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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Heteroatom-Doped Graphenes as Actively Interacting 2D Encapsulation Media for Mg-Based Hydrogen Storage

Nanoencapsulation using graphene derivatives enables the facile fabrication of two-dimensional (2D) nanocomposites with unique microstructures and has been generally applied to many fields of energy materials. Particularly, metal hydrides such as MgH 2 encapsulated by graphene derivatives have emerged as a promising hybrid material for overcoming the disadvantageous properties of Mg-based hydrogen storage. Although the behavior of the graphene–Mg nanoencapsulation interface has been studied for many composite materials, the direct modification of graphene with nonmetal foreign elements for changing the interfacial behavior has been limitedly reported. In this regard, using B-doped graphene and N-doped graphene as nanoencapsulation media for tuning the interfacial behavior of graphene derivative–Mg nanoparticles, we present altered hydrogen storage kinetics of heteroatom-doped (B and N) graphene–Mg composites. The effect of heteroatom doping is studied in terms of bonding configurations and heteroatom doping concentrations. The enhancement in hydrogen uptake was observed for all of the heteroatom-doped graphene–Mg nanocomposites. On the other hand, a few samples exhibit significantly low activation energy at the early stage of desorption, which can be related to the facilitated nucleus formation. Density functional theory calculation indicates that B-doping and N-doping accelerate hydrogen absorption kinetics in different ways, aiding charge transfer and inducing surface deformation of Mg nanoparticles, respectively. Their effects can be augmented in the presence of structural defects on graphene, such as vacancies, pores, or graphene edges. These results demonstrate that hydrogen storage kinetics of Mg-based systems can be altered by utilizing heteroatom-doped graphene oxide derivatives as 2D nanoencapsulation media, suggesting that the addition of a nonmetal doping element can also be applied to Mg-based hydrogen storage by modifying the nanoencapsulation interface without forming Mg alloy phases.

08 HYDROGEN↗
DOE OSTI2021

Epitaxy, exfoliation, and strain-induced magnetism in rippled Heusler membranes

Single-crystalline membranes of functional materials enable the tuning of properties via extreme strain states; however, conventional routes for producing membranes require the use of sacrificial layers and chemical etchants, which can both damage the membrane and limit the ability to make them ultrathin. Here we demonstrate the epitaxial growth of the cubic Heusler compound GdPtSb on graphene-terminated Al 2 O 3 substrates. Despite the presence of the graphene interlayer, the Heusler films have epitaxial registry to the underlying sapphire, as revealed by x-ray diffraction, reflection high energy electron diffraction, and transmission electron microscopy. The weak Van der Waals interactions of graphene enable mechanical exfoliation to yield free-standing GdPtSb membranes, which form ripples when transferred to a flexible polymer handle. Whereas unstrained GdPtSb is antiferromagnetic, measurements on rippled membranes show a spontaneous magnetic moment at room temperature, with a saturation magnetization of 5.2 bohr magneton per Gd. First-principles calculations show that the coupling to homogeneous strain is too small to induce ferromagnetism, suggesting a dominant role for strain gradients. Our membranes provide a novel platform for tuning the magnetic properties of intermetallic compounds via strain (piezomagnetism and magnetostriction) and strain gradients (flexomagnetism).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2021

Strong Electronic Coupling of Graphene Nanoribbons onto Basal Plane of a Glassy Carbon Electrode

The grafting of molecular motifs to the conductive carbon represents a promising approach toward improved hybrid materials for electrocatalytic applications. Here, we investigate the electrochemical behavior of graphene nanoribbons (GNR) deposited onto a glassy carbon electrode using pi - pi stacking interactions. Using the bipyrimidine moiety on the nanoribbon edges as a reporter of the proton-coupled electron transfer chemistry, we illustrate that the simple electrochemical treatment of as-deposited nanoribbon generates a hybrid material that is in strong electronic communication with the conductive support. Overall, this work shows a strategy for modifying the basal plane of carbon materials and provides a potential platform for the incorporation of catalytic metal sites via coordination through the N-functionalities of GNR.

