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At least 1,585 records · Page 88

Optical and Probe Diagnostics Applied to Reacting Flows

The general theme of the research my NASA colleague and I have planned is "Optical and probe diagnostics applied to reacting flows". We plan to explore three major threads during the fellowship period. The first interrogates the flame synthesis of carbon nanotubes using aerosol catalysts. Having demonstrated the viability of the technique for nanotube synthesis, we seek to understand the details of this reacting system which are important to its practical application. Laser light scattering will reveal changes in particle size at various heights above the burner. Analysis of the flame gas by mass spectroscopy will reveal the chemical composition of the mixture. Finally, absorption measurements will map the nanotube concentration within the flow. The second thread explores soot oxidation kinetics. Despite the impact of soot on engine performance, fire safety and pollution, models for its oxidation are inhibited by uncertainty in the values of the oxidation rate. We plan to employ both optical and microscopic measurements to refine this rate. Cavity ring-down absorption measurements of the carbonaceous aerosol can provide a measure of the mass concentration with time and, hence, an oxidation rate. Spectroscopic and direct probe measurements will provide the temperature of the system needed for subsequent modeling. These data will be benchmarked against changes in soot nanostructures as revealed by transmission electron microscopic images from directly sampled material.

Ticich, Thomas M.↗

Stardust in STARDUST - the C, N, and O Isotopic Compositions of Wild 2 Cometary Matter in Al Foil Impacts

In January 2006, the Stardust mission successfully returned dust samples from the tail of comet 81P/Wild 2 in two principal collection media, low density silica aerogel and Al foil. While hypervelocity impacts at the Stardust encounter velocity of 6.1 kilometers per second into Al foils are generally highly disruptive for natural, silicate-dominated impactors, previous studies have shown that many craters retain sufficient residue to allow a determination of the elemental and isotopic compositions of the original projectile. We have used two NanoSIMS ion microprobes to perform C, N, and O isotope imaging measurements on four large (59-295 micrometer diameter) and on 47 small (0.32-1.9 micrometer diameter) Al foil impact craters as part of the Stardust Preliminary Examination. Most analyzed residues in and around these craters are isotopically normal (solar) in their C, N, and O isotopic compositions. However, the debris in one large crater shows an average N-15 enrichment of approx. 450%o, which is similar to the bulk composition of some isotopically primitive interplanetary dust particles and to components of some primitive meteorites. A 250 nm grain in another large crater has an O-17 enrichment with approx. 2.65 times the solar O-17/O-16 ratio. Such an O isotopic composition is typical for circumstellar oxide or silicate grains from red giant or asymptotic giant branch stars. The discovery of this circumstellar grain clearly establishes that there is authentic stardust in the cometary samples returned by the Stardust mission. However, the low apparent abundance of circumstellar grains in Wild 2 samples and the preponderance of isotopically normal material indicates that the cometary matter is a diverse assemblage of presolar and solar system materials.

Stadermann, Frank J.↗

Aluminum is More Cytotoxic than Lunar Dust in Human Skin and Lung Fibroblasts

NASA plans to build a permanent space station on the moon to explore its surface. The surface of the moon is covered in lunar dust, which consists of fine particles that contain silicon, aluminum and titanium, among others. Because this will be a manned base, the potential toxicity of this dust has to be studied. Also, toxicity standards for potential exposure have to be set. To properly address the potential toxicity of lunar dust we need to understand the toxicity of its individual components, as well as their combined effects. In order to study this we compared NASA simulant JSC-1AVF (volcanic ash particles), that simulates the dust found on the moon, to aluminum, the 3rd most abundant component in lunar dust. We tested the cytotoxicity of both compounds on human lung and skin fibroblasts (WTHBF-6 and BJhTERT cell lines, respectively). Aluminum oxide was more cytotoxic than lunar dust to both cell lines. In human lung fibroblasts 5, 10 and 50 g/sq cm of aluminum oxide induced 85%, 61% and 30% relative survival, respectively. For human skin fibroblasts the same concentrations induced 58%, 41% and 58% relative survival. Lunar dust was also cytotoxic to both cell lines, but its effects were seen at higher concentrations: 50, 100, 200 and 400 g/sq cm of lunar dust induced a 69%, 46%, 35% and 30% relative survival in the skin cells and 53%, 16%, 8% and 2% on the lung cells. Overall, for both compounds, lung cells were more sensitive than skin cells. This work was supported by a NASA EPSCoR grant through the Maine Space Grant Consortium (JPW), the Maine Center for Toxicology and Environmental Health., a Fulbright Grant (JM) and a Delta Kappa Gamma Society International World Fellowship (JM).

