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At least 325 records · Page 18

Aluminum Metal Dissolution for Mark-18A Target Processing

The Mark-18A Program was established to preserve the unique materials found in Mark-18A targets for future research and development activity within the Department of Energy or other U.S. government agencies. The Savannah River Site has 65 Mark-18A targets to be provided for the recovery of high valued isotopes. The majority of the recovery work will be performed in the Savannah River National Laboratory (SRNL) Shielded Cells due to dose concerns. The recovered product will be transported to the Oak Ridge National Laboratory (ORNL) for future research and development tasks. The Mark-18A target material will be removed from their current configuration, dissolved, chemically separated, and calcined to a stable oxide. The baseline flowsheet is patterned after the flowsheet ORNL has previously used to process both Mark-18A and Mark-42 targets. However, it is necessary for SRNL to adapt its facility and the ORNL flowsheet to identify process improvements to successfully recover the actinide materials within the constraints of the SRNL Shielded Cells. These studies evaluated and demonstrated a chemical method for cladding removal using a mixture of sodium nitrate (NaNO 3 ) and sodium hydroxide (NaOH). Experiments provided better insights into dissolution of the Mark-18A aluminum cladding. In particular, these studies measured the effects of temperature on dissolution rate, flammable gas generation, and nitrite formation. Using the lessons learned from batch dissolution testing at SRNL, a continuous dissolution flowsheet was successfully demonstrated using prototypic-shaped materials and chemically-conservative materials. The SRNL target dissolution flowsheet departs from the baseline ORNL flowsheet in small but significant ways as discussed in the following paragraphs. These flowsheet changes facilitate faster initial reaction rates at a given temperature, enable cladding removal at a lower process temperature, and yield a more uniform dissolution rate throughout cladding removal. Multiple tests indicate that the total time at the dissolution temperatures will be about six hours for one fourth of a target. The shorter dissolution time provides the benefit of a single-shift dissolver operation. Off gas sampling determined that the quantities of flammable hydrogen (H 2 ) and ammonia (NH 3 ) expected in the process off gas will meet allowable flammable gas generation rates for the Shielded Cells Facility. The SRNL approach enables NaOH to be added at a constant rate, which simplifies operations in the shielded cells. In all six continuous dissolution tests, the process was easy to control with minimal operator interface. Analyses of process solutions throughout the experiments provide a better understanding of system behavior. The data show consistent behavior across several similar but different test conditions. Between the batch-test and continuous-test data, if future changes to the flowsheet are required, sufficient data exist to adequately predict how the system will respond to those changes. Future work will focus on design, fabrication, and evaluation of a system for dissolution of one-fourth of a Mark-18A target, which will be full-scale operations for SRNL. Based on these results, the process parameters are adequately understood and the system can be operated safely.

36 MATERIALS SCIENCE↗

Determine the utility of ERTS-1 imagery in the preparation of hydrologic atlases of arid land watersheds

The author has identified the following significant results. The 9x9-inch transparencies from the ERTS-1 system seem to have better contrast in vegetation and drainage features than the 70-mm transparencies. This imagery can be magnified about eight times before it becomes excessively grainy. Imagery in band 7 appears to be the best single band product for viewing landform-water complexes. Band 5 best defines vegetation patterns. Multispectral color-additive viewing would appear to improve the separation of vegetation types where the vegetation exhibits moderate to strong infrared reflectance. Multispectral viewing did not appear to improve relief of drainage channel detail. False-color aerial infrared photographs at a scale of 1:120,000 for the Utah test site are excellent quality and can be magnified as much as 15 times without serious loss of contrast or excessive fuzziness. In desert areas with sparse to moderate shrub cover, the contrast between the soil background and the plant cover is so low that texture cannot be seen, even under high magnification. In areas of higher rainfall during the summer it is possible to discriminate coniferous and deciduous trees, grass, and shrub communities and to identify different rangeland treatment practices.

Shown, L. M.↗

Polluted and turbid water masses in Osaka Bay and its vicinity revealed with ERTS-A imageries

ERTS-1 took very valuable MSS imageries of Osaka Bay and its vicinity on October 24, 1972. In the MSS-4 and MSS-5 imageries a complex grey pattern of water masses can be seen. Though some of grey colored patterns seen in black and white prints of the MSS-4 and MSS-5 imageries are easily identified from their shapes as cloud covers or polluted water masses characterized by their color tone in longer wavelengths in the visible region, any correct distribution pattern of polluted or turbid water masses can be hardly detected separately from thin cloud covers in a quick look analysis. In the present investigation, a simple photographic technique was applied using the fact that reflected sun light from cloud including smog and inclined water surfaces of wave have a certain component in the near infrared region, that MSS-7, whereas the light scattered from fine materials suspended in the sea water has nearly no component sensible in MSS-4 and MSS-5 channels.

