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Results for “metallic nanoparticles”

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

Surfactant-free syntheses and pair distribution function analysis of osmium nanoparticles

A surfactant-free synthesis of precious metal nanoparticles (NPs) performed in alkaline low-boiling-point solvents has been recently reported. Monoalcohols are here investigated as solvents and reducing agents to obtain colloidal Os nanoparticles by using low-temperature (<100 °C) surfactant-free syntheses. The effect of the precursor (OsCl 3 or H 2 OsCl 6 ), precursor concentration (up to 100 mM), solvent (methanol or ethanol), presence or absence of a base (NaOH), and addition of water (0 to 100 vol %) on the resulting nanomaterials is discussed. It is found that no base is required to obtain Os nanoparticles as opposed to the case of Pt or Ir NPs. The robustness of the synthesis for a precursor concentration up to 100 mM allows for the performance of X-ray total scattering with pair distribution function (PDF) analysis, which shows that 1–2 nm hexagonal close packed (hcp) NPs are formed from chain-like [OsO x Cl y ] complexes.

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

Effect of TiO x Substrate Interactions on the Electrocatalytic Oxygen Reduction Reaction at Au Nanoparticles

Here, we report a robust model for studying electrocatalytic reactions at metal nanoparticles (NPs) in contact with metal oxide surfaces. The metal oxide layer (TiO x ) is prepared by atomic layer deposition, and it is sufficiently thin that it does not hinder electron transfer from the underlying conductive electrode to the supported AuNP electrocatalysts. In advance of the experiments, density functional theory (DFT) predicted that direct contact between AuNPs and TiO x would lead to enhanced activity for the oxygen reduction reaction (ORR). DFT attributes the observed ORR enhancement to partial charge transfer from oxygen vacancies within the TiO x film to the supported AuNPs and hence formation of anionic Au species. The experimental findings are in near quantitative agreement with the DFT results. Specifically, compared to isolated AuNPs, decreases of ~ 100 and ~ 50 mV in the ORR onset potential are observed experimentally for AuNPs supported on TiO 1.9 and TiO 2.0 films, respectively.

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

Multicomponent Nanoparticle Synthesis for Advanced Manufactured Melt Wire Development

Additive manufacturing (AM) based direct-write technologies have emerged as a predominant enabler for the fabrication of advanced passive sensors in-pile applications. This work continues previous efforts with the modification and optimization of synthesis methods for multi-component nanoparticle systems used to support the development, fabrication and testing of AM sensors for peak temperature detection. For this report, bismuth, bismuth/platinum, tin, tin/silver, tin/zinc, indium, and indium/silver bi-metallic nanoparticles were synthesized using the wet chemical methods. The nanoparticles were then characterized with x-ray fluorescence to evaluate the elemental composition and differential scanning to determine the melting point and mass loss of the samples. Results continue to show that bi-metallic nanoparticles are a viable pathway for the fabrication of high-resolution AM melt wires.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Monitoring Structural and Electronic Changes of Supported Metal Catalysts Using Combined X‐Ray Techniques

Supported metal nanoparticle catalysts have become increasingly crucial for many catalytic applications. However, long-term catalyst stability remains a problem due to catalyst deactivation caused by coke formation and sintering. The deposition of a thin overcoating via atomic layer deposition (ALD) onto metal-supported nanoparticles has shown to greatly inhibit catalyst deactivation. This work utilizes a model catalyst system comprised of Pt nanoparticles supported on Al 2 O 3 to demonstrate the effect of an atomically thin overcoating on supported metal nanoparticles. Continuous operando small-angle X-ray scattering (SAXS) and X-ray absorption near edge spectroscopy (XANES) monitor structural and electronic changes to the catalyst and overcoating during calcination. SAXS data fitting reveals the formation of nanopores in the overcoating at high temperatures, while XANES monitors the oxidation state of the Pt catalyst. Herein, the usefulness of combined X-ray techniques is demonstrated to characterize supported metal catalysts to further understanding of the synergistic effects of the ALD overcoating to aid in the design of new catalyst materials.