Hammond, D.↗

Different interfacial reactivity of lithium metal chloride electrolytes with high voltage cathodes determines solid-state battery performance

A deep understanding of the interaction of the surface of cathode materials with solid electrolytes is crucial to design advanced solid-state batteries (SSBs). This is especially true for the new class of lithium metal chloride (Li-M-Cl) solid electrolytes which are receiving rapidly growing attention due to their very high oxidative stability (>4 V) in combination with good ionic conductivity that can enable long cell cycle life. While Li-M-Cl electrolytes typically contain resource-limited metals (M) such as indium or rare earths, work has focused on substituting M with more abundant elements such as zirconium. Via operando resistance measurements using intermittent current interruption we explore the dynamic evolution of the interphase at the surface of Ni-rich NCM85 or NCM111 cathode particles inside a working SSB with three different Li-(M 1 ,M 2 )-Cl catholytes (Li 3 InCl 6 , Li 2 Sc 1/3 In 1/3 Cl 4 and Li 5/2 Y 1/2 Zr 1/2 Cl 6 ) to reveal the impact of the cationic metal substitution on the interfacial chemistry. We show that the metal plays a critical role in determining high voltage stability, contrary to prior assumptions. Using a combination of cyclic voltammetry and ultraviolet photoelectron spectroscopy measurements of the electronic band structure to assess oxidative stability; coupled with DFT calculations and ToF-SIMS to evaluate products formed at the interface at different upper cutoff potentials and degrees of delithiation, we are able to differentiate between electrochemical and chemical degradation. We find that Li 2 Sc 1/3 In 1/3 Cl 4 yields the highest (and Li 3 InCl 6 the lowest) stability against electrochemical oxidation, while Li 5/2 Y 1/2 Zr 1/2 Cl 6 undergoes a detrimental chemical reaction with oxygen released from Ni-rich NCM85 at high potentials, resulting in fast capacity fading. Altogether, our work establishes a platform for the metrics and an approach that can be utilized to efficiently evaluate the stability of new halide SEs in SSB cells.

25 ENERGY STORAGE↗

Imitating Architectural Mortise‐Tenon Structure for Stable Ni‐Rich Layered Cathodes

Ni-rich layered oxides are the most promising cathodes for Li-ion batteries, but chemo-mechanical failures during cycling and large first-cycle capacity loss hinder their applications in high-energy batteries. Herein, by introducing spinel-like mortise-tenon structures into the layered phase of LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811), the adverse volume variations in cathode materials can be significantly suppressed. Meanwhile, these mortise-tenon structures play the role of the expressway for fast lithium-ion transport, which is substantiated by experiments and calculations. Moreover, the particles with mortise-tenon structures usually terminate with the most stable (003) facet. The new cathode exhibits a discharge capacity of 215 mAh g –1 at 0.1 C with an initial Coulombic efficiency of 97.5%, and capacity retention of 82.2% after 1200 cycles at 1 C. Importantly, this work offers a viable lattice engineering to address the stability and low initial Coulombic efficiency of the Ni-rich layered oxides, and facilitates the implementation of Li-ion batteries with high-energy density and long durability.

25 ENERGY STORAGE↗

What Controls the Vertical Distribution of Aerosol? Relationships Between Process Sensitivity in HadGEM3-UKCA and Inter-Model Variation from AeroCom Phase II