Watanabe, K.↗

Classification of the LCVF AVIRIS test site with a Kohonen artificial neural network

We present a classification of an AVIRIS spectral image of the Lunar Crater Volcanic Field (LCVF). Geologic mapping from such data is made possible by distinctive mineral signatures: absorption features and the shape of the spectral continuum. The subtle spectral shape differences between some of the geological units in this scene along with the high dimensionality of the spectral presents a challenging pattern recognition task. We found an artificial neural network powerful in separating 13 geological units based on the full spectral resolution. The LCVF, in northern Nye County, Nevada, was the primary focus of the NASA-sponsored Geologic Remote Sensing Field Experiment in the summer of 1989. It consists of over 100 square miles of Quaternary basaltic pyroclastic and flow deposits. These deposits lie atop ignimbrites and silicic lava flows of Tertiary age and in turn are overlain by Quaternary alluvial and playa deposits. This AVIRIS image was collected on September 29, 1989 at 11:44 at 11:44 PDT. The 256-by-256 pixel subsection in this study contains oxidized basaltic cinder deposits, the southern half of the Lunar Lake playa, and outcrops of the Rhyollite of Big Sand Spring Valley. Vegetation in LCVF is sparse, but locally abundant within washes and near springs.

Merenyi, Erzsebet↗

Controller Strategies for Managing Air Traffic in High Altitude Arrival Sectors

Substantial increases in the volume of air traffic in the National Airspace System (NAS) are forecast for the next decade, with the number of passengers travelling on U.S. airlines expected to increase by as much as 60%. This increased demand on system capacity will be accompanied by increases in traffic complexity as air traffic service providers routinely accommodate user preferred routing requests. Changes to the NAS to meet these new demands are currently underway, including development of new decision support tools to aid controllers in monitoring and managing air traffic, and increased air-to-air and air-to-ground information exchange. Changes in roles and responsibilities of pilots and controllers in flight path management will accompany these changes in traffic patterns and information technology, however the ultimate responsibility for maintaining aircraft separation will remain with the air traffic controller. A thorough understanding of the methods controllers use to manage air traffic will help ensure that changes to the NAS are implemented in a way that maintains the controller's ability to separate aircraft as the system evolves. This presentation describes the strategies controllers use today to manage arrival traffic in its descent from cruise altitude to the Terminal Radar Approach Control (TRACON) boundary. Factors that increase the complexity of this task include the presence of overflight traffic, varying aircraft performance characteristics, winds aloft, ground speed variations with altitude, the need to merge arrival traffic into a single stream, and, when arrival traffic exceeds airport runway capacity, the added task of metering flow into the TRACON. Because of the limited information available to controllers to manage arrival traffic, their strategies are often driven by the need to reduce the task's complexity, which can result in de-optimized flight paths for individual aircraft (e.g., sub-optimal descent or speed profiles). Understanding these strategies and the cognitive demands that drive them will support a safe transition to a NAS that relies on enhanced technologies. In addition, it could enable system developers to identify opportunities for new automation-based procedures or information displays that could reduce the controller's workload and increase operational efficiency.

Smith, Nancy↗

Isotopic compositions of carbonates and organic carbon from upper Proterozoic successions in Namibia: stratigraphic variation and the effects of diagenesis and metamorphism