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

Combined Plasmonic Au-nanoparticle and Conducting Metal Oxide High-temperature Optical Sensing with LSTO

<span style="color: rgba(0, 0, 0, 0.79); font-family: &quot;Source Sans Pro&quot;, source-sans-pro, museo_sans300, museo-sans, Arial, sans-serif; font-size: 16px; background-color: rgb(255, 255, 255);">Fiber optic sensor technology offers several advantages for harsh-environment applications. However, the development of optical gas sensing layers that are stable under harsh environmental conditions is an ongoing research challenge. In this work, electronically conducting metal oxide lanthanum-doped strontium titanate (LSTO) films embedded with gold nanoparticles are examined as a sensing layer for application in reducing gas flows at high temperature (600–800 °C). A strong localized surface plasmon resonance (LSPR) based response to hydrogen is demonstrated in the visible region of the spectrum, while a Drude free electron-based response is observed in the near-IR. Characteristics of these responses are studied both on planar glass substrates and on silica fibers. Charge transfer between the oxide film and the gold nanoparticles is explored as a possible mechanism governing the Au LSPR response and is considered in terms of the corresponding properties of the conducting metal oxide-based matrix phase. Principal component analysis is applied to the combined plasmonic and free-carrier based response over a range of temperatures and hydrogen concentrations. It is demonstrated that the combined visible and near-IR response of these films provides improved versatility for multiwavelength interrogation, as well as improved discrimination of important process parameters (concentration and temperature) through application of multivariate analysis techniques.</span>

Wuenschell, Jeffrey K.↗
DOE OSTI2021

Revealing the etching process of water-soluble Au 25 nanoclusters at the molecular level

Etching (often considered as decomposition) is one of the key considerations in the synthesis, storage, and application of metal nanoparticles. However, the underlying chemistry of their etching process still remains elusive. Here, we use real-time electrospray ionization mass spectrometry to study the reaction dynamics and size/structure evolution of all the stable intermediates during the etching of water-soluble thiolate-protected gold nanoclusters (Au NCs), which reveal an unusual “recombination” process in the oxidative reaction environment after the initial decomposition process. Interestingly, the sizes of NC species grow larger and their ligand-to-metal ratios become higher during this recombination process, which are distinctly different from that observed in the reductive growth of Au NCs (e.g., lower ligand-to-metal ratios with increasing sizes). The etching chemistry revealed in this study provides molecular-level understandings on how metal nanoparticles transform under the oxidative reaction environment, providing efficient synthetic strategies for new NC species through the etching reactions.

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

High-Temperature Ferrofluids Based on Molten Salts

Molten metal chloride salts are promising candidates for advanced heat transfer fluids in generation IV nuclear reactors and beyond. However, research on the magnetic properties of suspended metallic nanoparticles at elevated temperatures is scarce, and there have been no attempts to develop a high-temperature, molten salt based ferrofluid. Such a ferrofluid would enable in situ manipulation of both the physical and thermal properties of the fluid via an external magnetic field. This study examines molten salt based ferrofluids comprised of metallic cobalt nanoparticles dispersed in molten metal chloride salts. High-temperature magnetometry and magneto-thermogalvometric measurements were conducted to evaluate the magnetic characteristics of the ferrofluid. Further analysis was conducted through a combination of microscopy, spectroscopy, solubility tests, and diffraction measurements. Furthermore, the metallic cobalt nanoparticles exhibited a notable degree of chemical stability and sustained magnetism from 25 to 800 °C when suspended in NaCl–MgCl 2 and KCl–ZnCl 2 mixtures.

