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At least 883 records · Page 49

Low Temperature CO 2 Hydrogenation on Unsupported Mo 2 C Catalysts

CO 2 hydrogenation to methanol, a key reaction for decarbonizing the fuel and chemical industries, requires catalyst formulations that hydrogenate CO 2 selectively to methanol at temperatures where methanol conversion is not significantly equilibrium limited (<423 K). Herein we report continuous CO 2 hydrogenation at low temperatures (348-408 K, H 2 /CO 2 = 0.1-50, 5-35 bar) with high selectivity to methanol (up to ca. 80%) over unsupported β-Mo 2 C catalysts. Active site density quantification via titration with trifluoroacetic acid at reaction temperatures enables an assessment of site-specific rates. Methanation and reverse water gas shift (RWGS) occur concurrently with methanol synthesis during CO 2 hydrogenation over Mo 2 C. Reaction pathway analysis, product cofeeds, and reversibility formalisms show that all products form through primary reaction pathways from CO 2 , but secondary reactions of CO contribute significantly to rates of methanation. Dependences of forward rates on reactant and product concentration determined by independently varying the CO 2 , H 2 , CO, H 2 O, CH 3 OH, and CH 4 pressure in conjunction with reversibility formalisms reveal that all products form through H-assisted CO 2 activation and involve partially hydrogenated CO 2 -derived intermediates. Here, these inferences were verified by quantitative agreement between measured site-time yields and site-time yields predicted by closed form kinetic rate expressions in an integral reactor model over widely varying conditions (85-2000 kPa H 2 , 80-1500 kPa CO 2 , 0-45 kPa H 2 O, 0-21 kPa CO, 0-25 kPa CH 3 OH, 0-75 kPa CH 4 , 5-87 mol Mo s s mol CO 2 -1 ). Coverages calculated based on the kinetic model reveal that the Mo 2 C surface is covered with bidentate CO- and CO 2 -derived intermediates of the stoichiometry H 2 CO 2 and H 2 CO, indicating that H 2 and CO x do not compete for surface occupancy but instead adsorb cooperatively to form partially hydrogenated intermediates. Hydrogenation of the CO-derived H 2 CO** intermediate favors methanation, while hydrogenation of CO 2 -derived H 2 CO 2 ** favors methanol synthesis. Together, these findings demonstrate the ability of unsupported Mo 2 C to catalyze the hydrogenation of CO 2 to methanol at low temperatures and provide insight into the reaction network and mechanisms involved in its formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spectral Fidelity of Earth's Terrestrial and Aquatic Ecosystems

The Surface Biology and Geology (SBG) investigation will create global maps of spectral surface reflectance and emissivity at a cadence of 16 days or better, with coverage to address global questions about Earth's geology, cryosphere and ecosystems. The revolutionary potential poses a commensurate challenge: creating contiguous maps free from regional biases induced by atmosphere, observation geometry, or inversion error. This will require an accurate calibration with precise knowledge of each channel's spectral response. In this work, we quantify the impact of spectral calibration on SBG's aquatic and terrestrial ecosystem objectives. We find that contemporary algorithms for ecosystem trait retrieval demand more accurate spectral calibration than historical missions. Errors due to drift or spatial nonuniformity in the wavelength calibration that have previously been considered acceptable can cause systematic errors larger than the instrument noise and of the same order as the variability SBG aims to measure. Moreover, their impact on atmospheric correction can induce climate-dependent systematic errors that thwart comparisons between ecosystems. These results underscore the importance of spectral response accuracy in SBG mission design.

54 ENVIRONMENTAL SCIENCES↗

Distribution of nickel(II) ions adsorbed at the muscovite mica (001)-water interface determined by in-situ resonant anomalous X-ray reflectivity