The carbon isotope geochemistry of carbonates and organic carbon in the late Proterozoic Damara Supergroup of Namibia, including the Nama, Witvlei, and Gariep groups on the Kalahari Craton and the Mulden and Otavi groups on the Congo Craton, has been investigated as an extension of previous studies of secular variations in the isotopic composition of late Proterozoic seawater. Subsamples of microspar and dolomicrospar were determined, through petrographic and cathodoluminescence examination, to represent the "least-altered" portions of the rock. Carbon-isotopic abundances in these phases are nearly equal to those in total carbonate, suggesting that 13C abundances of late Proterozoic fine-grained carbonates have not been significantly altered by meteoric diagenesis, although 18O abundances often differ significantly. Reduced and variable carbon-isotopic differences between carbonates and organic carbon in these sediments indicate that isotopic compositions of organic carbon have been altered significantly by thermal and deformational processes, likely associated with the Pan-African Orogeny. Distinctive stratigraphic patterns of secular variation, similar to those noted in other, widely separated late Proterozoic basins, are found in carbon-isotopic compositions of carbonates from the Nama and Otavi groups. For example, in Nama Group carbonates delta 13C values rise dramatically from -4 to +5% within a short stratigraphic interval. This excursion suggests correlation with similar excursions noted in Ediacaran-aged successions of Siberia, India, and China. Enrichment of 13C (delta 13C> +5%) in Otavi Group carbonates reflects those in Upper Riphean successions of the Akademikerbreen Group, Svalbard, its correlatives in East Greenland, and the Shaler Group, northwest Canada. The widespread distribution of successions with comparable isotopic signatures supports hypotheses that variations in delta 13C reflect global changes in the isotopic composition of late Proterozoic seawater. Within the Damara basin, carbon-isotopic compositions of carbonates provide a potentially useful tool for the correlation of units between the Kalahari and Congo cratons. Carbonates depleted in 13C were deposited during and immediately following three separate glacial episodes in Namibia. The correspondence between ice ages and negative delta 13C excursions may reflect the effects of lowered sea levels; enhanced circulation of deep, cold, O2-rich seawater; and/or the upwelling of 13C-depleted deep water. Iron-formation is additionally associated with one of the glacial horizons, the Chuos tillite. Carbon-13 enriched isotopic abundances in immediately pre-glacial carbonates suggest that oceanographic conditions favored high rates of organic burial. It is likely that marine waters were stratified, with deep waters anoxic. A prolonged period of ocean stratification would permit the build-up of ferrous iron, probably from hydrothermal sources. At the onset of glaciation, upwelling would have brought 13C-depleted and iron-rich deep water onto shallow shelves where contact with cold, oxygenated surface waters led to the precipitation of ferric iron.

NASA Program Exobiology↗

Coastal Land Change Due to Tectonic Processes and Implications for Relative Sea-Level Rise in the Samoan Islands

Of the major coastal land change mechanisms responsible for relative sea-level change, tectonic subsidence is generally quoted as ranging from < mm/yr to 1 cm/yr. However, we documented coseismic and ongoing post-earthquake surface displacements from continuous GPS and tide gauge/altimetry data that indicated rapid subsidence on two of the major Samoan Islands of 12 - 20 cm during and following the 8.1 2009 Tonga-Samoa earthquake. Earlier results and our modeling of GRACE-derived gravimetric data provided a preliminary forecast of future relative sea-level rise through rapid land subsidence [Han et al., 2019]. Of course these numerical forecasts of time-dependent deformation are only as good as our input observations and our assumed rheological models. As part of our current NASA Earth Surface and Interior study, we are obtaining a wider range of data to constrain and test alternate models of ongoing postseismic deformation across American Samoa and Upolu, Samoa: (1) times series of altimetry plus tide gauge data processed to complement the cGPS data available to provide high-temporal resolution, point measurements of uplift/subsidence, (2) InSAR derived observations of surface deformation across the highly vegetated Samoan Islands, (3) evaluating and using NASA satellite lidar data (ICESat-I & ICESat-II, GEDI) for fusion with multi-source topographic data sets and for estimating topographic change on the decadal time scale. We are evaluating and using these new observations to better understand and separate out local, island-wide, and multi-island subsidence patterns and to evaluate the high impact of rising sea-level in a tectonically active region.

Jeanne Sauber-Rosenberg↗

Collocation and Pattern Recognition Effects on System Failure Remediation

Previous research found that operators prefer to have status, alerts, and controls located on the same screen. Unfortunately, that research was done with displays that were not designed specifically for collocation. In this experiment, twelve subjects evaluated two displays specifically designed for collocating system information against a baseline that consisted of dial status displays, a separate alert area, and a controls panel. These displays differed in the amount of collocation, pattern matching, and parameter movement compared to display size. During the data runs, subjects kept a randomly moving target centered on a display using a left-handed joystick and they scanned system displays to find a problem in order to correct it using the provided checklist. Results indicate that large parameter movement aided detection and then pattern recognition is needed for diagnosis but the collocated displays centralized all the information subjects needed, which reduced workload. Therefore, the collocated display with large parameter movement may be an acceptable display after familiarization because of the possible pattern recognition developed with training and its use.

