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At least 343 records · Page 19

Inorganic Chemistry Solutions to Semiconductor Nanocrystal Problems

The optoelectronic and chemical properties of semiconductor nanocrystals heavily depend on their composition, size, shape and internal structure, surface functionality, etc. Available strategies to alter these properties through traditional colloidal syntheses and ligand exchange methods place a premium on specific reaction conditions and surfactant combinations. In this invited review, we apply a molecular-level understanding of chemical precursor reactivity to reliably control the morphology, composition and intimate architecture (core/shell vs. alloyed) of semiconductor nanocrystals. We also describe our work aimed at achieving highly selective, low-temperature photochemical methods for the synthesis of semiconductor–metal and semiconductor–metal oxide photocatalytic nanocomposites. In addition, we describe our work on surface modification of semiconductor nanocrystal quantum dots using new approaches and methods that bypass ligand exchange, retaining the nanocrystal's native ligands and original optical properties, as well as on spectroscopic methods of characterization useful in determining surface ligand organization and chemistry. Using recent examples from our group and collaborators, we demonstrate how these efforts have lead to faster, wider and more systematic application of semiconductor nanocrystal-based materials to biological imaging and tracking, and to photocatalysis of unconventional substrates. We believe techniques and methods borrowed from inorganic chemistry (including coordination, organometallic and solid state chemistry) have much to offer in reaching a better understanding of the synthesis, functionalization and real-life application of such exciting materials as semiconductor nanocrystals (quantum dots, rods, tetrapods, etc.).

36 MATERIALS SCIENCE↗

The K2 Ecliptic Plane Input Catalog (EPIC) and stellar classifications of 138,600 targets in campaigns 1–8

The K2 Mission uses the Kepler spacecraft to obtain high-precision photometry over ≈80 day campaigns in the ecliptic plane. The Ecliptic Plane Input Catalog (EPIC) provides coordinates, photometry, and kinematics based on a federation of all-sky catalogs to support target selection and target management for the K2 mission. We describe the construction of the EPIC, as well as modifications and shortcomings of the catalog. Kepler magnitudes (Kp) are shown to be accurate to ≈0.1 mag for the Kepler field, and the EPIC is typically complete to Kp ≈ 17 (Kp ≈ 19 for campaigns covered by Sloan Digital Sky Survey). We furthermore classify 138,600 targets in Campaigns 1–8 (≈88% of the full target sample) using colors, proper motions, spectroscopy, parallaxes, and galactic population synthesis models, with typical uncertainties for G-type stars of ≈3% in T{sub eff}, ≈0.3 dex in log g, ≈40% in radius, ≈10% in mass, and ≈40% in distance. Our results show that stars targeted by K2 are dominated by K–M dwarfs (≈41% of all selected targets), F–G dwarfs (≈36%), and K giants (≈21%), consistent with key K2 science programs to search for transiting exoplanets and galactic archeology studies using oscillating red giants. However, we find significant variation of the fraction of cool dwarfs with galactic latitude, indicating a target selection bias due to interstellar reddening and increased contamination by giant stars near the galactic plane. We discuss possible systematic errors in the derived stellar properties, and differences with published classifications for K2 exoplanet host stars. The EPIC is hosted at the Mikulski Archive for Space Telescopes (MAST): http://archive.stsci.edu/k2/epic/search.php.

79 ASTRONOMY AND ASTROPHYSICS↗

Synthesis and characterization of various zeolites and study of dynamic adsorption of dimethyl methyl phosphate over them

Graphical abstract: Thermal desorption pattern of DMMP over various zeolites (a) 1st desorption and (b) 2nd desorption. - Highlights: • Synthesis of Zeolite-A, MCM-22, Zeolite-X and Erionite by hydrothermal method. • Zeolites were characterized by using XRD, FTIR, BET, NH{sub 3}-TPD, SEM and EDS techniques. • Dynamic adsorption of DMMP on zeolites was carried out using TPD plus chemisorption system. • Thermal desorption of DMMP on zeolites was carried using the same system. - Abstract: Zeolite-A, MCM-22, Zeolite-X and Erionite were synthesized successfully under hydrothermal conditions and were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Brunauer–Emmett–Teller (BET) surface area analysis and thermal programmed desorption (TPD). Dynamic adsorption of dimethyl methyl phosphate (DMMP) was carried out on these zeolites. Zeolite-X having high surface area among all four zeolites shows highest adsorption capacity followed by Erionite and MCM-22 where as Zeolite-A shows the least. For all zeolites adsorption was found to be high initially and it then decreases with increase in injected volume. Then desorption pattern was analyzed which shows two types of peaks, sharp peak representing desorption of physisorbed DMMP and a broad peak representing desorption of strongly chemisorbed DMMP.

36 MATERIALS SCIENCE↗

Understanding Selectivity in CO2 Hydrogenation to Methanol for MoP Nanoparticle Catalysts Using In Situ Techniques

Molybdenum phosphide (MoP) catalyzes the hydrogenation of CO, CO2, and their mixtures to methanol, and it is investigated as a high-activity catalyst that overcomes deactivation issues (e.g., formate poisoning) faced by conventional transition metal catalysts. MoP as a new catalyst for hydrogenating CO2 to methanol is particularly appealing for the use of CO2 as chemical feedstock. Herein, we use a colloidal synthesis technique that connects the presence of MoP to the formation of methanol from CO2, regardless of the support being used. By conducting a systematic support study, we see that zirconia (ZrO2) has the striking ability to shift the selectivity towards methanol by increasing the rate of methanol conversion by two orders of magnitude compared to other supports, at a CO2 conversion of 1.4% and methanol selectivity of 55.4%. In situ X-ray Absorption Spectroscopy (XAS) and in situ X-ray Diffraction (XRD) indicate that under reaction conditions the catalyst is pure MoP in a partially crystalline phase. Results from Diffuse Reflectance Infrared Fourier Transform Spectroscopy coupled with Temperature Programmed Surface Reaction (DRIFTS-TPSR) point towards a highly reactive monodentate formate intermediate stabilized by the strong interaction of MoP and ZrO2. This study definitively shows that the presence of a MoP phase leads to methanol formation from CO2, regardless of support and that the formate intermediate on MoP governs methanol formation rate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Temperature Pretreatment Effect on Co/SiO 2 Active Sites and Ethane Dehydrogenation

Here, we report the synthesis, optimization, and characterization of Co/SiO 2 for ethane nonoxidative dehydrogenation. Co/SiO 2 is synthesized via strong electrostatic adsorption using the widely available Co(NO 3 ) 2 as the precursor. We demonstrate that high-temperature pretreatment (900 °C) in an inert atmosphere can significantly enhance the initial activity of the Co/SiO 2 catalyst. X-ray absorption near-edge spectroscopy (XANES), temperature-programmed reduction (TPR), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) suggest that highly dispersed Co(II) clusters are more active than Co 0 or CoO x nanoparticles. Fourier transform infrared (FTIR) and isopropanol (IPA) temperature-programmed desorption and density functional theory (DFT) calculations suggest that high-temperature treatment significantly increases the density of active Lewis acid sites, possibly via surface dehydroxylation of the catalyst.

36 MATERIALS SCIENCE↗

Random heteropolymers as enzyme mimics

Despite successes in replicating the primary–secondary–tertiary structure hierarchy of protein, it remains elusive to synthetically materialize protein functions that are deeply rooted in their chemical, structural and dynamic heterogeneities. We propose that for polymers with backbone chemistries different from that of proteins, programming spatial and temporal projections of sidechains at the segmental level can be effective in replicating protein behaviours; and leveraging the rotational freedom of polymer can mitigate deficiencies in monomeric sequence specificity and achieve behaviour uniformity at the ensemble level. Here, guided by the active site analysis of about 1,300 metalloproteins, we design random heteropolymers (RHPs) as enzyme mimics based on one-pot synthesis. We introduce key monomers as the equivalents of the functional residues of protein and statistically modulate the chemical characteristics of key monomer-containing segments, such as segmental hydrophobicity. The resultant RHPs form pseudo-active sites that provide key monomers with protein-like microenvironments, co-localize substrates with catalytic or cofactor-binding sidechains and catalyse reactions such as oxidation and cyclization of citronellal with isopulegol/menthoglycol selectivity. This RHP design led to enzyme-like materials that can retain catalytic activity under non-biological conditions, are compatible with scalable processing and have expanded substrate scope, including environmentally long-lasting antibiotic tetracycline.

