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At least 1,297 records · Page 72
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Self-similar mesocrystals form via interface-driven nucleation and assembly

Crystallization by particle attachment (CPA) is a frequently occurring mechanism of colloidal crystallization that results in hierarchical morphologies. CPA has been exploited to create nanomaterials with unusual properties and is implicated in the development of complex mineral textures. Oriented attachment–a form of CPA in which particles align along specific crystallographic directions–produces mesocrystals that diffract as single crystals do, although the constituent particles are still discernible. The conventional view of CPA is that nucleation provides a supply of particles that aggregate via Brownian motion biased by attractive interparticle potentials. However, mesocrystals often exhibit regular morphologies and uniform sizes. Although many crystal systems form mesocrystals and individual attachment events have been directly visualized10, how random attachment events lead to well defined, self-similar morphologies remains unknown, as does the role of surface-bound ligands, which are ubiquitous in nanoparticle systems. Attempts to understand mesocrystal formation are further complicated in many systems by the presence of precursor nanoparticles with a phase distinct from that of the bulk. Some studies propose that such particles convert before attachment, whereas others attribute conversion to the attachment process itself and yet others conclude that transformation occurs after the mesocrystals exceed a characteristic size. Here we investigate mesocrystal formation by iron oxides, which are important colloidal phases in natural environments and classic examples of systems forming ubiquitous precursor phases and undergoing CPA accompanied by phase transformations. Combining in situ transmission electron microscopy (TEM) at 80 degrees Celsius with ‘freeze-and-look’ TEM, we tracked the formation of haematite (Hm) mesocrystals in the presence of oxalate (Ox), which is abundant in soils, where iron oxides are common. In this work, we find that isolated Hm particles rarely appear, but once formed, interfacial gradients at the Ox-covered surfaces drive Hm particles to nucleate repeatedly about two nanometres from the surfaces, to which they then attach, thereby generating mesocrystals. Comparison to natural and synthetic systems suggests that interface-driven pathways are widespread.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Light‐driven Transformation of Carbon Monoxide into Hydrocarbons using CdS@ZnS : VFe Protein Biohybrids

Enzymatic Fisher-Tropsch (FT) process catalyzed by vanadium (V)-nitrogenase can convert carbon monoxide (CO) to longer-chain hydrocarbons (>C2) under ambient conditions, although this process requires high-cost reducing agent(s) and/or the ATP-dependent reductase as electron and energy sources. Using visible light-activated CdS@ZnS (CZS) core-shell quantum dots (QDs) as alternative reducing equivalent for the catalytic component (VFe protein) of V-nitrogenase, we first report a CZS : VFe biohybrid system that enables effective photo-enzymatic C−C coupling reactions, hydrogenating CO into hydrocarbon fuels (up to C4) that can be hardly achieved with conventional inorganic photocatalysts. Surface ligand engineering optimizes molecular and opto-electronic coupling between QDs and the VFe protein, realizing high efficiency (internal quantum yield >56 %), ATP-independent, photon-to-fuel production, achieving an electron turnover number of >900, that is 72 % compared to the natural ATP-coupled transformation of CO into hydrocarbons by V-nitrogenase. The selectivity of products can be controlled by irradiation conditions, with higher photon flux favoring (longer-chain) hydrocarbon generation. The CZS : VFe biohybrids not only can find applications in industrial CO removal for high-value-added chemical production by using the cheap, renewable solar energy, but also will inspire related research interests in understanding the molecular and electronic processes in photo-biocatalytic systems.

Chemistry↗
NASA NTRS2007

Reconstructed Historical Land Cover and Biophysical Parameters for Studies of Land-Atmosphere Interactions within the Eastern United States