The vertical profile of aerosol is important for its radiative effects, but weakly constrained by observations on the global scale, and highly variable among different models. To investigate the controlling factors in one particular model, we investigate the effects of individual processes in HadGEM3-UKCA and compare the resulting diversity of aerosol vertical profiles with the inter-model diversity from the AeroCom Phase II control experiment. In this way we show that (in this model at least) the vertical profile is controlled by a relatively small number of processes, although these vary among aerosol components and particle sizes. We also show that sufficiently coarse variations in these processes can produce a similar diversity to that among different models in terms of the global-mean profile and, to a lesser extent, the zonal-mean vertical position. However, there are features of certain models' profiles that cannot be reproduced, suggesting the influence of further structural differences between models. In HadGEM3-UKCA, convective transport is found to be very important in controlling the vertical profile of all aerosol components by mass. In-cloud scavenging is very important for all except mineral dust. Growth by condensation is important for sulfate and carbonaceous aerosol (along with aqueous oxidation for the former and ageing by soluble material for the latter). The vertical extent of biomass-burning emissions into the free troposphere is also important for the profile of carbonaceous aerosol. Boundary-layer mixing plays a dominant role for sea salt and mineral dust, which are emitted only from the surface. Dry deposition and below-cloud scavenging are important for the profile of mineral dust only. In this model, the microphysical processes of nucleation, condensation and coagulation dominate the vertical profile of the smallest particles by number (e.g. total CN >3 nm), while the profiles of larger particles (e.g. CN>100 nm) are controlled by the same processes as the component mass profiles, plus the size distribution of primary emissions. We also show that the processes that affect the AOD-normalised radiative forcing in the model are predominantly those that affect the vertical mass distribution, in particular convective transport, in-cloud scavenging, aqueous oxidation, ageing and the vertical extent of biomass-burning emissions.

dust↗

Fluorine spillover for ceria- vs silica-supported palladium nanoparticles: A MD study using machine learning potentials

Supported metallic nanoparticles play a central role in catalysis. However, predictive modeling is particularly challenging due to the structural and dynamic complexity of the nanoparticle and its interface with the support, given that the sizes of interest are often well beyond those accessible via traditional ab initio methods. With recent advances in machine learning, it is now feasible to perform MD simulations with potentials retaining near-density-functional theory (DFT) accuracy, which can elucidate the growth and relaxation of supported metal nanoparticles, as well as reactions on those catalysts, at temperatures and time scales approaching those relevant to experiments. Furthermore, the surfaces of the support materials can also be modeled realistically through simulated annealing to include effects such as defects and amorphous structures. We study the adsorption of fluorine atoms on ceria and silica supported palladium nanoparticles using machine learning potential trained by DFT data using the DeePMD framework. We show defects on ceria and Pd/ceria interfaces are crucial for the initial adsorption of fluorine, while the interplay between Pd and ceria and the reverse oxygen migration from ceria to Pd control spillover of fluorine from Pd to ceria at later stages. In contrast, silica supports do not induce fluorine spillover from Pd particles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Combustion of Metals in Reduced-Gravity and Extra Terrestrial Environments

The combustion of metals is a field with important practical applications in rocket propellants, high-temperature flames, and material synthesis. Also, the safe operation of metal containers in high-pressure oxygen systems and with cryogenic fuels and oxidizers remains an important concern in industry. The increasing use of metallic components in spacecraft and space structures has also raised concerns about their flammability properties and fire suppression mechanisms. In addition, recent efforts to embark on unmanned and manned planetary exploration, such as on Mars, have also renewed the interest in metal/carbon-dioxide combustion as an effective in situ resource utilization technology. In spite of these practical applications, the understanding of the combustion properties of metals remains far behind that of the most commonly used fuels such as hydrocarbons. The lack of understanding is due to the many problems unique to metal- oxidizer reactions such as: low-temperature surface oxidation prior to ignition, heterogeneous reactions, very high combustion temperatures, product condensation, high emissivity of products, and multi-phase interactions. Very few analytical models (all neglecting the influence of gravity) have been developed to predict the burning characteristics and the flame structure details. Several experimental studies attempting to validate these models have used small metal particles to recreate gravity-free conditions. The high emissivity of the flames, rapid reaction, and intermittent explosions experienced by these particles have made the gathering of any useful information on burning rates and flame structure very difficult. The use of a reduced gravity environment is needed to clarify some of the complex interactions among the phenomena described above. First, the elimination of the intrusive buoyant flows that plague all combustion phenomena is of paramount importance in metal reactions due to the much higher temperatures reached during combustion. Second, a low-gravity environment is absolutely essential to remove the destructive effect of gravity on the shape of a molten metal droplet in order to study a spherically symmetric condition with large bulk samples. The larger size of the spherical metal droplet and the longer burning times available in reduced gravity extend the spatial and temporal dimensions to permit careful probing of the flame structure and dynamics. Third, the influence of the radiative heat transfer from the solid oxides can be studied more carefully by generating a stagnant spherical shell of condensed products undisturbed by buoyancy.

