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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 667 records · Page 37
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Pseudocapacitive Titanium Oxynitride Nanowires for Ultrahigh Capacitance Supercapacitors

High-quality, multifunctional two-dimensional (2D) titanium oxynitide (TiNO) thin films and one-dimensional (1D) TiNO nanowires have been synthesized using a pulsed laser deposition, a simple, fast, and congruent evaporation method. First-principles calculations as a function of surface orientation and termination indicate that surface oxidation of TiNO nanowires can stabilize the (110) orientation observed experimentally. The specific capacitance value for the TiNO nanowire samples (2725 mF/cm 2 ) has been found to be nearly six times more than that of the TiNO thin film samples (400 mF/cm 2 ), which is attributed to the high packing density of TiNO nanowires over a given area. The nanowire samples have also been found to exhibit a significantly higher energy density (1.35 μWh/cm 2 ) than the TiNO thin-film samples (0.33 μWh/cm 2 ). Thus, the TiNO material system in thin-film and nanowire forms has been demonstrated to be a promising candidate for use as an electrode material in supercapacitors and other charge-storage applications.

capacitors↗
DOE OSTI2020

Predicting the Activity and Selectivity of Bimetallic Metal Catalysts for Ethanol Reforming using Machine Learning

Machine learning is ideally suited for the pattern detection in large uniform datasets, but consistent experimental datasets on catalyst studies are often small. Here we demonstrate how a combination of machine learning and first-principles calculations can be used to extract knowledge from a relatively small set of experimental data. The approach is based on combining a complex machine-learning model trained on an extensive computational library of transition-state energies with simple linear regression models of experimental catalytic activities and selectivities from the literature. Using the combined model, we identify the key C–C bond scission reactions involved in ethanol reforming and perform a computational screening for ethanol reforming on monolayer bimetallic catalysts with architectures TM-Pt-Pt(111) and Pt-TM-Pt(111) (TM = 3d transition metals). The model also predicts four promising catalyst compositions for future experimental studies. In conclusion, the approach is not limited to ethanol reforming but is of general use for the interpretation of experimental observations as well as for the computational discovery of novel catalytic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Hydrogen Evolution on Restructured B-Rich WB: Metastable Surface States and Isolated Active Sites

Borides have been recently identified to be a class of earth-abundant and low-cost materials that are surprisingly active toward oxidative dehydrogenation and hydrogen evolution reaction (HER) catalysis. Here, we explain from first-principles calculations the HER activity of WB, an industrial material known for its superior physical properties and chemical inertness. We find that, compared to bulk termination, a major surface reconstruction takes place, leading to the off-stoichiometric B-rich surface termination that contains the active sites. The hydrogen adsorbate configurations are further investigated under various adsorbate coverages. Many competing configurations appear to be accessible in reaction conditions, and thus, a grand canonical ensemble is established to describe the catalytic system. A phase diagram of adsorbate coverages is constructed as a function of pH and the applied potential. A complex reaction network is presented based on the ensemble-averaged reaction rates, and the electrocatalytic activities are evaluated under different overpotentials. Here, the major contributors to the activity are found to be a few metastable surface states with a distinct electronic structure that are only accessible at high adsorbate coverages in reaction conditions. In addition, while the activity of the dominant active site is nearly the same as that on the unreconstructed WB, the B-rich formations play an important role of isolating the active sites and preventing the passivation of the surface with H 2 bubble formation.

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

Entropic Control of HD Exchange Rates over Dilute Pd-in-Au Alloy Nanoparticle Catalysts

Dilute Pd-in-Au alloy catalysts are promising materials for selective hydrogenation catalysis. Extensive surface science studies have contributed mechanistic insight on the energetic aspect of hydrogen dissociation, migration and recombination on dilute alloy systems. Yet, translating these fundamental concepts to the kinetics and free energy of hydrogen dissociation on nanoparticle catalysts operating at ambient pressures and temperatures remains challenging. Here, the effect of the Pd concentration and Pd ensemble size on the catalytic activity, apparent activation energy and rate limiting process is addressed by combining experiment and theory. Experiments in a flow reactor show that a compositional change from 4 to 8 atm% Pd of the Pd-in-Au alloy catalyst leads to strong increase in activity, even exceeding the activity per Pd atom of monometallic Pd under the same conditions, albeit with an increase in apparent activation energy. First-principles calculations show that the rate and apparent activation enthalpy for HD exchange increase when increasing the Pd ensemble size from single Pd atoms to Pd trimers in a Au surface, suggesting that the ensemble size distribution shifts from mainly single Pd atoms on the 4 atm% Pd alloy to larger Pd ensembles of at least three atoms for the 8 atm% Pd/Au catalyst. The DFT studies also indicated that the rate-controlling process is different: H 2 (D 2 ) dissociation determines the rate for single atoms whereas recombination of adsorbed H and D determines the rate on Pd trimers. Both experiment and theory suggest that the increased reaction rate with increasing Pd content and ensemble size stems from an entropic driving force. Lastly, our results support hydrogen migration between Pd sites via Au and indicate that the dilute alloy design prevents the formation of subsurface hydrogen, which is crucial in achieving high selectivity in hydrogenation catalysis.