The local environment where we live within the Earth's biosphere is often taken for granted. This environment can vary depending on whether the land cover is a forest, grassland, wetland, water body, bare soil, pastureland, agricultural field, village, residential suburb, or an urban complex with concrete, asphalt, and large buildings. In general, the type and characteristics of land cover influence surface temperatures, sunlight exposure and duration, relative humidity, wind speed and direction, soil moisture amount, plant life, birds, and other wildlife in our backyards. The physical and biological properties (biophysical characteristics) of land cover help to determine our surface environment because they directly affect surface radiation, heat, and soil moisture processes, and also feedback to regional weather and climate. Depending on the spatial scale and land use intensity, land cover changes can have profound impacts on our local and regional environment. Over the past 350 years, the eastern half of the United States, an area extending from the grassland prairies of the Great Plains to the Gulf and Atlantic coasts, has experienced extensive land cover and land use changes that began with land clearing in the 1600s, led to extensive deforestation and intensive land use practices by 1920, and then evolved to the present-day landscape. Determining the consequences of such land cover changes on regional and global climate is a major research issue. Such research requires detailed historical land cover data and modeling experiments simulating historical climates. Given the need to understand the effects of historical land cover changes in the eastern United States, some questions include: - What were the most important land cover transformations and how did they alter biophysical characteristics of the land cover at key points in time since the mid-1600s? - How have land cover and land use changes over the past 350 years affected the land surface environment including surface weather, hydrologic, and climatic variability? - How do the potential effects of regional human-induced land cover change on the environment compare to similar changes that are caused by the natural variations of the Earth's climate system? To help answer these questions, we reconstructed a fractional land cover and biophysical parameter dataset for the eastern United States at 1650, 1850, 1920, and 1992 time-slices. Each land cover fraction is associated with a biophysical parameter class, a suite of parameters defining the biophysical characteristics of that kind of land cover. This new dataset is designed for use in computer models of land-atmosphere interactions, to understand and quantify the effects of historical land cover changes on the water, energy, and carbon cycles

Steyaert, Louis T.↗
NASA NTRS2011

Sky and Elemental Planetary Mapping Via Gamma Ray Emissions

Low-energy gamma ray emissions ((is) approximately 30keV to (is) approximately 30MeV) are significant to astrophysics because many interesting objects emit their primary energy in this regime. As such, there has been increasing demand for a complete map of the gamma ray sky, but many experiments to do so have encountered obstacles. Using an innovative method of applying the Radon Transform to data from BATSE (the Burst And Transient Source Experiment) on NASA's CGRO (Compton Gamma-Ray Observatory) mission, we have circumvented many of these issues and successfully localized many known sources to 0.5 - 1 deg accuracy. Our method, which is based on a simple 2-dimensional planar back-projection approximation of the inverse Radon transform (familiar from medical CAT-scan technology), can thus be used to image the entire sky and locate new gamma ray sources, specifically in energy bands between 200keV and 2MeV which have not been well surveyed to date. Samples of these results will be presented. This same technique can also be applied to elemental planetary surface mapping via gamma ray spectroscopy. Due to our method's simplicity and power, it could potentially improve a current map's resolution by a significant factor.

BATSE (the Burst and Transient Source Experiment)↗
DOE OSTI2024

A comprehensive review of dwell time optimization methods in computer-controlled optical surfacing

Dwell time plays a vital role in determining the accuracy and convergence of the computer-controlled optical surfacing process. However, optimizing dwell time presents a challenge due to its ill-posed nature, resulting in non-unique solutions. To address this issue, several well-known methods have emerged, including the iterative, Bayesian, Fourier transform, and matrix-form methods. Despite their independent development, these methods share common objectives, such as minimizing residual errors, ensuring dwell time's positivity and smoothness, minimizing total processing time, and enabling flexible dwell positions. This paper aims to comprehensively review the existing dwell time optimization methods, explore their interrelationships, provide insights for their effective implementations, evaluate their performances, and ultimately propose a unified dwell time optimization methodology.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Deactivation of Cu-Exchanged Automotive-Emission NH 3 -SCR Catalysts Elucidated with Nanoscale Resolution Using Scanning Transmission X-ray Microscopy

To gain insight into the underlying mechanisms of catalyst durability for the selective catalytic reduction (SCR) of NO x with an ammonia reductant, we employed scanning transmission X-ray microscopy (STXM) to study Cu-exchanged zeolites with the CHA and MFI framework structures before and after simulated 135 000-mile aging. X-ray absorption near-edge structure (XANES) measurements were performed at the Al K- and Cu L-edges. The local environment of framework Al, the oxidation state of Cu, and geometric changes were analyzed, showing a multi-factor-induced catalytic deactivation. In Cu-exchanged MFI, a transformation of Cu II to Cu I and Cu x O y was observed. We also found a spatial correlation between extra-framework Al and deactivated Cu species near the surface of the zeolite as well as a weak positive correlation between the amount of CuI and tri-coordinated Al. By inspecting both Al and Cu in fresh and aged Cu-exchanged zeolites, we conclude that the importance of the preservation of isolated Cu II sites trumps that of Brønsted acid sites for NH 3 -SCR activity.