Branch, M.C.↗

Transition Metal Dissolution Mechanisms and Impacts on Electronic Conductivity in Composite LiNi 0.5 Mn 1.5 O 4 Cathode Films

The high-voltage LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel cathode material offers high energy density storage capabilities without the use of costly Co that is prevalent in other Li-ion battery chemistries (e.g., LiNi x Mn y Co z O 2 (NMC)). Unfortunately, LNMO-containing batteries suffer from poor cycling performance because of the intrinsically coupled processes of electrolyte oxidation and transition metal dissolution that occurs at high voltage. In this work, we use operando electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectroscopies to demonstrate that transition metal dissolution in LNMO is tightly coupled to HF formation (and thus, electrolyte oxidation reactions as detected with operando and in situ solution NMR), indicative of an acid-driven disproportionation reaction that occurs during delithiation (i.e., battery charging). Leveraging the temporal resolution (s-min) of magnetic resonance, we find that the LNMO particles accelerate the rate of LiPF 6 decomposition and subsequent Mn 2+ dissolution, possibly due to the acidic nature of terminal Mn-OH groups. X-ray photoemission electron microscopy (XPEEM) provides surface-sensitive and localized X-ray absorption spectroscopy (XAS) measurements, in addition to X-ray photoelectron spectroscopy (XPS), that indicate disproportionation is enabled by surface reconstruction upon charging, which leads to surface Mn 3+ sites on the LNMO particle surface that can disproportionate into Mn 2+ (dissolved) and Mn 4+ (s) . During discharge of the battery, we observe high quantities of metal fluorides (in particular, MnF 2 ) in the cathode electrolyte interphase (CEI) on LNMO as well as the conductive carbon additives in the composite. Electronic conductivity measurements indicate that the MnF 2 decreases film conductivity by threefold compared to LiF, suggesting that this CEI component may impede both the ionic and electronic properties of the cathode. Ultimately, to prevent transition metal dissolution and the associated side reactions in spinel-type cathodes (particularly those that operate at high voltages like LNMO), the use of electrolytes that offer improved anodic stability and prevent acid byproducts will likely be necessary.

36 MATERIALS SCIENCE↗

Continuous Encodable Reshaping of Gold Nanocrystals through Facet Modulation

Shape control of nanocrystals (NCs) is crucial for tuning their assembly behavior and functional properties, yet the precise manipulation of facet composition remains challenging. Here, we present a nanocrystal reshaping strategy to control and modulate the facets of gold (Au) NCs. Our one-pot approach, conducted at room temperature, requires only initial Au NCs, Au 3+ ions, and surfactants, distinguishing it from conventional reduction-mediated “etching-and-regrowth” methods. Detailed structural studies using electron microscopy, small-angle X-ray scattering (SAXS), and UV−vis spectroscopy reveal the surfactant-encoded pathway for NC transformation from shaped particles to spheres and then into various polyhedral shapes while preserving the individual particles' volume. The proposed reshaping mechanism involves the dissolution of surface Au atoms into Au + complexes in the presence of Au 3+ and surfactant, followed by surfactant-guided redeposition and formation of facets with different atomic planes. Using the ethanol oxidation reaction (EOR) as a probe, we observe a quasi-linear decrease in onset potential and an increase in activity with increasing {100} facet exposure. This work broadens synthetic strategies by offering precise NC reshaping and facet control.

36 MATERIALS SCIENCE↗

Nanometer Scale Imaging to Develop Quantitative Descriptors of Bipolar Membrane Junction Structure

Swings in pH can be achieved by electrically polarizing a bipolar membrane (BPM) to drive water dissociation at the BPM junction for electrochemical conversion and separation processes. BPM junction design is critical to tailor performance for specific applications; however, characterization techniques capable of resolving the nanometer scale physical structure of the junction are limited. We present sample preparation, imaging, and analysis workflows that are adaptable to a variety of BPM junction architectures. Atomic force microscopy produces BPM junction images with nanometer scale lateral resolution for samples with and without a graphene oxide water dissociation catalyst in the junction. Subsequent image segmentation and analysis quantify line edge roughness and catalyst layer thickness as descriptors of junction structure. Comparison of pre- and post-electrodialysis junctions suggests electric field-induced alignment of catalyst particles during electrodialysis. This characterization workflow can inform manufacturing protocols, computational modeling, and failure mode analysis for next-generation BPMs.