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

Hydrogen Dissociation Controls 1-Hexyne Selective Hydrogenation on Dilute Pd-in-Au Catalysts

Increasing the selectivity of the catalytic hydrogenation of alkynes to alkenes is of major importance for the processing of petrochemicals and the production of fine chemicals. Achieving high selectivity for alkene formation at high conversions, however, remains a long-standing challenge in heterogeneous catalysis. Here, the mechanism and origin of the high selectivity of dilute Pd-in-Au catalysts has been studied by a combination of first-principles calculations, microkinetic simulations, and isotopic exchange hydrogenation experiments using Pd 0.04 Au 0.96 nanoparticles embedded in raspberry colloid-templated silica. The Pd is predominantly in the form of isolated atoms, only surrounded by Au atoms, based on prior studies. The simulations indicate that the rate-limiting process for 1-hexyne hydrogenation on Pd monomers in Au(111) is H 2 dissociation, which has a large free energy barrier of 0.86 eV at 363 K and 0.2 bar of H 2 . The C–H bond formation steps, on the other hand, proceed with lower barriers, which contrasts with previous studies of extended Pd catalysts. The microkinetic simulations identify the sizable H 2 dissociation barrier and the small barrier for the hydrogenation of 1-hexyne as key factors that lead to a high selectivity for the production of 1-hexene from 1-hexyne, even at high conversion. The unconventional H 2 dissociation limiting process in combination with the low coverage of weakly bound hydrocarbon intermediates explains the near-zero order of 1-hexyne found experimentally. Furthermore, the partial hydrogenation of 1-hexyne to form 1-hexene is shown to be an irreversible process from our isotopic exchange hydrogenation experiments and is explained by the strongly exothermic nature of the reaction. Diluting active species, like Pd, in a less active host metal, like Au, hence appears promising as a means of tuning the binding energy of reactants and altering reaction profiles, leading to distinct kinetic behavior for an optimal catalytic activity and selectivity. Furthermore, the combination of microkinetic modeling, density functional theory calculations, and isotopic exchange experiments is thus demonstrated to be an effective approach to modeling important catalytic phenomena.

1-hexyne↗
DOE OSTI2020

Arylammonium-Assisted Reduction of the Open-Circuit Voltage Deficit in Wide-Bandgap Perovskite Solar Cells: The Role of Suppressed Ion Migration

Surface treatment using large alkyl/aryl ammonium cations has demonstrated reduced open-circuit voltage (V OC ) deficits in perovskite solar cells (PSCs), but the origin of the improvements has been vaguely attributed to defect passivation. Here, we combine the microscopic probing of the local electrical properties, thermal admittance spectroscopic analysis, and first principles calculations to elucidate the critical role of arylammonium interface layers on suppressing the ion migration in wide-bandgap (WBG) PSCs. Our results reveal that arylammonium surface treatment using phenethylammonium iodide increases the activation energy barrier for ion migration on the surface, which suppresses the accumulation of charge defects at surface and grain boundaries (GBs), leading to reduced dark saturation current density in WBG PSCs. Furthermore, with device optimization, our champion 1.73-eV PSC delivers a power conversion efficiency of 19.07% with a V OC of 1.25 V, achieving a V OC -deficit of 0.48 V.