36 MATERIALS SCIENCE↗

Innovative Gasification to Produce Fischer-Tropsch Jet and Diesel Fuel

The primary objective of this project and the U.S. DOE’s integrated biorefinery (“IBR”) program was to demonstrate conversion of biomass and waste-derived feedstocks into military spec liquid fuels. Frontline’s proposed integrated process was to incorporate several novel technologies and innovative applications of existing technologies that would serve both to increase plant efficiency and also to lower the cost of the produced biofuels. The project was intended to demonstrate Frontline Bioenergy’s technologies for gasification and synthesis gas clean-up configuration to produce a syngas stream suitable for a proven Fischer-Tropsch (“F-T”) unit that would produce F-T intermediate products. These F-T intermediate products were to be upgraded to military spec diesel and jet fuel, including F76, JP5, and JP8. Specifically, these technologies consisted of: 1. Frontline’s PMFreeGas® ultra low particulate matter (PM) hot gas filtration technology 2. Application of Frontline’s TarFreeGas® ultra low-tar gasification technology 3. Frontline’s novel approach to syngas conditioning The proposed gasifier system was to operate at 10 tpd capacity while the F-T plant was capable of approximately one barrel per day. Although the gasifier output would have been roughly ten times the F-T plant’s required input, the 10 tpd capacity was chosen to enable scaling to commercial capacity. Project partners included i) SGC Energia, owner of the F-T technology and owner of the proposed demonstration site in Pasadena, Texas; ii) Stanley Consultants, a reputable engineering company that provided detailed electrical engineering services; and iii) Delphi Engineering & Construction LLC, a consulting company that provided project management advisory services. The integrated plant was never constructed due to lack of cost share funds. However, the commercialization plan and associated financial model suggested such a plant could be economically viable when the price of oil exceeds $70 per barrel. The price of feedstock plays a significant role in the profitability of the plant for a given value of oil. An integrated biorefinery capable of producing liquid transportation fuels and other chemical feedstocks would benefit the public by providing a sustainable pathway to convert domestically available feedstocks into fuels that might otherwise be imported from countries or regions of the world that are typically hostile to the United States.

09 BIOMASS FUELS↗

Controlled synthesis of α-MnO{sub 2} nanowires and their catalytic performance for toluene combustion

Highlights: • One-dimensional α-MnO{sub 2} nanowires were prepared by a facile hydrothermal route. • Shape and crystal phase of the products were controlled by tuning reaction conditions. • A possible formation mechanism of the α-MnO{sub 2} nanowires was discussed. • The α-MnO{sub 2} nanowires showed great catalytic activity for toluene combustion. - Abstract: α-MnO{sub 2} nanowires with a length about 6–10 μm and an average diameter of 20 nm were synthesized through a facile hydrothermal process without any templates or surfactants. The products were characterized by X-ray powder diffraction, Raman spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, hydrogen temperature-programmed reduction techniques, X-ray photoelectron spectroscopy and surface area analysis. The effects of the hydrothermal temperature and the concentration of CH{sub 3}COOH on the crystal phase and morphology of the final products were studied in detail. The hydrothermal temperature and the concentration of CH{sub 3}COOH play crucial roles in determining the crystal phase and morphology of the products. The possible formation mechanism of the α-MnO{sub 2} nanowires was investigated and discussed. Additionally, the as-prepared α-MnO{sub 2} nanowires showed higher catalytic activity for toluene combustion than the commercial MnO{sub 2}, suggesting their potential applications in the elimination of volatile organic compounds.