Trujillo, Anna C.↗

Solute mixing regulates heterogeneity of mineral precipitation in porous media

Here, synchrotron X-ray microtomography was used to track the spatiotemporal evolution of mineral precipitation and the consequent alteration of the pore structure. Column experiments were conducted by injecting CaCl 2 and NaHCO 3 solutions into granular porous media either as a premixed supersaturated solution (external mixing) or as separate solutions that mixed within the specimen (internal mixing). The two mixing modes produced distinct mineral growth patterns. While internal mixing promoted transverse heterogeneity with precipitation at the mixing zone, external mixing favored relatively homogeneous precipitation along the flow direction. The impact of precipitation on pore water flow and permeability was assessed via 3-D flow simulations, which indicated anisotropic permeability evolution for both mixing modes. Under both mixing modes, precipitation decreased the median pore size and increased the skewness of the pore size distribution. Such similar pore-scale evolution patterns suggest that the clogging of individual pores depends primarily on local supersaturation state and pore geometry.

42 ENGINEERING↗

The Role of Ligand–Ligand Interactions in Multimodal Ligand Conformational Equilibria and Surface Pattern Formation

Multimodal chromatography uses multiple modes of interaction such as charge, hydrophobic, or hydrogen bonding to separate proteins. Recently, we used molecular dynamics (MD) simulations to show that ligands immobilized on surfaces can interact and associate with neighboring ligands to form hydrophobic and charge patches, which may have important implications for the nature of protein–surface interactions. Here, we study interfacial systems of increasing complexity—from a single immobilized multimodal ligand to high density surfaces—to better understand how ligand behavior is affected by the presence of a surface and the presence of other ligands in the vicinity, and how this behavior scales to larger systems. Furthermore, we find that tethering a ligand to a surface restricts its conformations to a subset of those observed in free solution, yet the ligand maintains flexibility in the plane of the surface and can form contacts with neighboring ligands. We find that although the formation of a contact between two neighboring ligands is slightly unfavorable, three neighboring ligands exhibit a preference for the formation of a fully connected cluster. To explore how these trends in ligand association extend to a larger surface with high density of ligands, we performed coarse-grained Monte Carlo (MC) simulations of a 132-ligand surface using ligand interactions parametrized based on free energies obtained from the three-ligand MD simulations. Despite their simplicity, the coarse-grained simulations qualitatively capture the cluster size distribution of ligands observed in detailed MD simulations. Quantitative differences between the two suggest opportunities for improvements in the coarse-grained energy function for efficient predictions of cluster and pattern formations. Our approach presents a promising route to the engineering of multimodal patterns for future chromatographic resin design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Features of steady magnetospheric convection

The large-scale patterns of ionospheric convection and particle precipitation are described during two intervals of steady magnetospheric convection (SMC) on November 24, 1981. The unique data set used in the analysis includes recordings from the worldwide network of magnetometers and all-sky cameras, global auroral images from the Dynamics Explorer (DE) 1 spacecraft, and particle precipitation data from low-altitude National Oceanic and Atmospheric Administration (NOAA) 6 and NOAA 7 spacecraft. The data show that intense magnetospheric convection continued during more than 10 hours under the steady southward interplanetary magnetic field without any distinct substorm signatures. All data sets available confirmed the stable character of the large-scale magnetospheric configuration during this period. In particular, the magnetic flux threading the polar cap was stable (within 10%) during 3.5 hours of continued DE 1 observations. The dayside cusp was located at an unusually low latitude (70 deg CGL). The nightside auroral pattern consisted of two distinct regions. The diffuse aurora in the equatorward half of the expanded (10 deg wide) auroral oval was well-separated from the bright, active auroral forms found in the vicinity of the poleward boundary of the oval. The twin-vortex convection pattern had no signature of the Harang discontinuity; its nightside 'convection throat' was spatially coincident with the poleward active auroras. This region of the auroral oval was identified as the primary site of the short-lived transient activations during the SMC intervals. The energetic particle observations show that the auroral precipitation up to its high-latitude limit is on closed field lines and that particle acceleration up to greater than 30-keV energy starts close to this limit. The isotropic boundaries of the greater than 30-keV protons and electrons were found close to each other, separating regions of discrete and diffuse precipitation. This suggests that these precipitation types originate on the very taillike and very dipolelike field lines, respectively.

