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Sample records for absorbable organic halides

  1. EVALUATION OF METHODS FOR THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER AND WASTE

    EPA Science Inventory

    Various methods for the determination of total organic halides (TOX) in groundwater and in waste oil samples have been evaluated. Of three inorganic halide species generation approaches and three inorganic halide determinative techniques evaluated for groundwater analyses, one co...

  2. Unraveling the Role of Monovalent Halides in Mixed-Halide Organic-Inorganic Perovskites.

    PubMed

    Deepa, Melepurath; Ramos, F Javier; Shivaprasad, S M; Ahmad, Shahzada

    2016-03-16

    The performance of perovskite solar cells is strongly influenced by the composition and microstructure of the perovskite. A recent approach to improve the power conversion efficiencies utilized mixed-halide perovskites, but the halide ions and their roles were not directly studied. Unraveling their precise location in the perovskite layer is of paramount importance. Here, we investigated four different perovskites by using X-ray photoelectron spectroscopy, and found that among the three studied mixed-halide perovskites, CH3 NH3 Pb(I0.74 Br0.26 )3 and CH3 NH3 PbBr3-x Clx show peaks that unambiguously demonstrate the presence of iodide and bromide in the former, and bromide and chloride in the latter. The CH3 NH3 PbI3-x Clx perovskite shows anomalous behavior, the iodide content far outweighs that of the chloride; a small proportion of chloride, in all likelihood, resides deep within the TiO2 /absorber layer. Our study reveals that there are many distinguishable structural differences between these perovskites, and that these directly impact the photovoltaic performances. PMID:26717046

  3. Kinetic Studies of the Solvolysis of Two Organic Halides

    ERIC Educational Resources Information Center

    Duncan, J. A.; Pasto, D. J.

    1975-01-01

    Describes an undergraduate organic chemistry laboratory experiment which utilizes the solvolysis of organic halides to demonstrate first and second order reaction kinetics. The experiment also investigates the effect of a change of solvent polarity on reaction rate, common-ion and noncommon-ion salt effects, and the activation parameters of a…

  4. Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

    ERIC Educational Resources Information Center

    Cruz-Ramirez de Arellano, Daniel

    2013-01-01

    Organic chemistry is an essential subject for many undergraduate students completing degrees in science, engineering, and pre-professional programs. However, students often struggle with the concepts and skills required to successfully solve organic chemistry exercises. Since alkyl halides are traditionally the first functional group that is…

  5. Charge Transfer Dynamics between Carbon Nanotubes and Hybrid Organic Metal Halide Perovskite Films.

    PubMed

    Schulz, Philip; Dowgiallo, Anne-Marie; Yang, Mengjin; Zhu, Kai; Blackburn, Jeffrey L; Berry, Joseph J

    2016-02-01

    In spite of the rapid rise of metal organic halide perovskites for next-generation solar cells, little quantitative information on the electronic structure of interfaces of these materials is available. The present study characterizes the electronic structure of interfaces between semiconducting single walled carbon nanotube (SWCNT) contacts and a prototypical methylammonium lead iodide (MAPbI3) absorber layer. Using photoemission spectroscopy we provide quantitative values for the energy levels at the interface and observe the formation of an interfacial dipole between SWCNTs and perovskite. This process can be ascribed to electron donation from the MAPbI3 to the adjacent SWCNT making the nanotube film n-type at the interface and inducing band bending throughout the SWCNT layer. We then use transient absorbance spectroscopy to correlate this electronic alignment with rapid and efficient photoexcited charge transfer. The results indicate that SWCNT transport and contact layers facilitate rapid charge extraction and suggest avenues for enhancing device performance. PMID:26757105

  6. THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER: AN INTERLABORATORY COMPARATIVE STUDY OF TWO METHODS

    EPA Science Inventory

    Total organic halide (TOX) analyzers are commonly used to measure the amount of dissolved halogenated organic byproducts in disinfected waters. Because of the lack of information on the identity of disinfection byproducts, rigorous testing of the dissolved organic halide (DOX) pr...

  7. THE DETERMINATION OF TOTAL ORGANIC HALIDE IN WATER: A COMPARATIVE STUDY OF TWO INSTRUMENTS

    EPA Science Inventory

    Total organic halide (TOX) analyzers are commonly used to measure the amount of dissolved halogenated organic byproducts in disinfected waters. ecause of the lack of information on the identity of disinfection byproducts, rigorous testing of the dissolved organic halide (DOX) pro...