36 MATERIALS SCIENCE↗

USD Catalysis Group for Alternative Energy (Final Report)

Project Summary Catalytic processes are a major technological underpinning of modern society, and are essential to the energy sector in the processing of chemical fuels from natural resources, fine chemicals synthesis, and energy conversion. Advances in catalyst technology are enormously valuable since these lead to reduced chemical waste, reduced energy loss, and reduced costs. New energy technologies, which are critical to future economic growth, are also heavily reliant on catalysts, including fuel cells and photo-electrochemical cells. Currently, the state of South Dakota is underdeveloped in terms of research infrastructure related to catalysis. If South Dakota intends to participate in significant economic growth opportunities that result from advances in catalyst technology, then this area of research needs to be made a high priority for investment. To this end, a focused research effort is proposed in which investigators from The University of South Dakota (USD) and The South Dakota School of Mines and Technology (SDSMT) will contribute to form the South Dakota Catalysis Group (SDCG). The multidisciplinary team of the (SDCG) include: (USD) Dan Engebretson, James Hoefelmeyer, Ranjit Koodali, and Grigoriy Sereda; (SDSMT) Phil Scott Ahrenkiel, Hao Fong, Jan Puszynski, Rajesh Shende, and Jacek Swiatkiewicz. The group is well suited to engage in a collaborative project due to the resources available within the existing programs. Activities within the SDCG will be monitored through an external committee consisting of three distinguished professors in chemistry. The committee will provide expert advice and recommendations to the SDCG. Advisory meetings in which committee members interact with South Dakota investigators will be accompanied by individual oral and poster presentations in a materials and catalysis symposium. The symposium will attract prominent scientists, and will enhance the visibility of research in the state of South Dakota. The SDCG requests funding through the Department of Energy (DoE) to establish this multidisciplinary research cluster in the area of catalysis. This long-term approach includes synthesis, characterization, catalyst evaluation, modeling, and scale-up. The project includes plans to acquire instrumentation critical to enabling competitive research. These acquisitions will complement existing resources in the state. The effect of implementation of the proposed efforts will be to significantly enhance state infrastructure in personnel and equipment, and lead to a nationally and internationally recognized research center.

Hoefelmeyer, James↗

Effect of Preparation Conditions of Fe@SiO2 Catalyst on Its Structure Using High-Pressure Activity Studies in a 3D-Printed SS Microreactor

Fischer–Tropsch synthesis (FTS) in a 3D-printed stainless steel (SS) microchannel microreactor was investigated using Fe@SiO2 catalysts. The catalysts were prepared by two different techniques: one pot (OP) and autoclave (AC). The mesoporous structure of the two catalysts, Fe@SiO2 (OP) and Fe@SiO2 (AC), ensured a large contact area between the reactants and the catalyst. They were characterized by N2 physisorption, H2 temperature-programmed reduction (H2-TPR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron microscopy (XPS), and thermogravimetric analysis–differential scanning calorimetry (TGA-DSC) techniques. The AC catalyst had a clear core–shell structure and showed a much greater surface area than that prepared by the OP method. The activities of the catalysts in terms of FTS were studied in the 200–350 °C temperature range at 20-bar pressure with a H2/CO molar ratio of 2:1. The Fe@SiO2 (AC) catalyst showed higher selectivity and higher CO conversion to olefins than Fe@SiO2 (OP). Stability studies of both catalysts were carried out for 30 h at 320 °C at 20 bar with a feed gas molar ratio of 2:1. The Fe@SiO2 (AC) catalyst showed higher stability and yielded consistent CO conversion compared to the Fe@SiO2 (OP) catalyst.