Yahnin, A.↗

The split comets - Gravitational interaction between the fragments

The gravitational interaction between two fragments of a split comet nucleus in the sun's gravitational field is studied by means of the n-body computer program of Schubart and Stumpff (1966). Patterns of interactions are found for combinations of the masses, mass ratios and densities of the parent nucleus and the fragment, directions of separation, and regions of separation for nucleus separations occurring at perihelion and at true anomalies of +90 deg and -90 deg. It has been found that solar gravitational effects become noticeable about 0.5 to 1 day after separation at perihelion, and about 1 to 2 days after separation at twice the perihelion distance. Mass ratios and bulk density do not appreciably affect the appearance of the calculated trajectories. The calculated patterns vary from zero to very high inclinations, from a prograde to a retrograde sense of motion, and from escape of the companion to its pursuance of periodic quasi-stable orbits around the principal nucleus, terminated in some cases by collision of the fragments.

Sekanina, Z.↗

Active control of Boundary Layer Separation & Flow Distortion in Adverse Pressure Gradient Flows via Supersonic Microjets

Inlets to aircraft propulsion systems must supply flow to the compressor with minimal pressure loss, flow distortion or unsteadiness. Flow separation in internal flows such as inlets and ducts in aircraft propulsion systems and external flows such as over aircraft wings, is undesirable as it reduces the overall system performance. The aim of this research has been to understand the nature of separation and more importantly, to explore techniques to actively control this flow separation. In particular, the use of supersonic microjets as a means of controlling boundary layer separation was explored. The geometry used for the early part of this study was a simple diverging Stratford ramp, equipped with arrays of supersonic microjets. Initial results, based on the mean surface pressure distribution, surface flow visualization and Planar Laser Scattering (PLS) indicated a reverse flow region. We implemented supersonic microjets to control this separation and flow visualization results appeared to suggest that microjets have a favorable effect, at least to a certain extent. However, the details of the separated flow field were difficult to determine based on surface pressure distribution, surface flow patterns and PLS alone. It was also difficult to clearly determine the exact influence of the supersonic microjets on this flow. In the latter part of this study, the properties of this flow-field and the effect of supersonic microjets on its behavior were investigated in further detail using 2-component (planar) Particle Image Velocimetry (PIV). The results clearly show that the activation of microjets eliminated flow separation and resulted in a significant increase in the momentum of the fluid near the ramp surface. Also notable is the fact that the gain in momentum due to the elimination of flow separation is at least an order of magnitude larger (two orders of magnitude larger in most cases) than the momentum injected by the microjets and is accomplished with very little mass flow through the microjets.

Alvi, Farrukh S.↗

Hybrid Analytics Solution to Improve Coal Power Plant Operations

This project focused on developing advanced methods for thermal performance monitoring of a coal-fueled power plant. The specific goal was to develop and demonstrate a new thermal performance monitoring approach using a hybrid model that integrates a physics-based heat balance model with a machine learning-based pattern recognition model. The hybrid model enables increased accuracy and scope of the thermal analysis and an improved ability to monitor and detect changes in plant operation. This new approach takes full advantage of the individual model capabilities and creates an important new set of capabilities not previously possible using the two types of models separately. Using the heat balance model, a rich set of derived parameters (virtual sensors) are calculated from the measured plant operating data at each time point. The combined measured and derived data values are used by machine learning algorithms to create pattern recognition models over the range of normal unit operation. To create the monitoring models, historical data from normal operation of the plant is first processed by the heat balance model to compute the derived parameter data. The result is a greatly expanded set of normal operating data that can be used as input to create the pattern recognition model. Once the models are calibrated for normal operation, the hybrid model is suitable for use in continuous online monitoring. During online monitoring, new plant operating data is processed first by the heat balance model and then by the pattern recognition model. Results from the pattern recognition model quantify the deviation of each measured or derived parameter from its expected value in normal operation. The hybrid models can detect abnormal changes in plant operating data with very high accuracy and sensitivity. When abnormal behavior is detected, alerts are generated automatically for evaluation by the plant monitoring staff. The new hybrid solution product was developed and verified in the performance of the project. The hybrid solution was tested first in a simulation environment that mimicked the plant data systems and infrastructure used by U.S. power generating plants and utilities. The hybrid solution was then deployed for real-time, online monitoring of an operating coal-fueled power plant at a field test site. Field testing demonstrated that all hybrid solution development objectives were accomplished. The project work was based on combining the capabilities of two existing software products to create the new hybrid solution product. One of these was the existing MapEx® heat balance product and the other was the existing SureSense® advanced pattern recognition product. Each of these separate products was assessed to be at a Technology Readiness Level (TRL) of 9 at the start of the effort. The hybrid solution product was assessed to be at a TRL of 2 at the start of the project based on early feasibility work by the project team. At completion of the field testing performed in the project, the hybrid solution product was assessed to be at a TRL of 7. The project team expects that the hybrid solution product will be deployed commercially and will achieve a TRL of 9 within one year after completion of the project.