97 MATHEMATICS AND COMPUTING↗

Editorial: Applications of spectroscopy and chemometrics in nuclear materials analysis

Optical analysis techniques, including spectroscopy and image analysis, have many advantages when applied to the study of nuclear materials. They require small sample sizes, can be performed remotely, and can be proceduralized through consistent practice. Most importantly, they provide a wealth of information by generating multivariate data. For example, ultraviolet–visible–near-infrared absorbance spectroscopy of actinides in aqueous and organic solutions is dependent on the oxidation state, anionic complexation, and temperature. These variables are important for solution-based separation processes, and sensitivity to these factors, combined with online monitoring, can drive the efficiency and control of these processes. The morphology and chemical composition of actinide particles can also provide a vital clue to the mechanisms by which the particles were formed, providing forensic information on the origins of the particles.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Molecular wake shield gas analyzer

Techniques for measuring and characterizing the ultrahigh vacuum in the wake of an orbiting spacecraft are studied. A high sensitivity mass spectrometer that contains a double mass analyzer consisting of an open source miniature magnetic sector field neutral gas analyzer and an identical ion analyzer is proposed. These are configured to detect and identify gas and ion species of hydrogen, helium, nitrogen, oxygen, nitric oxide, and carbon dioxide and any other gas or ion species in the 1 to 46 amu mass range. This range covers the normal atmospheric constituents. The sensitivity of the instrument is sufficient to measure ambient gases and ion with a particle density of the order of one per cc. A chemical pump, or getter, is mounted near the entrance aperture of the neutral gas analyzer which integrates the absorption of ambient gases for a selectable period of time for subsequent release and analysis. The sensitivity is realizable for all but rare gases using this technique.

Hoffman, J. H.↗

Sol-gel synthesis and densification of aluminoborosilicate powders. Part 1: Synthesis

Aluminoborosilicate powders high in alumina content were synthesized by the sol-gel process utilizing various methods of preparation. Properties and microstructural effects related to these syntheses were examined. After heating to 600 C for 2 h in flowing air, the powders were amorphous with the metal oxides comprising 87 percent of the weight and uncombusted organics the remainder. DTA of dried powders revealed a T(sub g) at approximately 835 C and an exotherm near 900 C due to crystallization. Powders derived from aluminum secbutoxide consisted of particles with a mean diameter 5 microns less than those from aluminum isopropoxide. Powders synthesized with aluminum isopropoxide produced agglomerates comprised of rod shaped particulates while powders made with the secbutoxide precursor produced irregular glassy shards. Compacts formed from these powders required different loadings for equivalent densities according to the method of synthesis.

Bull, Jeffrey↗

Issues/considerations and performance prediction of LEO protective coatings

Organic materials can be used in low earth orbit for long periods only if they are made to be durable to atomic oxygen in addition to the threats of ultraviolet radiation, micrometeoroid and debris impact, thermal cycling, and charged particle radiation. In many materials applications, it is more cost-effective to utilize atomic oxygen protective coatings over materials which are vulnerable to attack by atomic oxygen rather than developing alternative materials which are inherently durable. Many metal and metal oxide coatings have been shown to be potentially suitable for long term protection of organic polymers in low earth orbit. The protection afforded by thin film coatings on polymeric substrates is highly dependent on the completeness of coverage of the coating. Thus, the prime indicator of durability is the size and abundance of pin windows and scratches in the protective coating. Such defects depend on the deposition technique, smoothness of the surface to be protected, and presence of particulate contaminants. Issues and considerations relevant to substrate preparation, deposition of protective coatings, ground laboratory simulation and evaluation of threats in low earth orbit to protective materials, results of in-space tests, and the use of Monte Carlo modeling techniques to predict in-space durability are presented in graphic form.