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

Quantum Dots on Silicon-on-Insulator (QD/SOI): Nanoscale Strain and Band Structure Engineering (Final Report)

As the project titles indicate, the work focused on Group IV nanomembranes (NMs), thin functional layers, and interfaces, all with one or more dimensions at the nanoscale. The primary focus was discovery driven fundamental science. This approach led to surprising new, unexpected results that ended up being patentable and creating commercial value, but that were also high-impact science. Our effort divided into several overlapping thrusts: 1) strain engineering of NMs, via both lattice strain and externally applied strain, 2) interfaces between crystalline semiconductor NMs and other 2D sheets that are stacked or grown on each other, and 3) charge transport (electronics and optoelectronics) in thin layers, sheets, and surfaces. We accomplish these goals via 1) fabrication of new or higher-quality materials using NM approaches, 2) growth of new combinations, or 3) transfer and stacking to create new composites. The range of materials included combinations of Si, Ge, graphene, and several III-V compounds. The work has foundations in both nano- and mesoscale science.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Nonlinear Nano‐Imaging of Interlayer Coupling in 2D Graphene‐Semiconductor Heterostructures

The emergent electronic, spin, and other quantum properties of 2D heterostructures of graphene and transition metal dichalcogenides are controlled by the underlying interlayer coupling and associated charge and energy transfer dynamics. However, these processes are sensitive to interlayer distance and crystallographic orientation, which are in turn affected by defects, grain boundaries, or other nanoscale heterogeneities. This obfuscates the distinction between interlayer charge and energy transfer. Here, nanoscale imaging in coherent four‐wave mixing (FWM) and incoherent two‐photon photoluminescence (2PPL) is combined with a tip distance‐dependent coupled rate equation model to resolve the underlying intra‐ and inter‐layer dynamics while avoiding the influence of structural heterogeneities in mono‐ to multi‐layer graphene/WSe 2 heterostructures. With selective insertion of hBN spacer layers, it is shown that energy, as opposed to charge transfer, dominates the interlayer‐coupled optical response. From the distinct nano‐FWM and ‐2PPL tip‐sample distance‐dependent modification of interlayer and intralayer relaxation by tip‐induced enhancement and quenching, an interlayer energy transfer time of τ ET ≈ ( 0 . 35 − 0.15 + 0.65 ) $\tau _{\rm ET} \approx (0.35^{+0.65}_{-0.15})$ ps consistent with recent reports is derived. As a local probe technique, this approach highlights the ability to determine intrinsic sample properties even in the presence of large sample heterogeneity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Impact of 2D–3D Heterointerface on Remote Epitaxial Interaction through Graphene

Remote epitaxy has drawn attention as it offers epitaxy of functional materials that can be released from the substrates with atomic precision, thus enabling production and heterointegration of flexible, transferrable, and stackable freestanding single-crystalline membranes. In addition, the remote interaction of atoms and adatoms through two-dimensional (2D) materials in remote epitaxy allows investigating and utilizing electrical/chemical/physical coupling of bulk (3D) materials via 2D materials (3D-2D-3D coupling). Here, we unveil the respective roles and impacts of the substrate material, graphene, substrate-graphene interface, and epitaxial material for electrostatic coupling of these materials, which governs cohesive ordering and can lead to single-crystal epitaxy in the overlying film. Further, we show that simply coating a graphene layer on wafers does not guarantee successful implementation of remote epitaxy, since atomically precise control of the graphene-coated interface is required, and provide key considerations for maximizing the remote electrostatic interaction between the substrate and adatoms. This was enabled by exploring various material systems and processing conditions, and we demonstrate that the rules of remote epitaxy vary significantly depending on the ionicity of material systems as well as the graphene-substrate interface and the epitaxy environment. The general rule of thumb discovered here enables expanding 3D material libraries that can be stacked in freestanding form.

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

A deep learning interatomic potential developed for atomistic simulation of carbon materials

Interatomic potentials based on neural-network machine learning method have attracted considerable attention in recent years owing to their outstanding ability to balance the accuracy and efficiency in atomistic simulations. In this work, a neural-network potential (NNP) for carbon is generated to simulate the structural properties of various carbon structures. The potential is trained using a database consisting of crystalline and liquid structures obtained by the first-principles density functional theory (DFT) calculations. The developed potential accurately predicts the energies and forces in crystalline and liquid carbon structures, the energetic stability of defected graphene, and the structures of amorphous carbon as the function of density. As a result, the excellent accuracy and transferability of the NNP provide a promising tool for accurate atomistic simulations of various carbon materials with faster speed and much lower cost.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Scalable bottom-up synthesis of Co-Ni–doped graphene

Introducing heteroatoms into graphene is a powerful strategy to modulate its catalytic, electronic, and magnetic properties. At variance with the cases of nitrogen (N)– and boron (B)–doped graphene, a scalable method for incorporating transition metal atoms in the carbon (C) mesh is currently lacking, limiting the applicative interest of model system studies. This work presents a during-growth synthesis enabling the incorporation of cobalt (Co) alongside nickel (Ni) atoms in graphene on a Ni(111) substrate. Single atoms are covalently stabilized within graphene double vacancies, with a Co load ranging from 0.07 to 0.22% relative to C atoms, controllable by synthesis parameters. Structural characterization involves variable-temperature scanning tunneling microscopy and ab initio calculations. The Co- and Ni-codoped layer is transferred onto a transmission electron microscopy grid, confirming stability through scanning transmission electron microscopy and electron energy loss spectroscopy. This method holds promise for applications in spintronics, gas sensing, electrochemistry and catalysis, and potential extension to graphene incorporation of similar metals.

Science & Technology - Other Topics↗
DOE OSTI2020

Elucidating the Influence of Residual Polymer and Gas Environment on the Electronic Structure of a Graphene Layer Using in Situ APXPS

We use in situ ambient pressure X-ray photoelectron spectroscopy (APXPS) and ultraviolet photoelectron spectroscopy (UPS) to develop an effective method for studying changes in the graphene (Gr) electronic structure according to certain circumstance. The amount of polymethyl methacrylate (PMMA) residual polymer (RP), inevitably generated during the Gr transfer process, is significantly reduced from Gr surface by thermal annealing. This processed Gr is then sequentially exposed to specific gas environments (Ar, N 2 , O 2 , and CO 2 ), and APXPS or UPS is carried out to investigate the variations in the Gr electronic structure including the work function. When the amount of PMMA RP on Gr is reduced, the position of the main carbon peak shifts by more than 0.4 eV to a higher binding energy (in XPS spectra), and the secondary electron cutoff moves by about 0.2 eV to a lower binding energy (in UPS spectra). These changes are generally caused by a decrease in the Gr work function. On the other hand, exposure to the gas environments at different temperatures that we investigated did not produce significant changes in the work function and chemical states of Gr. These results confirm that the material in contact with Gr should be considered to achieve the desired Gr performance in electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A systematic approach to generating accurate neural network potentials: the case of carbon

Abstract Availability of affordable and widely applicable interatomic potentials is the key needed to unlock the riches of modern materials modeling. Artificial neural network-based approaches for generating potentials are promising; however, neural network training requires large amounts of data, sampled adequately from an often unknown potential energy surface. Here we propose a self-consistent approach that is based on crystal structure prediction formalism and is guided by unsupervised data analysis, to construct an accurate, inexpensive, and transferable artificial neural network potential. Using this approach, we construct an interatomic potential for carbon and demonstrate its ability to reproduce first principles results on elastic and vibrational properties for diamond, graphite, and graphene, as well as energy ordering and structural properties of a wide range of crystalline and amorphous phases.

Chemistry↗
DOE OSTI2022

Implementation of real‐time TDDFT for periodic systems in the open‐source PySCF software package

Abstract We present a new implementation of real‐time time‐dependent density functional theory (RT‐TDDFT) for calculating excited‐state dynamics of periodic systems in the open‐source Python‐based PySCF software package. Our implementation uses Gaussian basis functions in a velocity gauge formalism and can be applied to periodic surfaces, condensed‐phase, and molecular systems. As representative benchmark applications, we present optical absorption calculations of various molecular and bulk systems and a real‐time simulation of field‐induced dynamics of a (ZnO) 4 molecular cluster on a periodic graphene sheet. We present representative calculations on optical response of solids to infinitesimal external fields as well as real‐time charge‐transfer dynamics induced by strong pulsed laser fields. Due to the widespread use of the Python language, our RT‐TDDFT implementation can be easily modified and provides a new capability in the PySCF code for real‐time excited‐state calculations of chemical and material systems.