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

Engineering metal-oxide interface by depositing ZrO 2 overcoating on Ni/Al 2 O 3 for dry reforming of methane

Zirconium oxide (ZrO 2 ) was deposited onto Ni/Al 2 O 3 catalyst as overcoating by atomic layer deposition (ALD) for dry reforming of methane (DRM). High-temperature heating during H-2-reduction could transform the ALD-prepared ZrO 2 thin film to tetragonal phase and crack the encapsulating layer on Ni sites, which constructed a beneficial Ni-ZrO x interface. Here, interfacial surface oxygen vacancies on ZrO 2 overcoating were induced by the partial reduction of ZrO 2 surface during high-temperature H 2 reduction, with the assistance of Ni. During DRM, the interfacial oxygen vacancies enhanced CO 2 activation by dissociating CO 2 and releasing active O, thereby limiting carbon formation. For DRM at 700 °C and 800 °C, Ni/Al 2 O 3 with 5 cycles of ZrO 2 ALD overcoating enhanced both activity and stability significantly. For a 100-h DRM test at 600 °C, no deactivation was observed for the Ni/Al 2 O 3 catalyst with 10 cycles of ZrO 2 ALD overcoating, as compared to 59% relative activity loss of Ni/Al 2 O 3 .

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

Unseeded, spontaneous nucleation of spherulitic magnesium calcite

Most of the sedimentary carbonates deposited in the marine environments are composed of calcium carbonate minerals with varying amounts of incorporated Mg 2+ . However, understanding how interactions of impurities with carbonate and their incorporation affect sediments behavior remains a challenge. Here, a new insight is obtained by monitoring solution composition, morphology, and electrokinetic potential of carbonate particles formed in a spontaneous unseeded batch precipitation experiment using electrochemical and scanning electron microscopy methods. The solid composition and growth rate are extracted from changes in the bulk composition and fitted to chemical affinity rate law, revealing that the precipitation pathway consists of second-order dissolution and first-order precipitation. The molecular dynamics simulations show that the lattice strain induced by randomly substituting Ca 2+ by Mg 2+ stabilizes spherical nanoparticles and reduces their surface area and volume. Combining kinetics and thermodynamics insight, we conclude that variation in the carbonate bulk and interfacial energies, along with the solution supersaturation, lead to the dissolution-precipitation transformation pathway from Mg-rich to Mg-poor carbonate phase that preserves spherulitic morphology. Furthermore, our findings are relevant for long-standing questions of how impurities influence diagenesis of carbonate sediments and spherulitic carbonate particles' origin.

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

Enhancing Nitrogen Activation in Electrochemical Reduction: The Role of Rare Earth Oxide Surface Configurations

The pursuit of sustainable ammonia synthesis has prompted the exploration of ambient electrochemical nitrogen reduction reaction (e-NRR) as an alternative to the energy-intensive Haber-Bosch process. Here, this study conducted a theoretical investigation into the use of rare earth oxide materials, specifically dysprosium oxide (Dy 2 O 3 ), as potential electrocatalysts for NRR. Utilizing spin-polarized density functional theory calculations, we explored the interaction between Dy 2 O 3 surfaces and nitrogen (N 2 ) molecules, examining the capability of Dy 2 O 3 to adsorb and activate N 2 under ambient conditions. The results indicate that Dy 2 O 3 surfaces exhibit diverse configurations and bonding environments, providing a variety of reactive sites that display different behaviors in N 2 adsorption and activation. The distinctive electronic structure and surface chemistry of a particular Dy 2 O 3 surface configuration were found to significantly enhance the activation of N 2 by promoting charge transfer, which facilitates the NRR process. This research provides deep insights into the mechanistic pathways of N 2 reduction over Dy 2 O 3 , highlighting the surface properties as pivotal in catalysis. These theoretical insights serve as a foundation for the development of novel rare earth-based electrocatalytic materials for efficient ambient e-NRR, potentially transforming ammonia production into a greener and more energy-efficient process.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Multipolar Raman Scattering vs Interfacial Nanochemistry: Case of 4-Mercaptopyridine on Gold

Caution needs to be exercised in associating changes in plasmon-enhanced Raman spectra with chemical transformations. This is demonstrated through a detailed analysis of tip-enhanced Raman (TER) scattering from 4-mercaptopyridine (MPY) on gold. The substrate used consists of gold nanoplates atop a gold surface featuring heterogeneous grooves, all coated with a monolayer of MPY. The brightest spectra across the substrate exhibit features that can only be recovered by considering the generalized polarizability of oriented MPY molecules. Finally, the complex TER spectra we observe do not mark interfacial chemistry, but rather, multipolar TER scattering driven by local field gradients.