Biochemistry & Molecular Biology↗

Method and apparatus for in situ synthesis of SiC, SiC ceramic matrix composites, and SiC metal matrix composites during additive manufacturing

Methods and apparatuses for in situ synthesis of SiC, CMCs, and MMCs are disclosed, comprising: providing an apparatus having: an electromagnetic energy source; an autofocusing scanner; a powder system for SiC and one or more powders; a powder delivery system; a shielding gas comprising argon and/or nitrogen; and a computer coupled to and configured to control the energy source, scanner, powder system, and powder delivery system to deposit layers of the sample; programming the computer with specifications of the sample; using the computer to control electromagnetic radiation, mixing ratio, and powder deposition parameters based on the specifications of the sample; and using the autofocusing scanner to focus and scan the electromagnetic radiation onto the sample while the powders are concurrently deposited by the powder delivery system onto the sample to create a melting pool to deposit one or more layers onto the sample. Other embodiments are described and claimed.

Liu, Jian↗

Synthesis and characterization of Mo-doped SrFeO 3-δ as cathode materials for solid oxide fuel cells

This paper demonstrates the potential application of Mo-doped SrFeO 3-δ perovskites as new cathode materials for solid oxide fuel cells (SOFCs). SrFe 1-x MoxO 3-δ (x = 0, 0.05, 0.1, 0.2 and 0.25) perovskite materials have been synthesized by a microwave-assisted combustion method. By doping with Mo, the electrical conductivity of the doped SrFeO 3-δ in air is reduced with increasing amounts of Mo. At 800 °C, the conductivity drops from about 62 to 22 S cm -1 when the doping level is increased to 25%. According to X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and temperature programmed reduction (TPR) results, a decrease in the concentration of charge carrier Fe 4+ ions may account for the decrease in electrical conductivity. In contrast, the resistance to sintering and tolerance to reduction of SrFeO 3-δ are improved by Mo-doping. Additionally, the thermal expansion coefficient at 800 °C drops from 40.8 × 10 -6 K -1 for SrFeO 3-δ to 25.7 × 10 -6 K -1 for SrFe 0.8 Mo 0.2 O 3-δ and 20.9 × 10 -6 K -1 for SrFe0.75Mo0.25O 3-δ . This significant decrease in the thermal expansion coefficient makes Mo-doped SrFeO 3-δ materials attractive as cathode candidates for SOFCs. Finally, a relatively low polarization resistance of 0.074 Ω cm2 is obtained for SrFe 0.8 Mo 0.2 O 3-δ at 800 °C in air.

25 ENERGY STORAGE↗

THE SIZE EVOLUTION OF PASSIVE GALAXIES: OBSERVATIONS FROM THE WIDE-FIELD CAMERA 3 EARLY RELEASE SCIENCE PROGRAM

We present the size evolution of passively evolving galaxies at z {approx} 2 identified in Wide-Field Camera 3 imaging from the Early Release Science program. Our sample was constructed using an analog to the passive BzK galaxy selection criterion, which isolates galaxies with little or no ongoing star formation at z {approx}> 1.5. We identify 30 galaxies in {approx}40 arcmin{sup 2} to H < 25 mag. By fitting the 10-band Hubble Space Telescope photometry from 0.22 {mu}m {approx}< {lambda}{sub obs} {approx}< 1.6 {mu}m with stellar population synthesis models, we simultaneously determine photometric redshift, stellar mass, and a bevy of other population parameters. Based on the six galaxies with published spectroscopic redshifts, we estimate a typical redshift uncertainty of {approx}0.033(1 + z). We determine effective radii from Sersic profile fits to the H-band image using an empirical point-spread function. By supplementing our data with published samples, we propose a mass-dependent size evolution model for passively evolving galaxies, where the most massive galaxies (M{sub *} {approx} 10{sup 11} M{sub Sun }) undergo the strongest evolution from z {approx} 2 to the present. Parameterizing the size evolution as (1 + z){sup -{alpha}}, we find a tentative scaling of {alpha} Almost-Equal-To (- 0.6 {+-} 0.7) + (0.9 {+-} 0.4)log (M{sub *}/10{sup 9} M{sub Sun }), where the relatively large uncertainties reflect the poor sampling in stellar mass due to the low numbers of high-redshift systems. We discuss the implications of this result for the redshift evolution of the M{sub *}-R{sub e} relation for red galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗

Non-LTE analysis of neutral copper in late-type metal-poor stars

We investigated the copper abundances of 64 late-type stars in the Galactic disk and halo with effective temperatures from 5400 to 6700 K and [Fe/H] from −1.88 to −0.17. For the first time, the copper abundances are derived using both local thermodynamic equilibrium (LTE) and non-local thermodynamic equilibrium (non-LTE) calculations. High-resolution (R>40,000), high signal-to-noise ratio (S/N>100) spectra from the FOCES spectrograph are used. The atmospheric models are calculated based on the MAFAGS opacity sampling code. All the abundances are derived using spectrum synthesis methods. Our results indicate that the non-LTE effects of copper are important for metal-poor stars, showing a departure of ∼0.17 dex at a metallicity of ∼−1.5. We also find that the copper abundances derived from non-LTE calculations are enhanced compared with those from LTE. The enhancements show clear dependence on the metallicity, which gradually increases with decreasing [Fe/H] for our program stars, leading to a flatter distribution of [Cu/Fe] with [Fe/H] than previous work. There is a hint that the thick- and thin-disk stars have different behaviors in [Cu/Fe], and bending of the disk stars may exist.

79 ASTRONOMY AND ASTROPHYSICS↗

Analysis of rapidly synthesized guest-filled porous complexes with synchrotron radiation: practical guidelines for the crystalline sponge method

This report describes complete practical guidelines and insights for the crystalline sponge method, which have been derived through the first use of synchrotron radiation on these systems, and includes a procedure for faster synthesis of the sponges. These guidelines will be applicable to crystal sponge data collected at synchrotrons or in-house facilities, and will allow researchers to obtain reliable high-quality data and construct chemically and physically sensible models for guest structural determination. A detailed set of synthetic and crystallographic guidelines for the crystalline sponge method based upon the analysis of expediently synthesized crystal sponges using third-generation synchrotron radiation are reported. The procedure for the synthesis of the zinc-based metal–organic framework used in initial crystal sponge reports has been modified to yield competent crystals in 3 days instead of 2 weeks. These crystal sponges were tested on some small molecules, with two being unexpectedly difficult cases for analysis with in-house diffractometers in regard to data quality and proper space-group determination. These issues were easily resolved by the use of synchrotron radiation using data-collection times of less than an hour. One of these guests induced a single-crystal-to-single-crystal transformation to create a larger unit cell with over 500 non-H atoms in the asymmetric unit. This led to a non-trivial refinement scenario that afforded the best Flack x absolute stereochemical determination parameter to date for these systems. The structures did not require the use of PLATON/SQUEEZE or other solvent-masking programs, and are the highest-quality crystalline sponge systems reported to date where the results are strongly supported by the data. A set of guidelines for the entire crystallographic process were developed through these studies. In particular, the refinement guidelines include strategies to refine the host framework, locate guests and determine occupancies, discussion of the proper use of geometric and anisotropic displacement parameter restraints and constraints, and whether to perform solvent squeezing/masking. The single-crystal-to-single-crystal transformation process for the crystal sponges is also discussed. The presented general guidelines will be invaluable for researchers interested in using the crystalline sponge method at in-house diffraction or synchrotron facilities, will facilitate the collection and analysis of reliable high-quality data, and will allow construction of chemically and physically sensible models for guest structural determination.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Design, Synthesis, and Characterization of Novel Small Molecules as Broad Range Antischistosomal Agents

Schistosomiasis is a major human parasitic disease afflicting more than 250 million people, historically treated with chemotherapies praziquantel or oxamniquine. Since oxamniquine is species-specific, killing Schistosoma mansoni but not other schistosome species ( S. haematobium or S. japonicum ) and evidence for drug resistant strains is growing, research efforts have focused on identifying novel approaches. Guided by data from X-ray crystallographic studies and Schistosoma worm killing assays on oxamniquine, our structure-based drug design approach produced a robust structure–activity relationship (SAR) program that identified several new lead compounds with effective worm killing. We report these studies culminated in the discovery of compound 12a , which demonstrated broad-species activity in killing S. mansoni (75%), S. haematobium (40%), and S. japonicum (83%).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