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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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Temperature-induced hexagonal–orthorhombic phase transition in lutetium ferrite nanoparticles

The x-ray diffraction, Raman, and infrared spectroscopies and magnetic measurements were used to explore the correlated changes of the structure, lattice dynamics, and magnetic properties of the LuFeO3 nanoparticles, which appear in dependence on their sintering temperature. We revealed a gradual substitution of the hexagonal phase by the orthorhombic phase in the nanoparticles, with sintering temperature increasing from 700 to 1100 °C. The origin and stability of the hexagonal phase in the LuFeO3 nanoparticles are of the special interest, because the nanoparticles in the phase can be a room-temperature multiferroic with a weak ferromagnetic and pronounced structural and ferroelectric long-range ordering. The antiferromagnetic and nonpolar orthorhombic phase is more stable in the bulk LuFeO3. To define the ranges of the hexagonal phase stability, we determine the bulk and interface energy densities of different phases from the comparison of the Gibbs model with experimental results. Using effective parameters of the Gibbs model, we predict the influence of size effects and temperature on the structural and polar properties of the LuFeO3 nanoparticles. Analysis of the obtained results shows that the combination of the x-ray diffraction, Raman and infrared spectroscopies, magnetic measurements, and theoretical modeling of structural and polar properties allows us to establish the interplay between the phase composition, lattice dynamics, and multiferroic properties of the LuFeO3 nanoparticles prepared under different conditions.

Materials Science↗
DOE OSTI2021

Structural and magnetic properties of iodide-mediated chemically synthesized L1 2 FePt 3 nanoparticles

In this work, we study the effect of elemental iodine as a halide intermediary in the synthesis of FePt 3 nanoparticles using a co-reduction of Fe(acac) 3 and (NH 4 ) 2 PtCl 2 with 1,2-hexadecanediol. Our study shows that elemental iodine facilitates the formation of FePt 3 nanoparticles with the L1 2 structure. When iodine is not used, the as-made nanoparticles have mostly the disordered fcc FePt 3 structure. The as-made nanoparticles are ferromagnetic and have a Curie temperature close to 380 K. Annealing of the as-made nanoparticles leads to an increased particle size and a transformation to the ordered L1 2 FePt 3 phase. Nanoparticles annealed at 700°C for 30 minutes show a mixture of two magnetic phases, a ferromagnetic phase with a lower ordering temperature of ~300 K and an antiferromagnetic phase with a Néel temperature around 135 K.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Partial PdAu nanoparticle embedding into TiO 2 support accentuates catalytic contributions from the Au/TiO 2 interface

Despite the broad catalytic relevance of metal–support interfaces, controlling their chemical nature, the interfacial contact perimeter (exposed to reactants), and consequently, their contributions to overall catalytic reactivity, remains challenging, as the nanoparticle and support characteristics are interdependent when catalysts are prepared by impregnation. Here, we decoupled both characteristics by using a raspberry-colloid-templating strategy that yields partially embedded PdAu nanoparticles within well-defined SiO 2 or TiO 2 supports, thereby increasing the metal–support interfacial contact compared to nonembedded catalysts that we prepared by attaching the same nanoparticles onto support surfaces. Between nonembedded PdAu/SiO 2 and PdAu/TiO 2 , we identified a support effect resulting in a 1.4-fold higher activity of PdAu/TiO 2 than PdAu/SiO 2 for benzaldehyde hydrogenation. Notably, partial nanoparticle embedding in the TiO 2 raspberry-colloid-templated support increased the metal–support interfacial perimeter and consequently, the number of Au/TiO 2 interfacial sites by 5.4-fold, which further enhanced the activity of PdAu/TiO 2 by an additional 4.1-fold. Theoretical calculations and in situ surface-sensitive desorption analyses reveal facile benzaldehyde binding at the Au/TiO 2 interface and at Pd ensembles on the nanoparticle surface, explaining the connection between the number of Au/TiO 2 interfacial sites (via the metal–support interfacial perimeter) and catalytic activity. Our results demonstrate partial nanoparticle embedding as a synthetic strategy to produce thermocatalytically stable catalysts and increase the number of catalytically active Au/TiO 2 interfacial sites to augment catalytic contributions arising from metal–support interfaces.

Lim, Kang Rui Garrick (ORCID:0000000321599844)↗
DOE OSTI2020

Magnetic properties of γ-Fe 2 O 3 nanoparticles in a porous SiO 2 shell for drug delivery

A method is presented for synthesizing core–shell nanoparticles with a magnetic core and a porous shell suitable for drug delivery and other medical applications. The core contains multiple γ -Fe 2 O 3 nanoparticles (~15 nm) enclosed in a SiO 2 (~100–200 nm) matrix using either methyl (denoted TMOS- γ -Fe 2 O 3 ) or ethyl (TEOS- γ -Fe 2 O 3 ) template groups. Low-temperature Mössbauer spectroscopy showed that the magnetic nanoparticles have the maghemite structure, γ -Fe 2 O 3 , with all the vacancies in the octahedral sites. Saturation magnetization measurements revealed that the density of γ -Fe 2 O 3 was greater in the TMOS- γ -Fe 2 O 3 nanoparticles than TEOS- γ -Fe 2 O 3 nanoparticles, presumably because of the smaller methyl group. Magnetization measurements showed that the blocking temperature is around room temperature for the TMOS- γ -Fe 2 O 3 and around 250 K for the TEOS- γ -Fe 2 O 3 . Three dimensional topography analysis shows clearly that the magnetic nanoparticles are not only at the surface but have penetrated deep in the silica to form the core–shell structure.

Physics↗
DOE OSTI2020

Enhancing ZnO nanowire gas sensors using Au/Fe 2 O 3 hybrid nanoparticle decoration

Heterojunctions are an important strategy for designing high performance electrical sensor materials and related devices. Herein, a new type of metal-semiconductor hybrid nanoparticle has been successfully used to remarkably sensitize the surface of ZnO nanowires for detecting NO 2 with high responses over a broad temperature window ranging from room temperature to 600 °C. These hybrid nanoparticles are comprised of iron oxide nanowires with well dispersed single crystalline Au nanoparticles. The hybrid nanoparticle decorated ZnO nanowires have achieved a giant response, as high as 74 500 toward NO 2 gas, about 42 times that of Au decorated ZnO nanowire sensors. This dramatic enhancement may be attributed to the efficient charge transfer across the Au–Fe 2 O 3 Schottky and Fe 2 O 3 –ZnO semiconductor heterojunction interfaces. Due to the incorporation of thermally-stable Fe 2 O 3 nanoparticles as the support of Au nanoparticles, the working temperature of nanowire sensors was successfully extended to higher temperatures, with an increase of 200 °C, from 400 °C to 600 °C. Such a combination of semiconductor heterojunction and semiconductor-metal Schottky contact presents a new strategy for designing high performance electrical sensors with high sensitivity, stability, selectivity, and wide operation temperature window, which are potentially suitable for advanced energy systems such as automotive engines and power plants.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

Investigation of Nanoparticle Degradation in Hydrogen Fuel Cell Systems through Automated Electron Microscopy

Proton exchange membrane fuel cells (PEMFC) are promising devices for the deployment of hydrogen-powered heavy-duty vehicles, providing a higher efficiency for similar driving range and fueling time than the existing ones. However, PEMFCs still encounter durability challenges mainly due to catalyst degradation in the cathode. Mitigating these performance losses requires a better understanding of the degradation mechanisms under heavy-duty accelerated stress tests (ASTs) [1]. Scanning transmission electron microscopy (STEM) combined with energy dispersive X-ray spectroscopy (EDS) are key tools for the analysis of Pt and PtCo nanoparticle size, spatial distribution and composition [2]. Electron tomography is also used to determine the rate and type of degradation of catalyst nanoparticles as a function of their position on the carbon support. In this work, automated data acquisition software, paired with a custom Python code, have been used to study the effect of different accelerated stress tests (ASTs) on nanoparticle coarsening [2]. Figure 1 shows high-angle annular dark-field (HAADF)-STEM images and EDS maps comparing the cathodes of membrane electrode assemblies (MEAs) following an electrocatalyst AST performed under H2/N2 with that of the heavy-duty AST performed under H2/air. We will discuss how AST conditions affect considerably the spatial distribution of the nanoparticles across the electrode between the membrane and microporous layer. Although the median particle size increased more in the MEA aged under the heavy-duty AST, as determined using a high-throughput image analysis, the quantitative EDS measurements demonstrate that the electrocatalyst AST resulted in more Pt and Co dissolution from the cathode, which is another important indicator of electrocatalyst degradation. We will further present the impact of the relative humidity (% RH) on the degradation mechanisms demonstrated using the same approach. Electron tomography has been used to distinguish the Pt nanoparticles residing on the carbon support surface (exterior) from those within the pore structure (interior) in order to determine the relative stability of interior and exterior nanoparticles. As shown in Figure 2, we will compare the Pt catalyst particle size at the beginning of test (BOT) and end of test (EOT), and discuss the importance of automating the electron tomography workflow, i.e. acquisition, reconstruction, and visualization, to increase sampling and determine the standard deviation of these measurement. The outlook for utilizing low-dose cryo-tomography for limiting damage to the catalyst, support, and especially proton-conducting ionomer will also be discussed [3].

Amichi, Lynda↗
DOE OSTI2024

Magnetic Nanoparticle Extraction of Lithium from Produced Waters - CRADA 483 (Final Report)

The demand for lithium in the energy production industry is expected to increase sharply, development of simple and cost-effective techniques for lithium production and recovery from various lithium sources is essential. In this project, core/shell magnetic nanoparticles were successfully designed to selectively extract lithium from aqueous lithium sources as an extension of Pacific Northwest National Laboratory’s magnetic nanofluid extraction technology. The core/shell magnetic nanoparticles are composed of manganese oxide-based lithium ion sieve shells, which allow selective lithium uptake from brines with multiple coexisting ions, over iron oxide cores, which can respond to external magnetic fields for effective recovery and reuse of adsorbents from a liquid. The synthesized lithium ion-sieves and core/shell magnetic nanoparticles were characterized using several techniques to reveal their crystallinity and morphology. The lithium uptake properties of the lithium ion-sieves and core/shell magnetic nanoparticles were evaluated in terms of lithium adsorption capacity, removal percentage, selectivity, and cycling performance in simulated and natural brines. Magnetic properties of the core/shell magnetic nanoparticles were tested by measuring magnetic saturation, and magnetic response of colloidal solutions containing the core/shell magnetic nanoparticles was tested with permanent magnets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Deposition of Nanostructured Thin Film from Size-Classified Nanoparticles

Materials comprising nanometer-sized grains (approximately 1_50 nm) exhibit properties dramatically different from those of their homogeneous and uniform counterparts. These properties vary with size, shape, and composition of nanoscale grains. Thus, nanoparticles may be used as building blocks to engineer tailor-made artificial materials with desired properties, such as non-linear optical absorption, tunable light emission, charge-storage behavior, selective catalytic activity, and countless other characteristics. This bottom-up engineering approach requires exquisite control over nanoparticle size, shape, and composition. We describe the design and characterization of an aerosol system conceived for the deposition of size classified nanoparticles whose performance is consistent with these strict demands. A nanoparticle aerosol is generated by laser ablation and sorted according to size using a differential mobility analyzer. Nanoparticles within a chosen window of sizes (e.g., (8.0 plus or minus 0.6) nm) are deposited electrostatically on a surface forming a film of the desired material. The system allows the assembly and engineering of thin films using size-classified nanoparticles as building blocks.

Camata, Renato P.↗
DOE OSTI2020

Superparamagnetic nanoparticles and nanocomposites

The present invention is directed to the syntheses of superparamagnetic nanoparticles and the incorporation of the nanoparticles as the magnetic component to form a strongly magnetic nanocomposite. The superparamagnetic nanoparticles possess no hysteresis and are too small to support eddy currents. The invention uses a ligand exchange procedure to produce aminated nanoparticles that are then cross-linked using epoxy chemistry. The result is a magnetic nanoparticle component that is covalently linked and well separated. By using this ‘matrix-free’ approach, it is possible to substantially increase the magnetic nanoparticle fraction, while still maintaining good separation, leading to a superparamagnetic nanocomposite with strong magnetic properties and low magnetic losses.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Systems and methods for scale-up synthesis multi-layered Pt-skin nanoparticle catalysts

A method for scaled-up synthesis of PtNi nanoparticles. Synthesizing a Pt nanoparticle catalyst comprises the steps of: synthesizing PtNi nanoparticles, isolating PtNi/substrate nanoparticles, acid leaching the PtNi/substrate, and annealing the leached PtNi/substrate nanoparticles, and forming a Pt-skin on the PtNi/substrate nanoparticles.

Stamenkovic, Vojislav↗
DOE OSTI2021

Structurally ordered nanoparticles, methods and applications

Embodiments provide a nanoparticle and a method for preparing the nanoparticle, as well as a membrane that includes the nanoparticle and a fuel cell that includes the membrane. The method comprises a thermal treatment method that provides from a nanoparticle comprising a structurally disordered material the nanoparticle comprising: (1) a structurally ordered core comprising a first material; and (2) a shell surrounding and further structurally aligned with the structurally ordered core and comprising a second material different from the first material. Particularly desirable is a nanoparticle comprising a Pt3Co@Pt/C structurally ordered core-shell composition supported upon a carbon support.

Abruna, Hector D.↗
DOE OSTI2021

Colloidal immobilized protein based on stable colloid of TiO 2 nanoparticles at neutral pH for protein microarray

A stable colloid of titanium dioxide nanoparticles was specially prepared at neutral pH so that horse radish peroxidase as a model protein can interact and be immobilized with colloidal titanium dioxide nanoparticles, while usually titanium dioxide colloid is only stable at acidic condition. Colloidal immobilized peroxidase based on titanium dioxide nanoparticles at neutral pH were highly active and stably dispersible in aqueous solution. The resulting colloidal immobilized peroxidase can be readily printed using a standard microarray printer for facile fabrication of protein microarrays. After printing, the colloidal immobilized protein formed uniform membrane of proteinated nanoparticles with 3-dimensional nanoconfiguration. Finally, the protein microarray sensitivity based on peroxidase-titanium dioxide nanoparticles was nearly 20 times as high as that using conventional technology.

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

Hairy nanoparticles by atom transfer radical polymerization in miniemulsion

Polymer nanoparticles with various architectures and functionalities are promising materials in numerous fields. Miniemulsion polymerization is one of the suitable pathways to prepare polymer nanoparticles since each droplet could act as a “nanoreactor”. A “smart” atom transfer radical polymerization (ATRP) catalytic system comprising Cu-TPMA/DS – (TPMA = tris(2-pyridylmethyl)amine, DS – = dodecyl sulfate anion) ion pair catalyst was efficiently applied in miniemulsion ATRP at low catalyst concentrations. Herein, hairy nanoparticles consisting of hydrophobic poly(n-butyl methacrylate) (P(BMA/EGDMA), EGDMA = ethylene glycol dimethacrylate) network “core” and hydrophilic oligo(ethylene oxide) methyl ether methacrylate (OEOMA) chains as “hair” were prepared by miniemulsion ATRP and a successive chain extension by aqueous ATRP from the particle surface. The addition of an inimer, 2-(α-bromoisobutyryloxy)ethyl methacrylate (HEMA-iBBr) to the P(BMA/EGDMA) network introduced more ATRP initiation sites for ATRP of OEOMA, enabling adjustment of the particle size from >400 nm to <150 nm. The miniemulsion system remained stable after the one pot synthesis of P(BMA/EGDMA)-g-POEOMA and P(BMA/EGDMA/HEMA-iBBr)-g-POEOMA, and the resulting polymer nanoparticles were re-dispersed in water for further modification. A zwitterionic monomer, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA), was grafted from P(BMA/EGDMA/HEMA-iBBr)-g-POEOMA. The resulting hairy nanoparticles provide an avenue for the design and preparation of novel nanostructured materials.

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

Evaluation of Force Fields for Molecular Dynamics Simulations of Platinum in Bulk and Nanoparticle Forms

Here, understanding the size- and shape-dependent properties of platinum nanoparticles is critical for enabling the design of nanoparticle-based applications with optimal and potentially tunable functionality. Toward this goal, we evaluated nine different empirical potentials with the purpose of accurately modeling faceted platinum nanoparticles using molecular dynamics simulation. First, the potentials were evaluated by computing bulk and surface properties - surface energy, lattice constant, stiffness constants, and the equation of state - and comparing these to prior experimental measurements and quantum mechanics calculations. Then, the potentials were assessed in terms of the stability of cubic and icosahedral nanoparticles with faces in the {100} and {111} planes, respectively. Although none of the force fields predicts all the evaluated properties with perfect accuracy, one potential - the embedded atom method formalism with a specific parameter set - was identified as best able to model platinum in both bulk and nanoparticle forms.

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

Extraordinary Thermal Stability and Sinter Resistance of Sub-2 nm Platinum Nanoparticles Anchored to a Carbon Support by Selenium

Nanoparticle sintering has long been a major challenge in developing catalytic systems for use at elevated temperatures. Here we report an in situ electron microscopy study of the extraordinary sinter resistance of a catalytic system comprised of sub-2 nm Pt nanoparticles on a Se-decorated carbon support. When heated to 700 °C, the average size of the Pt nanoparticles only increased from 1.6 to 2.2 nm, while the crystal structure, together with the {111} and {100} facets, of the Pt nanoparticles was well retained. Our electron microscopy analyses suggested that the superior resistance against sintering originated from the Pt–Se interaction. Confirmed by energy-dispersive X-ray elemental mapping and electron energy loss spectra, the Se atoms surrounding the Pt nanoparticles could survive the heating. This work not only offers an understanding of the physics behind the thermal behavior of this catalytic material but also sheds light on the future development of sinter-resistant catalytic systems.