  8. Optical Properties of Photovoltaic Organic-Inorganic Lead Halide Perovskites.

    PubMed

    Green, Martin A; Jiang, Yajie; Soufiani, Arman Mahboubi; Ho-Baillie, Anita

    2015-12-01

    Over the last several years, organic-inorganic lead halide perovskites have rapidly emerged as a new photovoltaic contender. Although energy conversion efficiency above 20% has now been certified, improved understanding of the material properties contributing to these high performance levels may allow the progression to even higher efficiency, stable cells. The optical properties of these new materials are important not only to device design but also because of the insight they provide into less directly accessible properties, including energy-band structures, binding energies, and likely impact of excitons, as well as into absorption and inverse radiative recombination processes. PMID:26560862

  9. EPA (ENVIRONMENTAL PROTECTION AGENCY) METHOD STUDY 32: METHOD 450.1 - TOTAL ORGANIC HALIDES (TOX)

    EPA Science Inventory

    The report describes the interlaboratory method study that was performed to evaluate interim Method 450.1 for total organic halides (TOX). In the method, a measured volume of water is passed through two columns in series each containing 40 mg of activated charcoal. Organic halide...

  10. Theory of hydrogen migration in organic-inorganic halide perovskites.

    PubMed

    Egger, David A; Kronik, Leeor; Rappe, Andrew M

    2015-10-12

    Solar cells based on organic-inorganic halide perovskites have recently been proven to be remarkably efficient. However, they exhibit hysteresis in their current-voltage curves, and their stability in the presence of water is problematic. Both issues are possibly related to a diffusion of defects in the perovskite material. By using first-principles calculations based on density functional theory, we study the properties of an important defect in hybrid perovskites-interstitial hydrogen. We show that differently charged defects occupy different crystal sites, which may allow for ionization-enhanced defect migration following the Bourgoin-Corbett mechanism. Our analysis highlights the structural flexibility of organic-inorganic perovskites: successive iodide displacements, combined with hydrogen bonding, enable proton diffusion with low migration barriers. These findings indicate that hydrogen defects can be mobile and thus highly relevant for the performance of perovskite solar cells. PMID:26073061

  11. Giant photostriction in organic-inorganic lead halide perovskites.

    PubMed

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-01-01

    Among the many materials investigated for next-generation photovoltaic cells, organic-inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge-orbital-lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices. PMID:27044485

  12. Giant photostriction in organic-inorganic lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-04-01

    Among the many materials investigated for next-generation photovoltaic cells, organic-inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge-orbital-lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices.

  13. Layered structures of organic/inorganic hybrid halide perovskites

    NASA Astrophysics Data System (ADS)

    Huan, Tran Doan; Tuoc, Vu Ngoc; Minh, Nguyen Viet

    2016-03-01

    Organic-inorganic hybrid halide perovskites, in which the A cations of an ABX3 perovskite are replaced by organic cations, may be used for photovoltaic and solar thermoelectric applications. In this contribution, we systematically study three lead-free hybrid perovskites, i.e., methylammonium tin iodide CH3NH3SnI3 , ammonium tin iodide NH4SnI3 , and formamidnium tin iodide HC (NH2)2SnI3 by first-principles calculations. We find that in addition to the commonly known motif in which the corner-shared SnI6 octahedra form a three-dimensional network, these materials may also favor a two-dimensional (layered) motif formed by alternating layers of the SnI6 octahedra and the organic cations. These two motifs are nearly equal in free energy and are separated by low barriers. These layered structures features many flat electronic bands near the band edges, making their electronic structures significantly different from those of the structural phases composed of three-dimension networks of SnI6 octahedra. Furthermore, because the electronic structures of HC (NH2)2SnI3 are found to be rather similar to those of CH3NH3SnI3 , formamidnium tin iodide may also be promising for the applications of methylammonium tin iodide.

  14. The effect of low solublility organic acids on the hygroscopicity of sodium halide aerosols

    NASA Astrophysics Data System (ADS)

    Miñambres, L.; Méndez, E.; Sánchez, M. N.; Castaño, F.; Basterretxea, F. J.

    2014-02-01

    In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be performed in this study. The hygroscopic properties of sodium halide submicrometer particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were generated by flowing atomized sodium halide particles (either dry or aqueous) through a heated oven containing the gaseous acid. The obtained results indicate that gaseous organic acids easily nucleate onto dry and aqueous sodium halide particles. On the other hand, Scanning Electron Microscopy (SEM) images indicate that lauric acid coating on NaCl particles makes them to aggregate in small clusters. The hygroscopic behaviour of covered sodium halide particles in deliquescence mode shows different features with the exchange of the halide ion: whereas the organic covering has little effect in NaBr particles, NaCl and NaI covered particles change their deliquescence relative humidities, with different trends observed for each of the acids studied. In efflorescence mode, the overall effect of the organic covering is to retard the loss of water in the particles. It has been observed that the presence of gaseous water in heterogeneously nucleated particles tends to displace the cover of hexanoic acid to energetically stabilize the system.

