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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 883 records · Page 49

Maximizing ion accessibility in MXene-knotted carbon nanotube composite electrodes for high-rate electrochemical energy storage

Improving the accessibility of ions in the electrodes of electrochemical energy storage devices is vital for charge storage and rate performance. In particular, the kinetics of ion transport in organic electrolytes is slow, especially at low operating temperatures. Herein, we report a new type of MXene-carbon nanotube (CNT) composite electrode that maximizes ion accessibility resulting in exceptional rate performance at low temperatures. The improved ion transport at low temperatures is made possible by breaking the conventional horizontal alignment of the two-dimensional layers of the MXene Ti 3 C 2 by using specially designed knotted CNTs. The large, knot-like structures in the knotted CNTs prevent the usual restacking of the Ti 3 C 2 flakes and create fast ion transport pathways. The MXene-knotted CNT composite electrodes achieve high capacitance (up to 130 F g -1 (276 F cm -3 )) in organic electrolytes with high capacitance retention over a wide scan rate range of 10 mV s -1 to 10 V s -1 . This study is also the first report utilizing MXene-based supercapacitors at low temperatures (down to -60 °C).

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Gaussian-preserved, non-volatile shape morphing in three-dimensional microstructures for dual-functional electronic devices

Motile plant structures such as Mimosa pudica leaves, Impatiens glandulifera seedpods, and Dionaea muscipula leaves exhibit fast nastic movements in a few seconds or less. This motion is stimuli-independent mechanical movement following theorema egregium rules. Artificial analogs of tropistic motion in plants are exemplified by shape-morphing systems, which are characterized by high functional robustness and resilience for creating 3D structures. However, all shape-morphing systems developed so far rely exclusively on continuous external stimuli and result in slow response. Here, we report a Gaussian-preserved shape-morphing system to realize ultrafast shape morphing and non-volatile reconfiguration. Relying on the Gaussian-preserved rules, the transformation can be triggered by mechanical or thermal stimuli within a microsecond. Moreover, as localized energy minima are encountered during shape morphing, non-volatile configuration is preserved by geometrically enhanced rigidity. Using this system, we demonstrate a suite of electronic devices that are reconfigurable, and therefore, expand functional diversification.

36 MATERIALS SCIENCE↗

Layer number dependent ferroelasticity in 2D Ruddlesden–Popper organic-inorganic hybrid perovskites

Ferroelasticity represents material domains possessing spontaneous strain that can be switched by external stress. Three-dimensional perovskites like methylammonium lead iodide are determined to be ferroelastic. Layered perovskites have been applied in optoelectronic devices with outstanding performance. However, the understanding of lattice strain and ferroelasticity in layered perovskites is still lacking. Here, using the in-situ observation of switching domains in layered perovskite single crystals under external strain, we discover the evidence of ferroelasticity in layered perovskites with layer number more than one, while the perovskites with single octahedra layer do not show ferroelasticity. Density functional theory calculation shows that ferroelasticity in layered perovskites originates from the distortion of inorganic octahedra resulting from the rotation of aspherical methylammonium cations. The absence of methylammonium cations in single layer perovskite accounts for the lack of ferroelasticity. These ferroelastic domains do not induce non-radiative recombination or reduce the photoluminescence quantum yield.

36 MATERIALS SCIENCE↗

Operando high-pressure investigation of size-controlled CuZn catalysts for the methanol synthesis reaction

Although Cu/ZnO-based catalysts have been long used for the hydrogenation of CO 2 to methanol, open questions still remain regarding the role and the dynamic nature of the active sites formed at the metal-oxide interface. Here, we apply high-pressure operando spectroscopy methods to well-defined Cu and Cu 0.7 Zn 0.3 nanoparticles supported on ZnO/Al2O 3 , γ-Al 2 O 3 and SiO 2 to correlate their structure, composition and catalytic performance. We obtain similar activity and methanol selectivity for Cu/ZnO/Al 2 O 3 and CuZn/SiO 2 , but the methanol yield decreases with time on stream for the latter sample. Operando X-ray absorption spectroscopy data reveal the formation of reduced Zn species coexisting with ZnO on CuZn/SiO 2 . Near-ambient pressure X-ray photoelectron spectroscopy shows Zn surface segregation and the formation of a ZnO-rich shell on CuZn/SiO 2 . In this work we demonstrate the beneficial effect of Zn, even in diluted form, and highlight the influence of the oxide support and the Cu-Zn interface in the reactivity.