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

Magnetic and Optical Properties of Au–Co Solid Solution and Phase-Separated Thin Films and Nanoparticles

The chemical composition and morphology of Au x Co 1–x thin films and nanoparticles are controlled via a combination of cosputtering, pulsed laser-induced dewetting (PLiD), and annealing, leading to tunable magnetic and optical properties. Regardless of chemical composition, the as-deposited thin films and as-PLiD nanoparticles are found to possess a face-centered cubic (FCC) Au x Co 1–x solid-solution crystal structure. Annealing results in large phase-separated grains of Au and Co in both the thin films and nanostructures for all chemical compositions. The magnetic and optical properties are characterized via vibrating sample magnetometry (VSM), ellipsometry, optical transmission spectroscopy, and electron energy loss spectroscopy (EELS). Despite the exceptionally high magnetic anisotropy inherent to Co, the presence of sufficient Au (72 atom %) in the Au x Co 1–x solid solution results in superparamagnetic thin films. Among the as-PLiD nanoparticle samples, an increased Co composition leads to a departure from traditional ferromagnetism in favor of wasp-waisted hysteresis caused by magnetic vortices. Phase separation resulting from annealing leads to ferromagnetism for all compositions in both the thin films and nanoparticles. The optical properties of Au x Co 1–x nanostructures are also largely influenced by the chemical morphology, where the Au x Co 1–x intermixed solid solution has significantly damped plasmonic performance relative to pure Au and comparable to pure Co. Phase separation greatly enhances the quality factor, optical absorption, and electron energy loss spectroscopy (EELS) signatures. The enhancement of the localized surface plasmon resonances (LSPRs) scales with the reduction in Co composition, despite EELS evidence that excitation of the Co portions of a nanoparticle can provide a similar, and in some instances enhanced, LSPR resonance compared to Au. This behavior, however, is seemingly limited to the LSPR dipole mode, while higher-order modes are greatly damped by a Co aloof position. As a result, this observed magneto-plasmonic functionality and tunability could be applicable in biomedicine, namely, cancer therapeutics.

annealing (metallurgy)↗
DOE OSTI2022

Covalently integrated silica nanoparticles in poly(ethylene glycol)-based acrylate resins: thermomechanical, swelling, and morphological behavior

Nanocomposites integrate functional nanofillers into viscoelastic matrices for electronics, lightweight structural materials, and tissue engineering. Herein, the effect of methacrylate-functionalized (MA-SiO 2 ) and vinyl-functionalized (V-SiO 2 ) silica nanoparticles on the thermal, mechanical, physical, and morphological characteristics of poly(ethylene glycol) (PEG) nanocomposites was investigated. The gel fraction of V-SiO 2 composites decreases upon addition of 3.8 wt% but increases with further addition (>7.4 wt%) until it reaches a plateau at 10.7 wt%. The MA-SiO 2 induced no significant changes in gel fraction and both V-SiO 2 and MA-SiO 2 nanoparticles had a negligible impact on the nanocomposite glass transition temperature and water absorption. The Young's modulus and ultimate compressive stress increased with increasing nanoparticle concentration for both nanoparticles. Due to the higher crosslink density, MA-SiO 2 composites reached a maximum mechanical stress at a concentration of 7.4 wt%, while V-SiO 2 composites reached a maximum at a concentration of 10.7 wt%. Scanning electron microscopy, transmission electron microscopy, and small-angle X-ray scattering revealed a bimodal size distribution for V-SiO 2 and a monomodal size distribution for MA-SiO 2 . Although aggregates were observed for both nanoparticle surface treatments, V-SiO 2 dispersion was poor while MA-SiO 2 were generally well-dispersed. Finally, these findings lay the framework for silica nanofillers in PEG-based nanocomposites for advanced manufacturing applications.

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

Regulating the Catalytic Activity of Pd Nanoparticles by Confinement in Ordered Mesoporous Supports

Studying structure-sensitive reactions requires the synthesis of catalytic nanoparticles with precisely controlled sizes. Here we demonstrate the facile production of size controlled Pd nanoparticles by confinement in the pores of mesoporous silica nanoparticles (MSN). We show that Pd particles 2.1 nm in size have a higher catalytic activity than larger nanoparticles for the Suzuki-Miyaura cross coupling between 4’-bromoacteophenone and phenyl boronic acid and for the hydrogenation of phenol in aqueous phase. The enhanced activity can be explained in terms of increased number of coordinatively unsaturated sites and higher back donation capacity of the small nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