs) stand out among MOCs for sustaining long-lived coherent optical phonons despite their distorted lattices. However, the strong electron–phonon coupling also leads to rapid charge carrier self-trapping, hindering carrier transport. Herein, we demonstrate that charge carrier self-trapping is suppressed in Se- and Te-based LOCs. Specifically, the expansive Se and Te orbitals give rise to more dispersive conduction bands and reduced electron effective masses, thereby mitigating carrier self-trapping. As a result of reduced carrier self-trapping, the Se- and Te-based LOCs exhibit enhanced band-to-band photoluminescence and improved charge transport performance. Furthermore, our results provide a synthetic route to Se- and Te-based LOC single crystals and demonstrate the potential of orbital engineering to tune their electronic and phononic properties.

Chalcogenides↗
DOE OSTI2020

Phonon-exciton Interactions in WSe 2 under a quantizing magnetic field

Strong many-body interaction in two-dimensional transitional metal dichalcogenides provides a unique platform to study the interplay between different quasiparticles, such as prominent phonon replica emission and modified valley-selection rules. A large out-of-plane magnetic field is expected to modify the exciton-phonon interactions by quantizing excitons into discrete Landau levels, which is largely unexplored. Here, we observe the Landau levels originating from phonon-exciton complexes and directly probe exciton-phonon interaction under a quantizing magnetic field. Phonon-exciton interaction lifts the inter-Landau-level transition selection rules for dark trions, manifested by a distinctively different Landau fan pattern compared to bright trions. This allows us to experimentally extract the effective mass of both holes and electrons. The onset of Landau quantization coincides with a significant increase of the valley-Zeeman shift, suggesting strong many-body effects on the phonon-exciton interaction. Our work demonstrates monolayer WSe 2 as an intriguing playground to study phonon-exciton interactions and their interplay with charge, spin, and valley.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Lithium-ion electrolytic substrates for sub-1V high-performance transition metal dichalcogenide transistors and amplifiers

Electrostatic gating of two-dimensional (2D) materials with ionic liquids (ILs), leading to the accumulation of high surface charge carrier densities, has been often exploited in 2D devices. However, the intrinsic liquid nature of ILs, their sensitivity to humidity, and the stress induced in frozen liquids inhibit ILs from constituting an ideal platform for electrostatic gating. Here we report a lithium-ion solid electrolyte substrate, demonstrating its application in high-performance back-gated n-type MoS 2 and p-type WSe 2 transistors with sub-threshold values approaching the ideal limit of 60 mV/dec and complementary inverter amplifier gain of 34, the highest among comparable amplifiers. Remarkably, these outstanding values were obtained under 1 V power supply. Microscopic studies of the transistor channel using microwave impedance microscopy reveal a homogeneous channel formation, indicative of a smooth interface between the TMD and underlying electrolytic substrate. These results establish lithium-ion substrates as a promising alternative to ILs for advanced thin-film devices.

42 ENGINEERING↗