Mineral-water interfaces mediate adsorption, ion exchange, and secondary mineral formation that control element mobility in natural and engineered systems. Reliable prediction and control of these processes require a fundamental understanding of the interfacial structure that links adsorbed ion speciation to macroscopic sorption capacity and strength. Here, we determine atomic-scale changes in hydration and distribution of Ni(II) at the muscovite mica (001)-water interface using in situ high-resolution X-ray reflectivity (XR) and resonant anomalous X-ray reflectivity (RAXR) at 1 mM NiCl2 and pH 5.7. XR reveals reorganization of the primary hydration structure relative to that in deionized water: the water layer adsorbed in the cavity sites at a height of ~1.3 Å disappears, while distinct solution layers emerge at ~2.3, ~4.1, and ~5.6 Å above the basal oxygen plane. RAXR resolves three interfacial Ni(II) species: a dominant outer-sphere complex at 3.65 Å (~80% of the total coverage), a minor inner-sphere complex at 0.75 Å, and a low-coverage, more distant outer-sphere species at 5.63 Å. These three adsorbed Ni(II) species account for a total Ni(II) coverage of 0.54 ± 0.02 ion per unit cell area that compensates for the surface charge. These results highlight the role of interfacial hydration in controlling the speciation and stability of adsorbate cations on the negatively charged mica surface, providing quantitative insight into predicting the geochemical behavior of divalent metal cations in the aqueous environments.

Lee, Sang Soo↗

Meteorological applications of remote sensing from satellites

Current and promising future contributions to meteorology from satellite-borne sensors are discussed, with emphasis on performance and the limitations thereto. The discussion covers (1) synoptic meteorology, where satellite observations of clouds provide measures of winds, cyclogenesis, and rainfall estimation; (2) atmospheric profiling, wherein vertical profiles of temperature, humidity, and certain gaseous constituents are provided; (3) radiation budget or the energy exchange between the earth and the space-sun environment; and (4) surface features of importance to meteorology-temperature, soil moisture, and sea ice coverage.

Yates, H. W.↗

Passive Microwave Remote Sensing of Rainfall Considering the Effects of Wind and Nonprecipitating Clouds

It has long been shown both in theory and in observation that emission from rain drops in a raining cloud results in upwelling brightness temperature above that caused by the sea surface alone. High brightness temperatures at microwave frequencies (e.g. 37 and 19 GHz) have usually been quantitatively associated with rainfall using physical or statistical models. By comparing concurrent special sensor microwave/imager and radar data, however, we noticed many cases where there is no appreciable rainfall in a field of view (FOV) which exhibits high brightness temperature (T(sub B)) at 37 and 19 GHz. On the basis of calculations and past literature it is shown that such high brightness temperatures can be caused by nonprecipitating clouds and by wind. The effect of the wind is to create wave and high-emissivity foam on the sea surface. A model is developed to relate T(sub B) to the fractional coverage of rain, f, within a FOV. The parameters of the model are calibrated by fitting the model to the observed brightness temperature and fractional rain coverage data. The critical parameter of the model, T(sub B min.), which is the threshold brightness temperature for the presence of rain, depends on the strength of the storm. The strength of the storm is characterized by the fraction of the FOVs within a large area that have T(sub B) higher than 240 K, which is readily obtainable from satellite data alone. The instantaneous FOV rain rate R can then be obtained through the f approximately R relationship which is empirically derived using radar data. An algorithm has been proposed based on the T(sub B) approximately f and f approximately R relationship. Application of the algorithm to TOGA-COARE and Darwin storms results in reasonable instantaneous FOV rain estimate. When averaged over the entire radar scan, a more accurate and unbiased areal rain estimate can be achieved.

Qihang Li.↗

NASA Low Visibility Landing and Surface Operations (LVLASO) Atlanta Demonstration: Surveillance Systems Performance Analysis

NASA conducted a series of flight experiments at Hartsfield Atlanta International Airport as part of the Low Visibility Landing and Surface Operations (LVLASO) Program. LVLASO is one of the subelements of the NASA Terminal Area Productivity (TAP) Program, which is focused on providing technology and operating procedures for achieving clear-weather airport capacity in instrument-weather conditions, while also improving safety. LVLASO is investigating various technologies to be applied to airport surface operations, including advanced flight deck displays and surveillance systems. The purpose of this report is to document the performance of the surveillance systems tested as part of the LVLASO flight experiment. There were three surveillance sensors tested: primary radar using Airport Surface Detection Equipment (ASDE-3) and the Airport Movement Area Safety System (AMASS), Multilateration using the Airport Surface Target Identification System (ATIDS), and Automatic Dependent Surveillance - Broadcast (ADS-B) operating at 1090 MHz. The performance was compared to the draft requirements of the ICAO Advanced Surface Movement Guidance and Control System (A-SMGCS). Performance parameters evaluated included coverage, position accuracy, and update rate. Each of the sensors was evaluated as a stand alone surveillance system.

Cassell, Rick↗

A Multiple Resource Inventory of Delaware Using an Airborne Profiling Laser

An airborne profiling laser is used to monitor multiple resources related to landscape structure, both natural and man-made, across regions encompassing hundreds of thousands of hectares. A small, lightweight, inexpensive airborne profiling laser is used to inventory Delaware forests, to estimate impervious surface area statewide, and to locate potentially Suitable Delmarva Fox Squirrel (Scrotum niger cinereus) habitat. Merchantable volume estimates are within 14% of US Forest Service estimates at the county level and within 4% statewide. Total above-ground dry biomass estimates are within 19% of USES estimates at the county level and within 16% statewide. Mature forest stands suitable for reintroduction of the Delmarva Fox Squirrel, an endangered species historically endemic to the eastern shores of Delaware, Maryland, and Virginia, are identified and mapped along the laser transacts. Intersection lengths with various types of impervious surface (roofs, concrete/asphalt) and open water are tallied to estimate percent and areal coverage statewide, by stratum and county. Laser estimates of open water are within 7% of photointerpreted GIS estimates at the county level and within 3% of the GIS at the state level.

Nelson, Ross↗

(abstract) Variations in Polarimetric Backscatter of Saline Ice Grown Under Diurnal Thermal Cycling Condition

An experiment was carried out in January 1994 at the Geophysical Research Facility in the Cold Regions Research and Engineering Laboratory. To investigate effects on polarimetric scattering signatures of sea ice growth under diurnal temperature variations, an ice sheet was grown for 2.5 days for the thickness of 10 cm and a polarimetric radar operating at C-band was used to obtain backscattering data in conjunction with ice-characterization measurements. The ice sheet was grown in the late morning of January 19, 1994. The initial growth rate was slow due to high insolation and temperature. As the air temperature dropped during the night, the growth rate increased significantly. The air temperature changed drastically from about -10(deg)C to -35(deg)C between day and night. The temperature cycle was repeated during the next day and the growth rate varied in the same manner. The surface of the ice was partially covered by frost flowers and the areal coverage increased as the ice became thicker. Throughout the ice growth duration of 2.5 days, polarimetric backscatter data were collected at roughly every centimeter of ice growth. For each set of radar measurements of saline ice, a set of calibration measurements was carried out with trihedrial corner reflectors and a metallic sphere. Measured polarimetric backscattering coefficients of the ice sheet reveal a strong correlation between radar data and temperature variations. As the temperature increased (decreased), the backscatter increased (decreased) correspondingly. From the ice-characterization data, temperatures of the air, at the ice-air interface, and in the ice layer had the same variation trend. Another interesting experimental observation is that the salinity measured as a function of ice depth from a sample of 10-cm thich ice indicated that the salinity variations had a similar cycle as the temperature; i.e., the salinity profile recorded the history of the temperature variations. Characterization data of the ice sheet are used in a theoretical model for scattering from saline ice with frost cover to explain the observed polarimetric signatures.

characterization polarimetric radar salinity tempe↗

A Regional CO2 Observing System Simulation Experiment Using ASCENDS Observations and WRF-STILT Footprints

Knowledge of the spatiotemporal variations in emissions and uptake of CO2 is hampered by sparse measurements. The recent advent of satellite measurements of CO2 concentrations is increasing the density of measurements, and the future mission ASCENDS (Active Sensing of CO2 Emissions over Nights, Days and Seasons) will provide even greater coverage and precision. Lagrangian atmospheric transport models run backward in time can quantify surface influences ("footprints") of diverse measurement platforms and are particularly well suited for inverse estimation of regional surface CO2 fluxes at high resolution based on satellite observations. We utilize the STILT Lagrangian particle dispersion model, driven by WRF meteorological fields at 40-km resolution, in a Bayesian synthesis inversion approach to quantify the ability of ASCENDS column CO2 observations to constrain fluxes at high resolution. This study focuses on land-based biospheric fluxes, whose uncertainties are especially large, in a domain encompassing North America. We present results based on realistic input fields for 2007. Pseudo-observation random errors are estimated from backscatter and optical depth measured by the CALIPSO satellite. We estimate a priori flux uncertainties based on output from the CASA-GFED (v.3) biosphere model and make simple assumptions about spatial and temporal error correlations. WRF-STILT footprints are convolved with candidate vertical weighting functions for ASCENDS. We find that at a horizontal flux resolution of 1 degree x 1 degree, ASCENDS observations are potentially able to reduce average weekly flux uncertainties by 0-8% in July, and 0-0.5% in January (assuming an error of 0.5 ppm at the Railroad Valley reference site). Aggregated to coarser resolutions, e.g. 5 degrees x 5 degrees, the uncertainty reductions are larger and more similar to those estimated in previous satellite data observing system simulation experiments.

Wang, James S.↗

Spectral Fidelity of Earth's Terrestrial and Aquatic Ecosystems

The Surface Biology and Geology (SBG) investigation will create global maps of spectral surface reflectance and emissivity at a cadence of 16 days or better, with coverage to address global questions about Earth's geology, cryosphere and ecosystems. The revolutionary potential poses a commensurate challenge: creating contiguous maps free from regional biases induced by atmosphere, observation geometry, or inversion error. This will require an accurate calibration with precise knowledge of each channel's spectral response. Here, we quantify the impact of spectral calibration on SBG's aquatic and terrestrial ecosystem objectives. We find that contemporary algorithms for ecosystem trait retrieval demand more accurate spectral calibration than historical missions. Errors due to drift or spatial nonuniformity in the wavelength calibration that have previously been considered acceptable can cause systematic errors larger than the instrument noise and of the same order as the variability SBG aims to measure. Moreover, their impact on atmospheric correction can induce climate-dependent systematic errors that thwart comparisons between ecosystems. These results underscore the importance of spectral response accuracy in SBG mission design.

imaging spectroscopy↗

Self Assembled Monolayers for Passivated Contacts

Passivated contacts mitigate defects typically encountered due metallization of solar cells. We deposit amorphous silicon (a-Si:H) on an oxidized silicon wafer via PECVD and anneal at high temperature to crystallize into polysilicon passivated contact. One drawback is the absorption of the polysilicon between grid fingers, so removal of this material is desirable to maximize Jsc. Alternatively, interdigitated back contact cells rely on a gap between n- and p- fingers, which is commonly etched to ensure electronic isolation. We utilize a self assembled monolayer (SAM) using hexamethyldisilazane (HMDS) as a precursor to pattern and etch amorphous silicon (a-Si:H) and polysilicon without the need for photoresist. Ultraviolet light exposure oxidizes the HMDS by photocleaving the organic groups [1] of the SAM leaving a patterned SiO2. Directly soaking this in TMAH will eventually etch the SAM and the silicon, where the SiO2 serves as an etch mask. Inversely, a dilute HF dip selectively etches this SiO2 and the SAM remains. A subsequent soak in TMAH selectively etches the underlying silicon, where the SAM serves as an etch mask. Importantly, we find that the SAM can remain intact for metallization, where we measure 10 mO-cm2 specific contact resistivity on n-type polysilicon.

passivation↗

Theoretical Investigation of the Adsorbate and Potential–Induced Stability of Cu Facets During Electrochemical CO 2 and CO Reduction

The activity and product selectivity of electrocatalysts for reactions like the carbon dioxide reduction reaction (CO 2 RR) are intimately dependent on the catalyst's structure and composition. While engineering catalytic surfaces can improve performance, discovering the key sets of rational design principles remains challenging due to limitations in modeling catalyst stability under operating conditions. Herein, we perform first-principles density functional calculations adopting implicit solvation methods with potential control to study the influence of adsorbates and applied potential on the stability of different facets of model Cu electrocatalysts. Using coverage dependencies extracted from microkinetic models, we describe an approach for calculating potential and adsorbate-dependent contributions to surface energies under reaction conditions, where Wulff constructions are used to understand the morphological evolution of Cu electrocatalysts under CO 2 RR conditions. Here we identify that CO*, a key reaction intermediate, exhibits higher kinetically and thermodynamically accessible coverages on (100) relative to (111) facets, which can translate into an increased relative stabilization of the (100) facet during CO 2 RR. Our results support the known tendency for increased (111) faceting of Cu nanoparticles under more reducing conditions and that the relative increase in (100) faceting observed under CO 2 RR conditions is likely attributed to differences in CO* coverage between these facets.

30 DIRECT ENERGY CONVERSION↗

TOPEX/POSEIDON - Mapping the ocean surface

Global efforts are under way to model the earth as a complete planet so that weather patterns may be predicted on time scales of months and years. A major limitation in developing models of global weather is the inability to model the circulation of the oceans including the geostrophic surface currents. NASA will soon be initiating a satellite program to correct this deficiency by directly measuring these currents using the science of radar altimetry. Measurement of the ocean topography with broad, frequent coverage of all ocean basins for a long period of time will allow the derivation of the spatial and temporal behavior of surface ocean currents. The TOPEX/POSEIDON mission is a cooperative effort between NASA and the French Centre National d'Etudes Spatiales. This paper describes the goals of this research mission, the data type to be acquired, the satellite and sensors to be used to acquire the data, and the methods by which the data are to be processed and utilized.

Yamarone, C. A.↗

A Lens into the Cu Nanograin by In Situ Vibrational Spectroscopy

Cu-based catalysts are uniquely capable of C-C coupling during electrochemical CO 2 reduction (CO 2 R), yet further mechanistic understanding remains hampered by the lack of spectroscopically resolved descriptors that demonstrate how surface adsorbates emerge and evolve within their catalytic environment. Here, in this study, we correlate in situ surface-enhanced Raman spectroscopy (SERS) and surface-enhanced infrared absorption spectroscopy (SEIRAS) to resolve the potential-dependent dynamics during CO 2 R on Cu nanograin catalysts. By building on previous benchmarking of low overpotential performance and nanograin structural evolution, we offer a diagnostic framework linking vibrational signatures to catalytic function, unveiling which species appear, persist, and turnover as the electrified surface and interfacial environment evolve under bias. The onset of linear CO is marked below -0.45 V, coincident with persistent adsorbed *OH/*O domains beyond the CO 2 R onset. In this context, Cu nanograins serve as a platform to dissect contributions of adsorbate coverage. By carefully dissecting the potential dependence of emergent twin-defect/step CO stretch bands (P1-P2), alongside the prototypical terrace-site CO stretch band (P3), we provide important context for interpreting coupled spectroscopic trends driven by coverage effects and resolve this for the evidently complex nanograin morphology. Together, these observations highlight the intertwined roles of surface stabilization and interfacial flux in steering multicarbon product formation. By directly linking vibrational signatures to catalytic behavior, this work aims to bridge the gap between observation and control and help guide toward a predictive framework of fine-tuned selectivity for CO 2 R.

Fonseca Guzman, Maria V. [University of California↗

A study of mesoscale surface heat and moisture budgets and their relationship to airmass cumulus clouds observed in LANDSAT imagery

The author has identified the following significant results. The three budget analyses show a weak correspondence between LANDSAT cloud patterns and elements of the energy and moisture budgets. It was found that a little more energy is contributed by the ground to heat the air in cloudy areas. Improvements are warranted in the budget models and data coverage necessary to describe the environment. These models can serve as a basis for more complex models of surface air heat and moisture exchanges which would utilize readily available meteorological data on a mesoscale.

Merritt, E. S.↗

(abstract) Ekman Pumping/Suction and Wind-Driven Ocean Circulation from ERS-1 Scatterometer Measurements Over the Arabian Sea During October 1994-October 1995

Spatial variations of the east-west and north-south components of surface wind stress are critical in studies of ocean circulation and biological-physical interactions because surface wind stress curl produces a vertical velocity in the upper ocean at the bottom of the Ekman Layer.The ERS-1 scatterometer provides reasonable coverage and direct measurements of vector of winds. Three schemes are evaluated relative to high-quality moored-bouy wind observations recorded in the central Arabian Sea, where high surface waves and high atmospheric water content during the southeast monsoon adversely affect the estimation of satellite-derived winds.

scatterometer↗

Observations of oceanic white caps for moderate to highwind speeds

A series of photographs of sea surface whitecap conditions for wind speeds of 10 to 25 m/sec was obtained and analyzed for areal coverage of white water. The results are in good agreement with semiempirical calculations based on the wind speed and the development of the wave spectrum only when the contribution of thin foam streaks oriented in the direction of the wind is neglected. Since both the actively forming whitecaps and the thin foam streaks contribute significantly to the microwave emissivity of the sea surface, it is important that the foam streaks be included in the theory but differentiated from large white caps and foam patches. A simple relationship that accounts for the foam streaks based on the rate of energy transfer, the wind speed, and the wave spectrum is proposed. By means of empirically derived constant terms for the microwave signatures of white caps and foam streaks, this theory was adapted to the prediction of the increase in brightness temperature due to foam, with reasonable results to wind speeds of 20 m/sec.

Ross, D. B.↗