01 COAL, LIGNITE, AND PEAT↗

Planetary noble gas components in Orgueil

In the reported investigation, the approach employed by Jeffery and Anders (1970) and Eberhardt (1974), who used colloidal suspensions in separating minerals of the Orgueil carbonaceous chondrite (C1), was extended to an application involving the enrichment of a planetary noble gas carrier in several C1 and C2 meteorites. The thermal release pattern of Orgueil 'carbon' is considered, taking into account elemental effects, a comparison of noble gas release from 'carbon' separates and bulk meteorite samples, isotopic effects, and a comparison with Murray 'carbon'. An evaluation is conducted of the noble gas components in carbonaceous chondrites. The origin of primordial noble gases in carbonaceous chondrites is also discussed, giving attention to the origin of solar gases, the role of 'carbon' as the novel vehicle for planetary gases, and plausible astrophysical sites for the production of anomalous krypton and xenon.

Frick, U.↗

Domain Wall Patterning and Giant Response Functions in Ferrimagnetic Spinels

Abstract The manipulation of mesoscale domain wall phenomena has emerged as a powerful strategy for designing ferroelectric responses in functional devices, but its full potential is not yet realized in the field of magnetism. This work shows a direct connection between magnetic response functions in mechanically strained samples of Mn 3 O 4 and MnV 2 O 4 and stripe‐like patternings of the bulk magnetization which appear below known magnetostructural transitions. Building off previous magnetic force microscopy data, a small‐angle neutron scattering is used to show that these patterns represent distinctive magnetic phenomena which extend throughout the bulk of two separate materials, and further are controllable via applied magnetic field and mechanical stress. These results are unambiguously connected to the anomalously large magnetoelastic and magnetodielectric response functions reported for these materials, by performing susceptibility measurements on the same crystals and directly correlating local and macroscopic data.

36 MATERIALS SCIENCE↗

Internally cooled membrane-based absorber for dehumidification and water heating: Validated model and simulation study

This report presents a comprehensive model for advanced membrane-based absorber components accounting for three separate fluid streams, one of them providing internal cooling, with complex flow patterns. The model was implemented with various liquid desiccants and their properties (including LiCl, CaCl 2 , and [emim][OMS] ionic liquid [IL]). The model has been validated using data from two laboratory prototype absorbers, one with CaCl 2 as the working fluid and one with an IL as the working fluid. Entropy analysis was further carried out to verify the model and understand effect of internal cooling on the entropy variation of three fluid streams. The developed model and codes are expected to enable detailed configuration optimization and provide in-depth understanding of three-fluid heat and mass exchanger (HMX) performance. The paper also describes parametric studies of the HMX components in utilizing the latent heat removed in space cooling to heat water and numerically explores the unique benefit of its application in a semi-open absorption heat pump water heater. The results show that a single three-fluid HMX has the potential to achieve simultaneous dehumidification and water heating efficiently at cost effectiveness, particularly in hot and humid climates.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Direct synthesis of all-inorganic heterostructured CdSe/CdS QDs in aqueous solution for improved photocatalytic hydrogen generation

Here we present a facile aqueous approach to synthesize heterostructured CdSe/CdS QDs with all-inorganic chalcogenide S2- ligands under mild conditions. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and steady-state emission spectroscopy demonstrate that the heterostructured CdSe/CdS QDs with sulfur-rich surface composition are formed by heterogeneous nucleation of Cd2+ and S2- precursors on the CdSe QDs. After adsorption of small Ni(OH)(2) clusters over the surface in situ, the CdSe/CdS-Ni(OH)(2) photocatalyst enables H-2 production efficiently with an internal quantum yield of 52% under visible light irradiation at 455 nm, up to an 8-fold increase of activity to that of spherical CdSe QDs-Ni(OH)(2) under the same conditions. Femtosecond transient absorption spectroscopy, X-ray transient absorption (XTA) spectroscopy, steady-state and time-resolved emission spectroscopy show that the quasi-type-II band alignment in the CdSe/CdS heterostructure is responsible for the efficiency enhancement of light harvesting and surface/interfacial charge separation in solar energy conversion. The unprecedented results exemplify an easily accessible pattern of aqueous synthesis of all-inorganic heterostructured QDs for advanced photosynthetic H-2 evolution.

Li, Zhi-Jun↗