Banks, Bruce A.↗

Leonid's Particle Analyses from Stratospheric Balloon Collection on Xerogel Surfaces

Recovered from a stratospheric balloon above 20 km on 17-18 November 1998, at least eight candidate microparticles were collected and analyzed from low-density silica xerogel collection plates. Capture time at Leonids' storm peak was validated locally along the balloon trajectory by direct video imaging of meteor fluence up to 24/hr above 98% of the Earth's atmosphere. At least one 30 micron particle agrees morphologically to a smooth, unmelted spherule and compares most closely in non-volatile elemental ratios (Mg/Si, Al/Si, and Fe/Si) to compositional data in surface/ocean meteorite collections. A Euclidean tree diagram based on composition makes a most probable identification as a non-porous stratospherically collected particle and a least probable identification as terrestrial matter or an ordinary chondrite. If of extraterrestrial origin, the mineralogical class would be consistent with a stony (S) type of silicate, olivine [(Mg,Fe)2SiO4] and pyroxene [(Mg, Fe)Si!O3)--or oxides, herecynite [(Fe,Mg) Al2O4].

Noever, David↗

Chronic Lunar Dust Exposure on Rat Cornea: Evaluation by Gene Expression Profiling

Lunar dust is capable of entering habitats and vehicle compartments by sticking to spacesuits or other objects that are transferred into the spacecraft from the lunar surface and has been reported to cause irritation upon exposure. During the Apollo missions, crewmembers reported irritation specifically to the skin and eyes after contamination of the lunar and service modules. It has since been hypothesized that ocular irritation and abrasion might occur as a result of such exposure, impairing crew vision. Recent work has shown that both ultrafine and unground lunar dust exhibited minimal irritancy of the ocular surface (i.e., cornea); however, the assessment of the severity of ocular damage resulting from contact of lunar dust particles to the cornea has focused only on macroscopic signs of mechanical irritancy and cytotoxicity. Given the chemical reactive properties of lunar dust, exposure of the cornea may contribute to detrimental effects at the molecular level including but not limited to oxidative damage. Additionally, low level chronic exposures may confound any results obtained in previous acute studies. We report here preliminary results from a tissue sharing effort using 10‐week‐old Fischer 344 male rats chronically exposed to filtered air or jet milled lunar dust collected during Apollo 14 using a Jaeger‐NYU nose‐only chamber for a total of 120 hours (6 hours daily, 5 days a week) over a 4‐week period. RNA was isolated from corneas collected from rats at 1 day and 7 days after being exposed to concentrations of 0, 20, and 60 mg/m3 of lunar dust. Microarray analysis was performed using the Affymetrix GeneChip Rat Genome 230 2.0 Array with Affymetrix Expression Console and Transcriptome Analysis Console used for normalization and secondary analysis. An Ingenuity iReport"TM" was then generated for canonical pathway identification. The number of differentially expressed genes identified increases with dose compared to controls suggesting a more severe response to the lunar dust insult at higher levels. Pathways of interests that have been identified in all exposed samples include oxidative stress response, mitochondrial dysfunction, fibrosis, epithelial healing, TGF-Beta signaling, and extracellular matrix remodeling. Several biological processes related to cell migration, cellular proliferation, and eye development were also identified to be altered by exposure to lunar dust. Our preliminary results suggest that even a chronic insult of lunar dust as low as 20 mg/m(exp 3) elicits a molecular response in cornea tissue. Lunar dust on the surface of the moon would have the added properties of ionization and activation potentially leading to further damage to the cornea and greater sensitivity to any other environmental insult such as exposure to radiation. Additional studies are required to fully assess the risk of vision impairment and the mechanistic responses initiated in cornea exposed to lunar dust as well as the potential for long‐term effects to astronaut health

Theriot, C. A.↗

Materials and methods for improved pyrolysis processing

The present disclosure relates to a catalyst that includes a support that includes a metal oxide and a metal deposited on the support, where the metal oxide includes at least one of TiO 2 , Al 2 O 3 , SiO 2 , CeO 2 , and/or ZrO 2 , the metal includes at least one of Pt, Pd, Ru Rh, Ni, and/or Mo, the metal is in the form of a particle, and the metal is present on the support at a concentration between about 0.1 wt % and about 5.0 wt %.

Griffin, Michael Brandon↗