36 MATERIALS SCIENCE↗

Room-temperature intrinsic ferromagnetism in epitaxial CrTe 2 ultrathin films

While the discovery of two-dimensional (2D) magnets opens the door for fundamental physics and next-generation spintronics, it is technically challenging to achieve the room-temperature ferromagnetic (FM) order in a way compatible with potential device applications. Here in this paper, we report the growth and properties of single- and few-layer CrTe 2 , a van der Waals (vdW) material, on bilayer graphene by molecular beam epitaxy (MBE). Intrinsic ferromagnetism with a Curie temperature (TC) up to 300 K, an atomic magnetic moment of ~0.21 μ B /Cr and perpendicular magnetic anisotropy (PMA) constant (K u ) of 4.89 × 10 5 erg/cm 3 at room temperature in these few-monolayer films have been unambiguously evidenced by superconducting quantum interference device and X-ray magnetic circular dichroism. This intrinsic ferromagnetism has also been identified by the splitting of majority and minority band dispersions with ~0.2 eV at Г point using angle-resolved photoemission spectroscopy. The FM order is preserved with the film thickness down to a monolayer (T C ~ 200 K), benefiting from the strong PMA and weak interlayer coupling. The successful MBE growth of 2D FM CrTe 2 films with room-temperature ferromagnetism opens a new avenue for developing large-scale 2D magnet-based spintronics devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Dynamic self-assembly of compartmentalized DNA nanotubes

Abstract Bottom-up synthetic biology aims to engineer artificial cells capable of responsive behaviors by using a minimal set of molecular components. An important challenge toward this goal is the development of programmable biomaterials that can provide active spatial organization in cell-sized compartments. Here, we demonstrate the dynamic self-assembly of nucleic acid (NA) nanotubes inside water-in-oil droplets. We develop methods to encapsulate and assemble different types of DNA nanotubes from programmable DNA monomers, and demonstrate temporal control of assembly via designed pathways of RNA production and degradation. We examine the dynamic response of encapsulated nanotube assembly and disassembly with the support of statistical analysis of droplet images. Our study provides a toolkit of methods and components to build increasingly complex and functional NA materials to mimic life-like functions in synthetic cells.

59 BASIC BIOLOGICAL SCIENCES↗

Ultrafast coherent motion and helix rearrangement of homodimeric hemoglobin visualized with femtosecond X-ray solution scattering

Ultrafast motion of molecules, particularly the coherent motion, has been intensively investigated as a key factor guiding the reaction pathways. Recently, X-ray free-electron lasers (XFELs) have been utilized to elucidate the ultrafast motion of molecules. However, the studies on proteins using XFELs have been typically limited to the crystalline phase, and proteins in solution have rarely been investigated. Here we applied femtosecond time-resolved X-ray solution scattering (fs-TRXSS) and a structure refinement method to visualize the ultrafast motion of a protein. We succeeded in revealing detailed ultrafast structural changes of homodimeric hemoglobin involving the coherent motion. In addition to the motion of the protein itself, the time-dependent change of electron density of the hydration shell was tracked. Besides, the analysis on the fs-TRXSS data of myoglobin allows for observing the effect of the oligomeric state on the ultrafast coherent motion.

59 BASIC BIOLOGICAL SCIENCES↗

Designed and biologically active protein lattices

Versatile methods to organize proteins in space are required to enable complex biomaterials, engineered biomolecular scaffolds, cell-free biology, and hybrid nanoscale systems. Here, we demonstrate how the tailored encapsulation of proteins in DNA-based voxels can be combined with programmable assembly that directs these voxels into biologically functional protein arrays with prescribed and ordered two-dimensional (2D) and three-dimensional (3D) organizations. We apply the presented concept to ferritin, an iron storage protein, and its iron-free analog, apoferritin, in order to form single-layers, double-layers, as well as several types of 3D protein lattices. Our study demonstrates that internal voxel design and inter-voxel encoding can be effectively employed to create protein lattices with designed organization, as confirmed by in situ X-ray scattering and cryo-electron microscopy 3D imaging. The assembled protein arrays maintain structural stability and biological activity in environments relevant for protein functionality. The framework design of the arrays then allows small molecules to access the ferritins and their iron cores and convert them into apoferritin arrays through the release of iron ions. The presented study introduces a platform approach for creating bio-active protein-containing ordered nanomaterials with desired 2D and 3D organizations.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Visualizing the strongly reshaped skyrmion Hall effect in multilayer wire devices

Magnetic skyrmions are nanoscale spin textures touted as next-generation computing elements. When subjected to lateral currents, skyrmions move at considerable speeds. Their topological charge results in an additional transverse deflection known as the skyrmion Hall effect (SkHE). While promising, their dynamic phenomenology with current, skyrmion size, geometric effects and disorder remain to be established. Here we report on the ensemble dynamics of individual skyrmions forming dense arrays in Pt/Co/MgO wires by examining over 20,000 instances of motion across currents and fields. The skyrmion speed reaches 24 m/s in the plastic flow regime and is surprisingly robust to positional and size variations. Meanwhile, the SkHE saturates at ~22 ° , is substantially reshaped by the wire edge, and crucially increases weakly with skyrmion size. Particle model simulations suggest that the SkHE size dependence - contrary to analytical predictions - arises from the interplay of intrinsic and pinning-driven effects. These results establish a robust framework to harness SkHE and achieve high-throughput skyrmion motion in wire devices.

36 MATERIALS SCIENCE↗

The effect of water on colloidal quantum dot solar cells

Almost all surfaces sensitive to the ambient environment are covered by water, whereas the impacts of water on surface-dominated colloidal quantum dot (CQD) semiconductor electronics have rarely been explored. Here, strongly hydrogen-bonded water on hydroxylated lead sulfide (PbS) CQD is identified. The water could pilot the thermally induced evolution of surface chemical environment, which significantly influences the nanostructures, carrier dynamics, and trap behaviors in CQD solar cells. The aggravation of surface hydroxylation and water adsorption triggers epitaxial CQD fusion during device fabrication under humid ambient, giving rise to the inter-band traps and deficiency in solar cells. To address this problem, meniscus-guided-coating technique is introduced to achieve dense-packed CQD solids and extrude ambient water, improving device performance and thermal stability. Our works not only elucidate the water involved PbS CQD surface chemistry, but may also achieve a comprehensive understanding of the impact of ambient water on CQD based electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polarized X-ray scattering measures molecular orientation in polymer-grafted nanoparticles

Polymer chains are attached to nanoparticle surfaces for many purposes, including altering solubility, influencing aggregation, dispersion, and even tailoring immune responses in drug delivery. The most unique structural motif of polymer-grafted nanoparticles (PGNs) is the high-density region in the corona where polymer chains are stretched under significant confinement, but orientation of these chains has never been measured because conventional nanoscale-resolved measurements lack sensitivity to polymer orientation in amorphous regions. Here, we directly measure local chain orientation in polystyrene grafted gold nanoparticles using polarized resonant soft X-ray scattering (P-RSoXS). Using a computational scattering pattern simulation approach, we measure the thickness of the anisotropic region of the corona and extent of chain orientation within it. These results demonstrate the power of P-RSoXS to discover and quantify orientational aspects of structure in amorphous soft materials and provide a framework for applying this emerging technique to more complex, chemically heterogeneous systems in the future.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Macroscopic weavable fibers of carbon nanotubes with giant thermoelectric power factor

Low-dimensional materials have recently attracted much interest as thermoelectric materials because of their charge carrier confinement leading to thermoelectric performance enhancement. Carbon nanotubes are promising candidates because of their one-dimensionality in addition to their unique advantages such as flexibility and light weight. However, preserving the large power factor of individual carbon nanotubes in macroscopic assemblies has been challenging, primarily due to poor sample morphology and a lack of proper Fermi energy tuning. Here, we report an ultrahigh value of power factor (14± 5 mW m -1 K -2 ) for macroscopic weavable fibers of aligned carbon nanotubes with ultrahigh electrical and thermal conductivity. The observed giant power factor originates from the ultrahigh electrical conductivity achieved through excellent sample morphology, combined with an enhanced Seebeck coefficient through Fermi energy tuning. We fabricate a textile thermoelectric generator based on these carbon nanotube fibers, which demonstrates high thermoelectric performance, weavability, and scalability. The giant power factor we observe make these fibers strong candidates for the emerging field of thermoelectric active cooling, which requires a large thermoelectric power factor and a large thermal conductivity at the same time.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

A contorted nanographene shelter

Nanographenes have kindled considerable interest in the fields of materials science and supramolecular chemistry as a result of their unique self-assembling and optoelectronic properties. Encapsulating the contorted nanographenes inside artificial receptors, however, remains challenging. Herein, we report the design and synthesis of a trigonal prismatic hexacationic cage, which has a large cavity and adopts a relatively flexible conformation. It serves as a receptor, not only for planar coronene, but also for contorted nanographene derivatives with diameters of approximately 15 Å and thicknesses of 7 Å. A comprehensive investigation of the host-guest interactions in the solid, solution and gaseous states by experimentation and theoretical calculations reveals collectively an induced-fit binding mechanism with high binding affinities between the cage and the nanographenes. Notably, the photostability of the nanographenes is improved significantly by the ultrafast deactivation of their excited states within the cage. Encapsulating the contorted nanographenes inside the cage provides a noncovalent strategy for regulating their photoreactivity.