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

Computational Discovery of Active and Selective Metal‐Nitrogen‐Graphene Catalysts for Electrooxidation of Water to H 2 O 2

A direct electrosynthesis of H 2 O 2 from either O 2 or H 2 O is an attractive strategy to replace the energy-intensive industrial anthraquinone process. Two-electron water oxidation reaction (2e-WOR) offers several advantages over the oxygen reduction reaction such as better mass transfer due to the absence of gas-phase reactants. However, 2e-WOR is a more challenging and less studied process with only a handful of metal oxides exhibiting reasonable activity/selectivity properties. Herein, we employ density-functional-theory calculations to screen a variety of metal-nitrogen-graphene structures for 2e-WOR. As a consequence of scaling between the adsorption energies of reaction intermediates, we determine a linear relation between selectivities for the first and second reaction steps of 2e-WOR, viz. that if selectivity toward adsorbed OH is improved, then selectivity toward H 2 O 2 at the subsequent step is decreased. We also find that selectivity and activity are linearly scaled in such a way that a higher activity (i.e., a lower overpotential) leads to a lower selectivity for the H 2 O 2 formation step. Based on the obtained results several chemistries, e.g., containing NiN x -C moieties, are predicted to rival the best-performing metal oxides such as ZnO and CaSnO 3 in terms of combination of their activity/selectivity characteristics for 2e-WOR.

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

Lanthanum-Doped Graphene for Electrocatalytic Reduction of Nitrogen Monoxide

Electrocatalytic conversion of nitrogen oxides is a promising approach to address nitrogen pollution in underground water. Nitrogen oxides, such as nitrate and nitrite, can be reduced to N 2 and NH 3 over an electrocatalyst, with NO as the key intermediate, subsequent reaction of which controls the overall activity and selectivity. Here, we report density functional theory calculations of NO electrocatalytic reduction (NOER) over lanthanum embedded in graphene, through which we show that the localized states in La drive the reaction favorably due to more pronounced molecular adsorption and charge transfer than transition metals such as Co. The free energy profiles are compared between the La-based single-atom catalyst (SAC) and Co-based SAC, for producing N 2 and NH 3 . We find that the La-SAC intensifies the electron transfer to the adsorbed NO, promoting the first protonation step of NO, which is the potential-limiting step on the Co-SAC. Also, an intriguing effect of the water solvent is revealed on the La-SAC. In addition to stabilizing the intermediate species, water molecules that are coordinated with La participate directly in the protonation steps, enhancing the catalyst activity. Furthermore, this study reveals the unique mechanism of NOER over rare-earth-based catalysts, highlighting the potential application of atomically dispersed f-block elements for electrocatalytic reactions.

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

Time-Resolved Observation of Hole Tunneling in van der Waals Multilayer Heterostructures

We reported a time-resolved study of quantum-mechanical tunneling of holes between two MoSe 2 monolayers that are separated by a monolayer WS 2 energy barrier. Four-layer heterostructures of MoSe 2 /WS 2 /MoSe 2 /graphene, as well as control samples, were fabricated by mechanical exfoliation and dry transfer techniques. To time-resolve the hole tunneling process, an ultrashort laser pulse was used to excite electrons and holes in both MoSe 2 layers. Here, by utilization of the graphene layer to eliminate carriers in the third MoSe 2 layer, the first MoSe 2 layer is selectively populated with the holes, which then tunnel to the third MoSe 2 layer. By monitoring decay of the hole population with an ultrashort probe pulse, we measure a hole tunneling time of about 20 ps, which is found to slightly increase with the injected carrier density. Besides the fundamental interests of real-time observation of the quantum-mechanical tunneling effect across a nanometer barrier, these results provide quantitative understanding on tunneling mechanisms of charge transfer in van der Waals heterostructures, which is useful for designing sophisticated van der Waals multilayer heterostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Spin-dependent electron transfer in electrochemically transparent van der Waals heterostructures for oxygen evolution reaction