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

A New Cathode Material for a Li–O 2 Battery Based on Lithium Superoxide

Li–O 2 batteries suffer from large charge overpotentials due to the high charge transfer resistance of Li 2 O 2 discharge products. A potential solution to this problem is the development of LiO 2 -based batteries that possess low charge overpotentials due to the lower charge transfer resistance of LiO 2 . In this report, IrLi nanoparticles were synthesized and implemented for the first time as a LiO 2 battery cathode material. The IrLi nanoparticle synthesis was achieved by a temperature- and time-optimized thermal reaction between a precise ratio of iridium nanoparticles and lithium metal. Li–O 2 batteries employing the IrLi-rGO cathodes were cycled up to 100 cycles at moderate current densities with sustained low cell charge potentials (<3.5 V). Further, various characterization techniques, including SEM, DEMS, TEM, Raman, and titration, were used to demonstrate the LiO 2 discharge product and the absence of Li 2 O 2 . On the basis of first-principles calculations, it was concluded that the formation of crystalline LiO 2 can be stabilized by epitaxial growth on the (111) facets of IrLi nanoparticles present on the cathode surface. These findings demonstrate that, in addition to the previously studied Ir 3 Li intermetallic, the IrLi intermetallic also provides a means by which LiO 2 discharge products can be stabilized and confirms the importance of templating for the formation process.

25 ENERGY STORAGE↗
DOE OSTI2024

Dimensionality-Dependent Electronic Properties of the Highly Conducting n-Type Polymer, Poly(benzodifurandione)

Poly(benzodifurandione) (n-PBDF) has garnered significant interest as it displays the highest reported n-type electrical conductivity among π-conjugated polymers. Earlier theoretical studies of n-PBDF could not rationalize this high conductivity. Here, we explore the geometric and electronic properties of two-dimensional (2D) and three-dimensional (3D) n-PBDF networks using first-principles calculations and tight-binding models. In 2D networks, a metallic electronic configuration occurs when considering a coplanar geometry with BDF moieties bounded to protons on the same side; however, backbone torsions disrupt the metallic behavior. In contrast, all 3D architectures consistently lead to a metallic nature, which is not impacted by variations in proton positions and stacking patterns. Tight-binding models allowed us to evaluate the respective strengths of intra- and interchain electronic couplings in n-PBDF. Altogether, our investigations provide a comprehensive picture into the electronic properties of n-PBDF and shed light on how they are affected by system dimensionality, proton positions, and stacking patterns.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Localized Excitons in NbSe 2 -MoSe 2 Heterostructures

Neutral and charged excitons (trions) in atomically thin materials offer important capabilities for photonics, from ultrafast photodetectors to highly efficient light-emitting diodes and lasers. Recent studies of van der Waals (vdW) heterostructures comprised of dissimilar monolayer materials have uncovered a wealth of optical phenomena that are predominantly governed by interlayer interactions. Here, we examine the optical properties in NbSe 2 -MoSe 2 vdW hetero- structures, which provide an important model system to study metal–semiconductor interfaces, a common element in optoelectronics. Through low-temperature photoluminescence (PL) microscopy, we discover a sharp emission feature, L1, that is localized at the NbSe 2 -capped regions of MoSe 2 . L1 is observed at energies below the commonly studied MoSe 2 excitons and trions and exhibits temperature- and power-dependent PL consistent with exciton localization in a confining potential. This PL feature is robust, observed in a variety of samples fabricated with different stacking geometries and cleaning procedures. Using first-principles calculations, we reveal that the confinement potential required for exciton localization naturally arises from the in-plane band bending due to the changes in the electron affinity between pristine MoSe 2 and NbSe 2 -MoSe 2 heterostructure. Here, we discuss the implications of our studies for atomically thin optoelectronics devices with atomically sharp interfaces and tunable electronic structures.

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

Millisecond Conversion of Metastable 2D Materials by Flash Joule Heating

Controllable phase engineering is vital for precisely tailoring material properties since different phase structures have various electronic states and atomic arrangements. Rapid synthesis of thermodynamically metastable materials, especially two-dimensional metastable materials, with high efficiency and low cost remains a large challenge. Here we report flash Joule heating (FJH) as an electrothermal method to achieve the bulk conversion of transition metal dichalcogenides, MoS 2 and WS 2 , from 2H phases to 1T phases in milliseconds. The conversions can reach up to 76% of flash MoS 2 using tungsten powder as conductive additive. Different degrees of phase conversion can be realized by controlling the FJH conditions, such as reaction duration and additives, which allows the study of ratio-dependent properties. First-principles calculations confirm that structural processes associated with the FJH, such as vacancy formation and charge accumulation, result in stabilization of the 1T phases. Furthermore, FJH offers rapid access to bulk quantities of the hitherto hard-to-access 1T phases, a promising method for further fundamental research and diverse applications of metastable phases.