36 MATERIALS SCIENCE↗

Transport in helical Luttinger liquids in the fractional quantum Hall regime

Abstract Domain walls in fractional quantum Hall ferromagnets are gapless helical one-dimensional channels formed at the boundaries of topologically distinct quantum Hall (QH) liquids. Naïvely, these helical domain walls (hDWs) constitute two counter-propagating chiral states with opposite spins. Coupled to an s-wave superconductor, helical channels are expected to lead to topological superconductivity with high order non-Abelian excitations 1–3 . Here we investigate transport properties of hDWs in the ν = 2/3 fractional QH regime. Experimentally we found that current carried by hDWs is substantially smaller than the prediction of the naïve model. Luttinger liquid theory of the system reveals redistribution of currents between quasiparticle charge, spin and neutral modes, and predicts the reduction of the hDW current. Inclusion of spin-non-conserving tunneling processes reconciles theory with experiment. The theory confirms emergence of spin modes required for the formation of fractional topological superconductivity.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Transverse barrier formation by electrical triggering of a metal-to-insulator transition

Application of an electric stimulus to a material with a metal-insulator transition can trigger a large resistance change. Resistive switching from an insulating into a metallic phase, which typically occurs by the formation of a conducting filament parallel to the current flow, is a highly active research topic. Using the magneto-optical Kerr imaging, we found that the opposite type of resistive switching, from a metal into an insulator, occurs in a reciprocal characteristic spatial pattern: the formation of an insulating barrier perpendicular to the driving current. This barrier formation leads to an unusual N-type negative differential resistance in the current-voltage characteristics. We further demonstrate that electrically inducing a transverse barrier enables a unique approach to voltage-controlled magnetism. By triggering the metal-to-insulator resistive switching in a magnetic material, local on/off control of ferromagnetism is achieved using a global voltage bias applied to the whole device.

36 MATERIALS SCIENCE↗

Surface lattice engineering for fine-tuned spatial configuration of nanocrystals

Hybrid nanocrystals combining different properties together are important multifunctional materials that underpin further development in catalysis, energy storage, et al., and they are often constructed using heterogeneous seeded growth. Their spatial configuration (shape, composition, and dimension) is primarily determined by the heterogeneous deposition process which depends on the lattice mismatch between deposited material and seed. Precise control of nanocrystals spatial configuration is crucial to applications, but suffers from the limited tunability of lattice mismatch. Here, we demonstrate that surface lattice engineering can be used to break this bottleneck. Surface lattices of various Au nanocrystal seeds are fine-tuned using this strategy regardless of their shape, size, and crystalline structure, creating adjustable lattice mismatch for subsequent growth of other metals; hence, diverse hybrid nanocrystals with fine-tuned spatial configuration can be synthesized. This study may pave a general approach for rationally designing and constructing target nanocrystals including metal, semiconductor, and oxide.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Dynamic restructuring of supported metal nanoparticles and its implications for structure insensitive catalysis

Some fundamental concepts of catalysis are not fully explained but are of paramount importance for the development of improved catalysts. An example is the concept of structure insensitive reactions, where surface-normalized activity does not change with catalyst metal particle size. Here we explore this concept and its relation to surface reconstruction on a set of silica-supported Ni metal nanoparticles (mean particle sizes 1–6 nm) by spectroscopically discerning a structure sensitive (CO 2 hydrogenation) from a structure insensitive (ethene hydrogenation) reaction. Using state-of-the-art techniques, inter alia in-situ STEM, and quick-X-ray absorption spectroscopy with sub-second time resolution, we have observed particle-size-dependent effects like restructuring which increases with increasing particle size, and faster restructuring for larger particle sizes during ethene hydrogenation while for CO 2 no such restructuring effects were observed. Furthermore, a degree of restructuring is irreversible, and we also show that the rate of carbon diffusion on, and into nanoparticles increases with particle size. We finally show that these particle size-dependent effects induced by ethene hydrogenation, can make a structure sensitive reaction (CO 2 hydrogenation), structure insensitive. We thus postulate that structure insensitive reactions are actually apparently structure insensitive, which changes our fundamental understanding of the empirical observation of structure insensitivity.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Impact of bulk-edge coupling on observation of anyonic braiding statistics in quantum Hall interferometers

Abstract Quantum Hall interferometers have been used to probe fractional charge and statistics of quasiparticles. We present measurements of a small Fabry–Perot interferometer in which the electrostatic coupling constants which affect interferometer behavior can be determined experimentally. Near the center of the ν = 1/3 state this device exhibits Aharonov–Bohm interference interrupted by a few discrete phase jumps, and Φ 0 oscillations at higher and lower magnetic fields, consistent with theoretical predictions for detection of anyonic statistics. We estimate the electrostatic parameters K I and K I L by two methods: using the ratio of oscillation periods in compressible versus incompressible regions, and from finite-bias conductance measurements. We find that the extracted K I and K I L can account for the deviation of the phase jumps from the theoretical anyonic phase θ a = 2 π /3. At integer states, we find that K I and K I L can account for the Aharonov–Bohm and Coulomb-dominated behavior of different edge states.

77 NANOSCIENCE AND NANOTECHNOLOGY↗