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

Enhanced Methanol Synthesis from CO 2 Hydrogenation Achieved by Tuning the Cu–ZnO Interaction in ZnO/Cu 2 O Nanocube Catalysts Supported on ZrO 2 and SiO 2

The nature of the Cu–Zn interaction and especially the role of Zn in Cu/ZnO catalysts used for methanol synthesis from CO 2 hydrogenation are still debated. Migration of Zn onto the Cu surface during reaction results in a Cu–ZnO interface, which is crucial for the catalytic activity. However, whether a Cu–Zn alloy or a Cu–ZnO structure is formed and the transformation of this interface under working conditions demand further investigation. Here, ZnO/Cu 2 O core–shell cubic nanoparticles with various ZnO shell thicknesses, supported on SiO 2 or ZrO 2 were prepared to create an intimate contact between Cu and ZnO. The evolution of the catalyst’s structure and composition during and after the CO 2 hydrogenation reaction were investigated by means of operando spectroscopy, diffraction, and ex situ microscopy methods. The Zn loading has a direct effect on the oxidation state of Zn, which, in turn, affects the catalytic performance. High Zn loadings, resulting in a stable ZnO catalyst shell, lead to increased methanol production when compared to Zn-free particles. Low Zn loadings, in contrast, leading to the presence of metallic Zn species during reaction, showed no significant improvement over the bare Cu particles. Therefore, our work highlights that there is a minimum content of Zn (or optimum ZnO shell thickness) needed to activate the Cu catalyst. Furthermore, in order to minimize catalyst deactivation, the Zn species must be present as ZnO x and not metallic Zn or Cu–Zn alloy, which is undesirably formed during the reaction when the precatalyst ZnO overlayer is too thin.

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

Metapangenomics reveals depth-dependent shifts in metabolic potential for the ubiquitous marine bacterial SAR324 lineage

Abstract Background Oceanic microbiomes play a pivotal role in the global carbon cycle and are central to the transformation and recycling of carbon and energy in the ocean’s interior. SAR324 is a ubiquitous but poorly understood uncultivated clade of Deltaproteobacteria that inhabits the entire water column, from ocean surface waters to its deep interior. Although some progress has been made in elucidating potential metabolic traits of SAR324 in the dark ocean, very little is known about the ecology and the metabolic capabilities of this group in the euphotic and twilight zones. To investigate the comparative genomics, ecology, and physiological potential of the SAR324 clade, we examined the distribution and variability of key genomic features and metabolic pathways in this group from surface waters to the abyss in the North Pacific Subtropical Gyre, one of the largest biomes on Earth. Results We leveraged a pangenomic ecological approach, combining spatio-temporally resolved single-amplified genome, metagenomic, and metatranscriptomic datasets. The data revealed substantial genomic diversity throughout the SAR324 clade, with distinct depth and temporal distributions that clearly differentiated ecotypes. Phylogenomic subclade delineation, environmental distributions, genomic feature similarities, and metabolic capacities revealed strong congruence. The four SAR324 ecotypes delineated in this study revealed striking divergence from one another with respect to their habitat-specific metabolic potentials. The ecotypes living in the dark or twilight oceans shared genomic features and metabolic capabilities consistent with a sulfur-based chemolithoautotrophic lifestyle. In contrast, those inhabiting the sunlit ocean displayed higher plasticity energy-related metabolic pathways, supporting a presumptive photoheterotrophic lifestyle. In epipelagic SAR324 ecotypes, we observed the presence of two types of proton-pumping rhodopsins, as well as genomic, transcriptomic, and ecological evidence for active photoheterotrophy, based on xanthorhodopsin-like light-harvesting proteins. Conclusions Combining pangenomic and both metagenomic and metatranscriptomic profiling revealed a striking divergence in the vertical distribution, genomic composition, metabolic potential, and predicted lifestyle strategies of geographically co-located members of the SAR324 bacterial clade. The results highlight the utility of metapangenomic approaches employed across environmental gradients, to decipher the properties and variation in function and ecological traits of specific phylogenetic clades within complex microbiomes.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Arctic Aerosol Sources and Mixing States Field Campaign Report