2D materials↗
DOE OSTI2021

Intrinsic Defects in MoS 2 Grown by Pulsed Laser Deposition: From Monolayers to Bilayers

Pulsed laser deposition (PLD) can be considered a powerful method for the growth of two-dimensional (2D) transition-metal dichalcogenides (TMDs) into van der Waals heterostructures. However, despite significant progress, the defects in 2D TMDs grown by PLD remain largely unknown and yet to be explored. In this work, we combine atomic resolution images and first-principles calculations to reveal the atomic structure of defects, grains, and grain boundaries in mono- and bilayer MoS 2 grown by PLD. We find that sulfur vacancies and MoS antisites are the predominant point defects in 2D MoS 2 . We predict that the aforementioned point defects are thermodynamically favorable under a Mo-rich/S-poor environment. The MoS 2 monolayers are polycrystalline and feature nanometer size grains connected by a high density of grain boundaries. In particular, the coalescence of nanometer grains results in the formation of 180° mirror twin boundaries consisting of distinct 4- and 8-membered rings. We show that PLD synthesis of bilayer MoS 2 results in various structural symmetries, including AA' and AB, but also turbostratic with characteristic moiré patterns. Moreover, we report on the experimental demonstration of an electron beam-driven transition between the AB and AA' stacking orientations in bilayer MoS 2 . These results provide a detailed insight into the atomic structure of monolayer MoS 2 and the role of the grain boundaries on the growth of bilayer MoS 2 , which has importance for future applications in optoelectronics.

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

High-Entropy 2D Carbide MXenes: TiVNbMoC 3 and TiVCrMoC 3

Two-dimensional (2D) transition metal carbides and nitrides, known as MXenes, are a fast-growing family of 2D materials. MXenes 2D flakes have n + 1 (n = 1-4) atomic layers of transition metals interleaved by carbon/nitrogen layers, but to-date remain limited in composition to one or two transition metals. In this study, by implementing four transition metals, we report the synthesis of multi-principal-element high-entropy M 4 C 3 T x MXenes. Specifically, we introduce two high-entropy MXenes, TiVNbMoC 3 T x and TiVCrMoC 3 T x , as well as their precursor TiVNbMoAlC 3 and TiVCrMoAlC 3 high-entropy MAX phases. We used a combination of real and reciprocal space characterization (X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, and scanning transmission electron microscopy) to establish the structure, phase purity, and equimolar distribution of the four transition metals in high-entropy MAX and MXene phases. We use first-principles calculations to compute the formation energies and explore synthesizability of these high-entropy MAX phases. We also show that when three transition metals are used instead of four, under similar synthesis conditions to those of the four-transition-metal MAX phase, two different MAX phases can be formed (i.e., no pure single-phase forms). This finding indicates the importance of configurational entropy in stabilizing the desired single-phase high-entropy MAX over multiphases of MAX, which is essential for the synthesis of phase-pure high-entropy MXenes. The synthesis of high-entropy MXenes significantly expands the compositional variety of the MXene family to further tune their properties, including electronic, magnetic, electrochemical, catalytic, high temperature stability, and mechanical behavior.

2D materials↗
DOE OSTI2021

Revealing the Chemical Bonding in Adatom Arrays via Machine Learning of Hyperspectral Scanning Tunneling Spectroscopy Data

The adatom arrays on surfaces offer an ideal playground to explore the mechanisms of chemical bonding via changes in the local electronic tunneling spectra. While this information is readily available in hyperspectral scanning tunneling spectroscopy data, its analysis has been considerably impeded by a lack of suitable analytical tools. Here we develop a machine learning based workflow combining supervised feature identification in the spatial domain and unsupervised clustering in the energy domain to reveal the details of structure-dependent changes of the electronic structure in adatom arrays on the Co 3 Sn 2 S 2 cleaved surface. This approach, in combination with first-principles calculations, provides insight for using artificial neural networks to detect adatoms and classifies each based on their local neighborhood comprised of other adatoms. These structurally classified adatoms are further spectrally deconvolved. The unexpected inhomogeneity of electronic structures among adatoms in similar configurations is unveiled using this method, suggesting there is not a single atomic species of adatoms, but rather multiple types of adatoms on the Co 3 Sn 2 S 2 surface. This is further supported by a slight contrast difference in the images (or slight size variation) of the topography of the adatoms.

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

Fabrication of a Microcavity Prepared by Remote Epitaxy over Monolayer Molybdenum Disulfide

We report advances in epitaxy have enabled the preparation of high-quality material architectures consisting of incommensurate components. Remote epitaxy based on lattice transparency of atomically thin graphene has been intensively studied for cost-effective advanced device manufacturing and heterostructure formation. However, remote epitaxy on nongraphene two-dimensional (2D) materials has rarely been studied even though it has a broad and immediate impact on various disciplines, such as many-body physics and the design of advanced devices. Herein, we report remote epitaxy of ZnO on monolayer MoS 2 and the realization of a whispering-gallery-mode (WGM) cavity composed of a single crystalline ZnO nanorod and monolayer MoS 2 . Cross-sectional transmission electron microscopy and first-principles calculations revealed that the nongraphene 2D material interacted with overgrown and substrate layers and also exhibited lattice transparency. The WGM cavity embedding monolayer MoS 2 showed enhanced luminescence of MoS 2 and multimodal emission.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Engineering Magnetic Anisotropy and Emergent Multidirectional Soft Ferromagnetism in Ultrathin Freestanding LaMnO 3 Films

We report the combination of small coercive fields and weak magnetic anisotropy makes soft ferromagnetic films extremely useful for nanoscale devices that need to easily switch spin directions. However, soft ferromagnets are relatively rare, particularly in ultrathin films with thicknesses of a few nanometers or less. We have synthesized large-area, high-quality, ultrathin freestanding LaMnO 3 films on Si and found unexpected soft ferromagnetism along both the in-plane and out-of-plane directions when the film thickness was reduced to 4 nm. We argue that the vanishing magnetic anisotropy between the two directions is a consequence of two coexisting magnetic easy axes in different atomic layers of the LaMnO 3 film. Spectroscopy measurements reveal a change in Mn valence from 3+ in the film interior to approximately 2+ at the surfaces where considerable hydrogen infiltration occurs due to the water dissolving process. First-principles calculations show that protonation of LaMnO 3 decreases valence and Our the Mn switches the magnetic easy axis from in-plane to out-of-plane as the Mn valence approaches 2+ from its 3+ bulk value. Our work demonstrates that ultrathin freestanding films can exhibit functional properties that are absent in homogeneous materials, concomitant with their convenient compatibility with Si-based devices.

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

Local Structure of Sulfur Vacancies on the Basal Plane of Monolayer MoS 2

We report the nature of the S-vacancy is central to controlling the electronic properties of monolayer MoS 2 . Understanding the geometric and electronic structures of the S-vacancy on the basal plane of monolayer MoS 2 remains elusive. Here, operando S K-edge X-ray absorption spectroscopy shows the formation of clustered S-vacancies on the basal plane of monolayer MoS 2 under reaction conditions (H 2 atmosphere, 100–600 °C). First-principles calculations predict spectral fingerprints consistent with the experimental results. The Mo K-edge extended X-ray absorption fine structure shows the local structure as coordinatively unsaturated Mo with 4.1 ± 0.4 S atoms as nearest neighbors (above 400 °C in an H 2 atmosphere). Conversely, the 6-fold Mo–Mo coordination in the crystal remains unchanged. Electrochemistry confirms similar active sites for hydrogen evolution. The identity of the S-vacancy defect on the basal plane of monolayer MoS 2 is herein elucidated for applications in optoelectronics and catalysis.

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

Artificial Graphene Nanoribbons: A Test Bed for Topology and Low-Dimensional Dirac Physics

Here, we synthesize artificial graphene nanoribbons by positioning carbon monoxide molecules on a copper surface to confine its surface state electrons into artificial atoms positioned to emulate the low-energy electronic structure of graphene derivatives. We demonstrate that the dimensionality of artificial graphene can be reduced to one dimension with proper "edge" passivation, with the emergence of an effectively gapped one-dimensional nanoribbon structure. These one-dimensional structures show evidence of topological effects analogous to graphene nanoribbons. Guided by first-principles calculations, we spatially explore robust, zero-dimensional topological states by altering the topological invariants of quasi-one-dimensional artificial graphene nanostructures. The robustness and flexibility of our platform allow us to toggle the topological invariants between trivial and nontrivial on the same nanostructure. Ultimately, we spatially manipulate the states to understand fundamental coupling between adjacent topological states that are finely engineered and simulate complex Hamiltonians.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