  15. The effect of low solubility organic acids on the hygroscopicity of sodium halide aerosols

    NASA Astrophysics Data System (ADS)

    Miñambres, L.; Méndez, E.; Sánchez, M. N.; Castaño, F.; Basterretxea, F. J.

    2014-10-01

    In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be investigated in this study. The hygroscopic properties of sodium halide sub-micrometre particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were generated by flowing atomized sodium halide particles (either dry or aqueous) through a heated oven containing the gaseous acid. The obtained results indicate that gaseous organic acids easily nucleate onto dry and aqueous sodium halide particles. On the other hand, scanning electron microscopy (SEM) images indicate that lauric acid coating on NaCl particles makes them to aggregate in small clusters. The hygroscopic behaviour of covered sodium halide particles in deliquescence mode shows different features with the exchange of the halide ion, whereas the organic surfactant has little effect in NaBr particles, NaCl and NaI covered particles experience appreciable shifts in their deliquescence relative humidities, with different trends observed for each of the acids studied. In efflorescence mode, the overall effect of the organic covering is to retard the loss of water in the particles. It has been observed that the presence of gaseous water in heterogeneously nucleated particles tends to displace the cover of hexanoic acid to energetically stabilize the system.

  16. A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells.

    PubMed

    McMeekin, David P; Sadoughi, Golnaz; Rehman, Waqaas; Eperon, Giles E; Saliba, Michael; Hörantner, Maximilian T; Haghighirad, Amir; Sakai, Nobuya; Korte, Lars; Rech, Bernd; Johnston, Michael B; Herz, Laura M; Snaith, Henry J

    2016-01-01

    Metal halide perovskite photovoltaic cells could potentially boost the efficiency of commercial silicon photovoltaic modules from ∼20 toward 30% when used in tandem architectures. An optimum perovskite cell optical band gap of ~1.75 electron volts (eV) can be achieved by varying halide composition, but to date, such materials have had poor photostability and thermal stability. Here we present a highly crystalline and compositionally photostable material, [HC(NH2)2](0.83)Cs(0.17)Pb(I(0.6)Br(0.4))3, with an optical band gap of ~1.74 eV, and we fabricated perovskite cells that reached open-circuit voltages of 1.2 volts and power conversion efficiency of over 17% on small areas and 14.7% on 0.715 cm(2) cells. By combining these perovskite cells with a 19%-efficient silicon cell, we demonstrated the feasibility of achieving >25%-efficient four-terminal tandem cells. PMID:26744401

  17. Purcell effect in an organic-inorganic halide perovskite semiconductor microcavity system

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Cao, Runan; Da, Peimei; Wang, Yafeng; Hu, Tao; Wu, Lin; Lu, Jian; Shen, Xuechu; Xu, Fei; Zheng, Gengfeng; Chen, Zhanghai

    2016-01-01

    Organic-inorganic halide perovskite semiconductors with the attractive physics properties, including strong photoluminescence (PL), huge oscillator strengths, and low nonradiative recombination losses, are ideal candidates for studying the light-matter interaction in nanostructures. Here, we demonstrate the coupling of the exciton state and the cavity mode in the lead halide perovskite microcavity system at room temperature. The Purcell effect in the coupling system is clearly observed by using angle-resolved photoluminescence spectra. Kinetic analysis based on time-resolved PL reveals that the spontaneous emission rate of the halide perovskite semiconductor is significantly enhanced at resonance of the exciton energy and the cavity mode. Our results provide the way for developing electrically driven organic polariton lasers, optical devices, and on-chip coherent quantum light sources.

  18. Cusps, self-organization, and absorbing states.

    PubMed

    Bonachela, Juan A; Alava, Mikko; Muñoz, Miguel A

    2009-05-01

    Elastic interfaces embedded in (quenched) random media exhibit metastability and stick-slip dynamics. These nontrivial dynamical features have been shown to be associated with cusp singularities of the coarse-grained disorder correlator. Here we show that annealed systems with many absorbing states and a conservation law but no quenched disorder exhibit identical cusps. On the other hand, similar nonconserved systems in the directed percolation class are also shown to exhibit cusps but of a different type. These results are obtained both by a recent method to explicitly measure disorder correlators and by defining an alternative new protocol inspired by self-organized criticality, which opens the door to easily accessible experimental realizations. PMID:19518401

  19. Exciton Binding Energy in Organic-Inorganic Tri-Halide Perovskites.

    PubMed

    Askar, Abdelrahman M; