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At least 163 records · Page 9

Chiral selection on inorganic crystalline surfaces

From synthetic drugs to biodegradable plastics to the origin of life, the chiral selection of molecules presents both daunting challenges and significant opportunities in materials science. Among the most promising, yet little explored, avenues for chiral molecular discrimination is adsorption on chiral crystalline surfaces - periodic environments that can select, concentrate and possibly even organize molecules into polymers and other macromolecular structures. Here we review experimental and theoretical approaches to chiral selection on inorganic crystalline surfaces - research that is poised to open this new frontier in understanding and exploiting surface-molecule interactions.

Review↗

Methanol Partial Oxidation on Cu(111) and PtCu(111) Single-Atom Alloy Surfaces: Effect of Surface Oxygen Coverage on Selectivity

The selective oxidation of methanol to formaldehyde on Cu surfaces is an important and well-studied reaction. However, a systematic analysis of product selectivity as a function of oxygen coverage on Cu(111) and Cu-based single-atom alloys (SAAs) has not been previously reported. In this work, we present a comprehensive investigation of deuterated methanol (CD 3 OH) partial oxidation on Cu(111) and 1% PtCu(111) SAA surfaces as a function of preadsorbed oxygen coverage. Temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS) reveal that isolated Pt atoms inhibit the initial surface oxidation of Cu(111) under low oxygen exposures. Despite this difference in oxidation kinetics, the product selectivity remains largely unaffected: on both Cu(111) and PtCu(111), formaldehyde (CD 2 O) is the predominant partial oxidation product over a broad range of oxygen coverages. The selectivity toward formaldehyde peaks at intermediate oxygen coverages (∼0.3 monolayers, ML), indicating the existence of an optimal oxygen loading for partial oxidation. Notably, the similar product selectivities on Cu(111) and PtCu(111) over a range of surface oxygen coverage indicate that Pt single atoms do not significantly alter the reaction pathway or shift the optimal oxygen coverage for formaldehyde formation. Control experiments confirm that Cu(111) is unreactive toward methanol in the absence of oxygen, while PtCu(111) surfaces produce a small amount of formaldehyde even when oxygen is not preadsorbed, indicating that isolated Pt atoms facilitate O−H activation at below 150 K, leading to H 2 desorption, followed by C−D activation at higher temperatures (∼350 K). Density functional theory (DFT)-based calculations show that Pt atoms increase the O 2 dissociation barrier relative to Cu(111), consistent with the observed inhibition of oxidation at low exposures. Overall, this work provides the first detailed selectivity map for methanol oxidation on oxidized Cu(111) and PtCu(111) SAA surfaces. By linking classical mechanistic insights such as methoxy- and formate-mediated pathways with single-atom alloy catalyst design, this work demonstrates that while Pt substitution modulates the oxidation kinetics and oxygen binding, the overall selectivity toward formaldehyde is governed primarily by oxygen coverage. These findings underscore the potential of isolated dopants to tune surface oxidation behavior without compromising the intrinsic partial oxidation selectivity of copper-based catalysts.

36 MATERIALS SCIENCE↗

Solar Selective Coatings Developed for Space Power Applications

A solar collector having the combined properties of high solar absorptance, low infrared emittance, and high thermal conductivity is envisioned for space power applications on minisatellites. A high solar absorptance is needed to collect as much of the incident solar radiation as possible and a low infrared emittance is needed to minimize radiant energy losses. A lightweight material having a high thermal conductivity is needed to transport the absorbed energy to where it is needed. Such a solar collector may be used with a low temperature-differential heat engine to provide electric power to the minisatellite components or as a source of thermal energy for a thermal bus that would heat remote regions of the spacecraft. The key to such a collector is the use of cermet coatings. Cermet coatings are composed of molecular islands of metal embedded in a three-dimensional matrix of dielectric. Recent research on molecular mixtures of aluminum and aluminum oxide at the NASA Glenn Research Center has yielded cermet coatings with a solar absorptance a of 0.797 and an infrared emittance epsilon of 0.131, yielding an alpha/epsilon ratio of 6. Although additional work is needed to further increase the alpha/epsilon ratio, these coatings are attractive owing to their potential durability in the space environment. The aluminum oxide surface should provide substantial protection from the atomic oxygen found in low Earth orbit. To help minimize emittance, these coatings are deposited on a smooth surface. The selected surface is aluminum that has been diamond turned to a mirror finish. Cermet coatings are manufactured by sputter deposition. To achieve the desired variable composition, Glenn's researchers implemented a novel approach using a cylindrical target composed of aluminum and aluminum oxide. Rotating the cylinder during the deposition process yields a coating of variable composition. A photograph of the custom-made aluminum and aluminum oxide cylindrical target installed in the sputter deposition chamber is shown.

Jaworske, Donald A.↗

Ion Implantatiion Improves Bearing-Surface Properties

Selected ions fired into rolling elements to increase resistance to rolling-contact fatique. Mask strips confine implantation to 105 degree arcs on cylindrical surfaces. Specimens kept cool by copper block through which refrigerant is circulated. Implanting nitrogen or titanium ions in metals improves resistance to fatigue, corrosion, and wear without altering bulk properties. Unlike such surface treatments as conventional nitriding, conventional carburizing, and coating, ion implantation is low-temperature process, requires no finishing operations, and produces highly-alloyed surface layer. Implantation process also helps conserve such strategic materials as chromium and cobalt by using them only where needed.

Misra, M. S.↗

TPSAS-NF1676L-11084-DND

The solar radiation must be considered as the primary factor when we study the climatic system because it provides almost all energy that drives the climatic system and most atmospheric phenomena. The solar radiation at the TOA is partially transferred, transformed into other forms of energy that are eventually dissipated by the general circulation of the atmosphere and oceans, and partially used in chemical and biological processes. The absorption of solar energy in the atmosphere (Acol) plays a key role in the climate system, not only because it affects the amount of solar energy absorbed by the Earth system, but also because it changes the vertical distribution of absorbed energy, which in turn impacts surface evaporation, atmospheric convection and precipitation. To investigate Acol, we have collected the collocated satellite-surface observations over the 35 selected BSRN surface sites during the period 2000-2004. The surface radiation budgets are averaged from the BSRN Shortwave (SW) observations over a 1-hour interval centered at the time of the NASA Terra and Aqua satellites overpass, and the TOA radiation budgets are averaged from the closest FOV satellite data to the BSRN stations. Then the atmospheric column SW absorption will be inferred from the satellite TOA albedo and BSRN surface absorption (through the estimated surface albedo). Monthly means of Acol, TOA albedo, and surface absorption have been calculated under both clear- and all-sky conditions over the 35 selected BSRN sites which represent different climate regimes. To evaluate the GCM simulations, we have collected the ECHAM5-HAM simulated surface, TOA and atmospheric radiation budgets by researchers at ETH Zurich and compared those simulations with observations. The preliminary comparisons have shown that the ECHAM5 simulated clear-sky surface absorption, TOA albedo, and ACOL agree very well (1-3%) with observations. Under all-sky conditions, they have strong correlations with CERES-derived cloud fraction. The simulated surface absorption is lower and TOA albedo is higher than those under clear skies, but ACOL does not increase too much. However, there are relatively large differences over some regions and months. A further study is needed.

X. Dong↗

Adsorption of Neodymium, Dysprosium, and Ytterbium to Goethite under Varying Aqueous Chemistry Conditions

The adsorption of rare earth elements (REEs) to iron oxides can regulate the mobility of REEs in the environment and is heavily influenced by water chemistry. This study utilized batch experiments to examine the adsorption of Nd, Dy, and Yb to goethite under varying pH, electrolyte (type and concentration), and concentrations of dissolved inorganic carbon and citrate. REE adsorption was strongly influenced by pH, with an increase from essentially no adsorption at pH 3.0 to nearly complete adsorption at pH 6.5 and higher. Citrate enhanced the adsorption of REEs at low pH (<5.0), likely by forming goethite-REE-citrate ternary surface complexes. However, citrate inhibited the adsorption of REEs at higher pH (>5.0) by forming aqueous REE-citrate complexes. Ionic strength had a small influence on REE adsorption, and the presence of dissolved inorganic carbon had no discernible effect. Equilibrium adsorption was interpreted with a triple-layer surface complexation model (SCM). The selection of surface complexation reactions was guided by extended X-ray absorption fine structure spectra. An SCM with a single bidentate inner-sphere surface complexation reaction for Nd and two inner-sphere surface complexation reactions (one monodentate and one bidentate reaction) for Dy and Yb effectively simulated adsorption across a broad range of conditions in the absence of citrate. Accounting for the effects of citrate on REE adsorption required the addition of up to two ternary REE-citrate-goethite surface complexes. The SCM can enable predictions of REE transport in subsurface environments that have goethite as an important adsorbent mineral. Furthermore, this predictive capability could contribute to identifying potential REE sources and facilitating efficient extraction of REEs.

58 GEOSCIENCES↗

Adsorption of neodymium, dysprosium, and ytterbium to goethite under varying aqueous chemistry conditions [dataset]

The adsorption of rare earth elements (REEs) to iron oxides can regulate the mobility of REEs in the environment and is heavily influenced by water chemistry. This study utilized batch experiments to examine the adsorption of Nd, Dy, and Yb to goethite under varying pH, electrolyte (type and concentration), and concentrations of dissolved inorganic carbon and citrate. REE adsorption was strongly influenced by pH, with an increase from essentially no adsorption at pH 3.0 to nearly complete adsorption at pH 6.5 and higher. Citrate enhanced the adsorption of REEs at low pH (< 5.0), likely by forming goethite-REE-citrate ternary surface complexes. However, citrate inhibited the adsorption of REEs at higher pH (> 5.0) by forming aqueous REE-citrate complexes. Ionic strength had a small influence on REE adsorption, and the presence of dissolved inorganic carbon had no discernible effect. Equilibrium adsorption was interpreted with a triple layer surface complexation model (SCM). The selection of surface complexation reactions was guided by extended X-ray absorption fine structure spectra. A SCM with a single bidentate inner-sphere surface complexation reaction for Nd and two inner-sphere surface complexation reactions (one monodentate and one bidentate reaction) for Dy and Yb effectively simulated adsorption across a broad range of conditions in the absence of citrate. Accounting for the effects of citrate on REE adsorption required the addition of up to two ternary REE-citrate-goethite surface complexes. The SCM can enable predictions of REE transport in subsurface environments that have goethite as an important adsorbent mineral. This predictive capability could contribute to identifying potential REE sources and facilitating efficient extraction of REEs.

58 GEOSCIENCES↗

Mantle-flow tectonics and the origin of Ishtar Terra, Venus

It is proposed that western Ishtar Terra formed due to compression and crustal thickening above a cylindrical mantle downwelling. A model for crustal deformation due to downwelling successfully reproduces many observed characteristics of western Ishtar. Although axisymmetric downwelling occur in numerical models of constant-viscosity mantle convection, there is no evidence for their existence in earth's mantle, where downwellings are sheet-like. Either modes of downflow in Venus and earth are fundamentally different, or differences in near-surface conditions and material behavior selectively emphasize surface expressions of the different downwelling modes.

Bindschadler, D. L.↗

Modulur DIPS, 2.5-kWe modules for lunar/Mars surface applications, design point selection summary

The results are presented of a systematic series of studies leading to the selection and conceptual design development of a Dynamic Isotope Power System (DIPS) module for lunar and Martian surface applications. An optimum system configuration has been developed for the module that provides a system with a radiator area which is small and manageable without significantly impacting the system mass, efficiency, and technological risk. The maximum design temperature for the system has been determined.

Otting, William D.↗

Urban Climate Station Site Selection Through Combined Digital Surface Model and Sun Angle Calculations

Meteorological measurements within urban areas are becoming increasingly important due to the accentuating effects of climate change upon the Urban Heat Island (UHI). However, ensuring that such measurements are representative of the local area is often difficult due to the diversity of the urban environment. The evaluation of sites is important for both new sites and for the relocation of established sites to ensure that long term changes in the meteorological and climatological conditions continue to be faithfully recorded. Site selection is traditionally carried out in the field using both local knowledge and visual inspection. This paper exploits and assesses the use of lidar-derived digital surface models (DSMs) to quantitatively aid the site selection process. This is acheived by combining the DSM with a solar model, first to generate spatial maps of sky view factors and sun-hour potential and second, to generate site-specific views of the horizon. The results show that such a technique is a useful first-step approach to identify key sites that may be further evaluated for the location of meteorological stations within urban areas.

digital surface model↗

Numerical methods and a computer program for subsonic and supersonic aerodynamic design and analysis of wings with attainable thrust considerations

This paper describes methodology and an associated computer program for the design of wing lifting surfaces with attainable thrust taken into consideration. The approach is based on the determination of an optimum combination of a series of candidate surfaces rather than the more commonly used candidate loadings. Special leading-edge surfaces are selected to provide distributed leading-edge thrust forces which compensate for any failure to achieve the full theoretical leading-edge thrust, and a second series of general candidate surfaces is selected to minimize drag subject to constraints on the lift coefficient and, if desired, on the pitching moment coefficient. A primary purpose of the design approach is the introduction of attainable leading-edge thrust considerations so that relatively mild camber surfaces may be employed in the achievement of aerodynamic efficiencies comparable to those attainable if full theoretical leading-edge thrust could be achieved. The program provides an analysis as well as a design capability and is applicable to both subsonic and supersonic flow.

Carlson, H. W.↗

Improvement of Aerosol Optical Depth Retrieval over Hong Kong from a Geostationary Meteorological Satellite Using Critical Reflectance with Background Optical Depth Correction

Despite continuous efforts to retrieve aerosol optical depth (AOD) using a conventional 5-channelmeteorological imager in geostationary orbit, the accuracy in urban areas has been poorer than other areas primarily due to complex urban surface properties and mixed aerosol types from different emission sources. The two largest error sources in aerosol retrieval have been aerosol type selection and surface reflectance. In selecting the aerosol type from a single visible channel, the season-dependent aerosol optical properties were adopted from longterm measurements of Aerosol Robotic Network (AERONET) sun-photometers. With the aerosol optical properties obtained fromthe AERONET inversion data, look-up tableswere calculated by using a radiative transfer code: the Second Simulation of the Satellite Signal in the Solar Spectrum (6S). Surface reflectance was estimated using the clear sky composite method, awidely used technique for geostationary retrievals. Over East Asia, the AOD retrieved from the Meteorological Imager showed good agreement, although the values were affected by cloud contamination errors. However, the conventional retrieval of the AOD over Hong Kong was largely underestimated due to the lack of information on the aerosol type and surface properties. To detect spatial and temporal variation of aerosol type over the area, the critical reflectance method, a technique to retrieve single scattering albedo (SSA), was applied. Additionally, the background aerosol effect was corrected to improve the accuracy of the surface reflectance over Hong Kong. The AOD retrieved froma modified algorithmwas compared to the collocated data measured by AERONET in Hong Kong. The comparison showed that the new aerosol type selection using the critical reflectance and the corrected surface reflectance significantly improved the accuracy of AODs in Hong Kong areas,with a correlation coefficient increase from0.65 to 0.76 and a regression line change from τMI [basic algorithm] = 0.41τAERONET + 0.16 to τMI [new algorithm] = 0.70τAERONET + 0.01.

aerosols↗