The Arctic is warming at a faster rate than anywhere else on Earth, with rapidly shrinking sea ice extent transforming the region. Depending on chemical and physical properties, atmospheric aerosols directly scatter and/or absorb radiation, serve as cloud droplet and/or ice crystal nuclei, and/or reduce the reflectiveness of the snow surface, thereby altering the atmospheric energy budget. There is a wide spread in the magnitude of simulated arctic aerosol radiative forcing, and significant differences in aerosol concentration levels and seasonal cycles often exist between models and observations. Increasing local natural and anthropogenic emissions are significant, with uncertain climate impacts due to complex feedbacks. Model evaluations, however, are limited by the dearth of arctic aerosol observations available and an inadequate understanding of arctic aerosol processes. The majority of previous arctic aerosol observations have been made through intensive spring/summer field campaigns, with few intensive measurement studies focused on the fall-winter transition, a period when freeze-up is occurring later and thinning sea ice is resulting in wintertime ice fracturing. Aerosol monitoring at arctic coastal stations has provided knowledge of long-term seasonal trends in aerosol concentrations. The completed ARM field campaign addresses observational and knowledge gaps through detailed aerosol size and chemical composition measurements during the fall-winter transition in the coastal Arctic and through the entire annual cycle in the central Arctic. The observations are improving our understanding of the sources and processes controlling the aerosol population in the rapidly changing Arctic.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS1975

Combustion of bulk titanium in oxygen

The combustion of bulk titanium in one atmosphere oxygen is studied using laser ignition and several analytical techniques. These were high-speed color cinematography, time and space resolved spectra in the visible region, metallography (including SEM) of specimens quenched in argon gas, X-ray and chemical product analyses, and a new optical technique, the Hilbert transform method. The cinematographic application of this technique for visualizing phase objects in the combustion zone is described. The results indicate an initial vapor phase reaction immediately adjacent to the molten surface but as the oxygen uptake progresses the evaporation approaches the point of congruency and a much reduced evaporation rate. This and the accumulation of the various soluble oxides soon drive the reaction zone below the surface where gas formation causes boiling and ejection of particles. The buildup of rutile cuts off the oxygen supply and the reaction ceases.

Clark, A. F.↗
NASA NTRS1980

Numerical solution of flow problems using body-fitted coordinate systems

The paper deals with numerically generated boundary-fitted coordinate systems. This procedure eliminates the shape of the boundaries as a complicating factor and allows the flow about arbitrary boundaries to be treated essentially as easily as that about simple boundaries. The technique of boundary-fitted coordinate systems is based on a method of automatic numerical generation of a general curvilinear coordinate system having a coordinate line coincident with each boundary of a general multiconnected region involving any number of arbitrarily shaped boundaries. Once the curvilinear coordinate system is generated, any partial differential system of interest may be solved on the coordinate system by transforming the equations and solving the resulting system in finite-difference approximation on the rectangular transformed plane. Attention is given to the types of boundary-fitted coordinate systems, coordinate system control, operation of the coordinate codes, solution of partial differential equations, application to free-surface flow, and other applications of interest.

Thompson, J. F.↗
NASA NTRS1985

Munsell color analysis of Landsat color-ratio-composite images of limonitic areas in southwest New Mexico

The causes of color variations in the green areas on Landsat 4/5-4/6-6/7 (red-blue-green) color-ratio-composite (CRC) images, defined as limonitic areas, were investigated by analyzing the CRC images of the Lordsburg, New Mexico area. The red-blue-green additive color system was mathematically transformed into the cylindrical Munsell color coordinates (hue, saturation, and value), and selected areas were digitally analyzed for color variation. The obtained precise color characteristics were then correlated with properties of surface material. The amount of limonite (L) visible to the sensor was found to be the primary cause of the observed color differences. The visible L is, is turn, affected by the amount of L on the material's surface and by within-pixel mixing of limonitic and nonlimonitic materials. The secondary cause of variation was vegetation density, which shifted CRC hues towards yellow-green, decreased saturation, and increased value.

Kruse, F. A.↗
NASA NTRS1991

Program and Abstracts for Clay Minerals Society 28th Annual Meeting

This volume contains abstracts that were accepted for presentation at the annual meeting. Some of the main topics covered include: (1) fundamental properties of minerals and methods of mineral analysis; (2) surface chemistry; (3) extraterrestrial clay minerals; (4) geothermometers and geochronometers; (5) smectite, vermiculite, illite, and related reactions; (6) soils and clays in environmental research; (7) kaolinite, halloysite, iron oxides, and mineral transformations; and (8) clays in lakes, basins, and reservoirs.

Source record↗