Cobalt↗
DOE OSTI2021

Microwave synthesis of single-phase nanoparticles made of multi-principal element alloys

In this work, metal nanoparticles of multi-principal element alloys (MPEA) with a single crystalline phase have been synthesized by flash heating/cooling of nanosized metals encapsulated in micelle vesicles dispersed in an oil phase (e.g., cyclohexane). Flash heating is realized by selective absorption of a microwave pulse in metals to rapidly heat metals into uniform melts. The oil phase barely absorbs microwave and maintains the low temperature, which can rapidly quench the high-temperature metal melts to enable the flash cooling process. The precursor ions of four metals, including Au, Pt, Pd, and Cu, can be simultaneously reduced by hydrazine in the aqueous solution encapsulated in the micelle vesicles. The resulting metals efficiently absorb microwave energy to locally reach a temperature high enough to melt themselves into a uniform mixture. The duration of microwave pulse is crucial to ensure the reduced metals mix uniformly, while the temperature of oil phase is still low to rapidly quench the metals and freeze the single-phase crystalline lattices in alloy nanoparticles. The microwave-enabled flash heating/cooling provides a new method to synthesize single-phase MPEA nanoparticles of many metal combinations when the appropriate water-in-oil micelle systems and the appropriate reduction reactions of metal precursors are available.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Exsolution-Driven Surface Transformation in the Host Oxide

Exsolution synthesizes self-assembled metal nanoparticle catalysts via phase precipitation. An overlooked aspect in this method thus far is how exsolution affects the host oxide surface chemistry and structure. Such information is critical as the oxide itself can also contribute to the overall catalytic activity. Here, combining X-ray and electron probes, we investigated the surface transformation of thin-film SrTi 0.65 Fe 0.35 O 3 during Fe 0 exsolution. We found that exsolution generates a highly Fe-deficient near-surface layer of about 2 nm thick. Moreover, the originally single-crystalline oxide near-surface region became partially polycrystalline after exsolution. Such drastic transformations at the surface of the oxide are important because the exsolution-induced nonstoichiometry and grain boundaries can alter the oxide ion transport and oxygen exchange kinetics and, hence, the catalytic activity toward water splitting or hydrogen oxidation reactions. These findings highlight the need to consider the exsolved oxide surface, in addition to the metal nanoparticles, in designing the exsolved nanocatalysts.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Long-term Accumulation, Depth Distribution, and Speciation of Silver Nanoparticles in Biosolids-Amended Soils

Biosolids, when applied to soil, can be a source of metals and metal nanoparticles. One of the metals that forms nanoparticles is silver (Ag), which is commonly used in elemental (Ag(0)) form as an engineered nanomaterial in industrial or consumer products. The objective of this study was to quantify and characterize the accumulation and transport of Ag in a natural soil that has received agronomically-recommended rates of biosolids as fertilizer for the past 23 years (1994{2017). Total Ag concentrations were measured in biosolids and soil samples collected from 0 to 10 cm between 1996 and 2017. In addition, the depth distribution of Ag in the soil down to 60-cm depth was measured in 2017. Electron microscopy, in combination with X-ray spectroscopy, and X-ray absorption spectroscopy were used to identify the elemental association and oxidation state of the Ag in the samples. The Ag concentrations in the biosolids-amended soil increased steadily from 1996 until 2007, after which the concentrations leveled off at about 1.25 mg Ag kg-1 soil. This corresponded with a decrease of Ag concentrations in the biosolids over time. The majority of the Ag (82%) was confined to the top 10 cm of the soil, small amounts (14%) were detected in 10 to 20-cm depth, and trace amounts (4%) in 30 to 40-cm depth. The Ag in the biosolids and soil was identified as Ag-containing nanoparticles with a diameter of 10 to 12 nm. Ag was associated with S suggest that these 19 nanoparticles are Ag2S. This could be corroborated in biosolids with X-ray absorption spectroscopy (XANES); however, the Ag concentrations in the soil samples were too low to allow identification with XANES. Biosolids, when applied at agronomic rates in dryland cropping systems, represent an economically viable source of crop nutrients. In our study, long-term application of biosolids did not increase the concentration of total Ag in soil above a maximum of 1.5 mg Ag kg-1, and the Ag is present in the sulfide form. This concentration is below ecotoxicity limits for Ag2S in soil.

Taylor, Stephen E.↗
DOE OSTI2024

Structural Studies of Alloyed and Nanoparticle Transition Metal Dichalcogenides by Selenium-77 Solid-State Nuclear Magnetic Resonance Spectroscopy

Layered transition metal dichalcogenides (TMDCs) such as MoS 2 , MoSe 2 , and WSe 2 are under intense investigation because they are atomically thin semiconductors with photophysical properties that can be tuned by changing their composition or morphology. Mechanochemical processing has been proposed as a method to obtain alloyed TMDCs in the series Mo 1–x W x S y Se 2–y (x = 0–1; y = 0–2). However, elucidating the chemical transformations occurring at the atomic scale following mechanochemical processing can be challenging because the products are often amorphous or microcrystalline. To address this challenge, we probe TMDC mixing and alloying by using a combination of powder X-ray diffraction, Raman spectroscopy, diffuse reflectance spectroscopy, 77 Se solid-state nuclear magnetic resonance (SSNMR) spectroscopy, and planewave density functional theory (DFT) calculations. The nature of the milling material and reaction atmosphere are shown to be essential factors in limiting the formation of undesired oxide byproducts. We demonstrate acquisition of 77 Se SSNMR spectra using different combinations of Carr-Purcell Meiboom-Gill acquisition (CPMG) pulse sequences, magic angle spinning (MAS), and MAS dynamic nuclear polarization. Further, the combination of SSNMR with the other characterization methods clearly demonstrates that high energy impact ball milling induces molecular level alloying of Mo, W and chalcogen atoms in the family Mo 1–x W x S y Se 2–y . Gauge including projector augmented wave DFT calculations yield accurate 77 Se chemical shift (CS) tensor components. 77 Se SSNMR spectroscopy was also applied to study the structure of WSe 2 nanocrystals intercalated with ethylenediamine. The intercalated WSe 2 nanocrystals exhibit a more positive isotropic 77 Se CS as compared to bulk WSe 2 , however, the 77 Se CS anisotropy is the same, confirming the WSe 2 layers have a similar structure as in their bulk counterparts.

36 MATERIALS SCIENCE↗
DOE OSTI2021

LaMer's 1950 model of particle formation: a review and critical analysis of its classical nucleation and fluctuation theory basis, of competing models and mechanisms for phase-changes and particle formation, and then of its application to silver halide, semiconductor, metal, and metal-oxide nanoparticles

Are classical nucleation theory and the 1950 LaMer model of particle formation supported for a wide range of particle formations, or do competing models in the form of chemical reaction mechanisms have better experimental support? Read on to find out.

Whitehead, Christopher B.↗
DOE OSTI2023

Synthesizing and formulating metal oxide nanoparticle inks for perovskite solar cells

The perovskite solar cell has commercial potential due to the low-cost of materials and manufacturing processes with cell efficiencies on par with traditional technologies. Nanomaterials have many properties that make them attractive for the perovskite devices, including low-cost inks, low temperature processing, stable material properties and good charge transport. In this feature article, the use of nanomaterials in the hole transport and electron transport layers are reviewed. Specifically, SnO 2 and NiO x are the leading materials with the most promise for translation to large scale applications. Here, the review includes a discussion of the synthesis, formulation, and processing of these nanoparticles and provides insights for their further deployment towards commercially viable perovskite solar cells.

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

Annealed metal nano-particle decorated nanotubes

Disclosed are methods and systems of providing carbon nanotubes decorated with polymer coated metal nanoparticles. Then, annealing the metal coated carbon nanotubes to reduce a quantity of hydrophilic components of the polymer coating.

Iftime, Gabriel↗
DOE OSTI2024

Single-Atom Alloy Formation via Reaction-Driven Catalyst Restructuring

We demonstrate that single-atom alloy catalysts can be made by exposing physical mixtures of monometallic supported Cu and Pd catalysts to vinyl acetate (VA) synthesis reaction conditions. This reaction induces the formation of mobile clusters of metal diacetate species that drive extensive metal nanoparticle restructuring, leading to atomic dispersion of the precious metal, smaller nanoparticle sizes than the parent catalysts, and high activity and selectivity for both VA synthesis and ethanol dehydrogenation reactions. As a result, this approach is scalable and appears to be generalizable to other alloy catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