Spin selective catalysis is an emerging approach for improving the thermodynamics and kinetics of reactions. The role of electron spins has been scarcely studied in catalytic reactions. One exception is the oxygen evolution reaction (OER) where strongly correlated metals and oxides are used as catalysts. In OER, spin alignment facilitates the transition of singlet state of the reactant to the triplet state of O 2 . However, the influence of strong correlations on spin exchange mechanism and spin selective thermodynamics of most catalytic reactions remain unclear. Here we decouple the strongly correlated catalyst from the electrolyte to study spin exchange in two-dimensional (2D) magnetic iron germanium telluride (FGT) heterostructure. We demonstrate that transmission of spin and electrochemical information between the catalyst and the reactant can occur through quantum exchange interaction despite the catalyst of FGT being completely encapsulated by graphene or hexagonal boron nitride (hBN). The strong correlations in FGT that lead to enhanced spin exchange in OER are observed in graphene or hBN layers with thicknesses of up to 6 nm. We demonstrate that spin alignment in FGT leads to a lowering of thermodynamic barrier for adsorption of hydroxide ion and electron transfer to the catalyst. This results in up to fivefold enhancement in OER performance and improved kinetics. Our results provide clear evidence that transmission of both quantum mechanical and electrochemical information through quantum spin exchange interaction in FGT leads to an enhancement in catalytic performance.

2D materials↗
DOE OSTI2022

Hybrid SERS platform by adapting both chemical mechanism and electromagnetic mechanism enhancements: SERS of 4-ATP and CV by the mixture with GQDs on hybrid PdAg NPs

Surface-enhanced Raman spectroscopy (SERS) is a versatile analytical technique widely adapted for the identification of target analytes even at an extremely low concentration. Herein, a unique hybrid SERS platform is demonstrated by utilizing the graphene quantum dots (GQDs) and hybrid PdAg NPs for the detection of 4-amino-thiophenol (4-ATP) and crystal violet (CV). GQDs offer the rich charge transfer to the LUMO and HOMO of 4-ATP and CV by the CM enhancement. A significant EM enhancement is achieved by the strong localized surface plasmon resonance (LSPR) of uniquely designed hybrid core-shell PdAg NP, possessing the narrow nano-gaps with the highly dense small Ag NPs and Pd core Ag shell configuration. As a result, orders of enhancement of originally weak 4-ATP and CV Raman signal is witnessed by the combination of electromagnetic mechanism (EM) and chemical mechanism (CM) enhancements on a single SERS substrate. The hybrid GQD/HNP SERS substrate demonstrates significantly improved hot spots and strongly localized electromagnetic fields as confirmed by the finite-difference time-domain (FDTD) simulations. There for a proper mixture ratio of GQDs and probe molecules presents largely enhanced SERS signals by a strong adsorption of probe molecules through π - π interaction and the enhancement factors vary by the mixture ratio depending on the adsorption kinetics and Raman cross-section of molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Mechanical properties of freestanding few-layer graphene/boron nitride/polymer heterostacks investigated with local and non-local techniques

van der Waals two-dimensional materials and heterostructures combined with polymer films continue to attract research attention to elucidate their functionality and potential applications. This study presents the fabrication and mechanical testing of 2D material heterostacks, consisting of few-layer boron nitride and graphene heterostructures synthesized via chemical vapor deposition, capped with a polymethyl methacrylate layer and suspended across ∼200 μm wide trenches using a combined wet–dry transfer method. The mechanical characterization of the heterostacks was performed using two independent approaches: (a) non-local testing with a custom-built tensile testing platform and (b) local load–displacement testing employing atomic force microscopy probes, complemented by finite element simulations. Both approaches provided new results, which are in good agreement with each other. Overall, our findings offer new insights into a combined load capacity in complex multi-material two-dimensional systems, and can contribute to advancing micro and nano-scale device designs and implementations.

Lespasio, Marcus↗
DOE OSTI2021

Superconductivity-induced spectral weight transfer due to quantum geometry

Optical spectral weight transfer associated with the onset of superconductivity at high-energy scales compared with the superconducting gap has been observed in several systems such as high-T c cuprates. While there are still debates on the origin of this phenomenon, a consensus is that it is due to strong correlation effects beyond the BCS theory. Here, we show that there is another route to a nonzero spectral weight transfer based on the quantum geometry of the conduction band in multiband systems. Further, we discuss applying this idea to the cuprates and twisted multilayer graphene.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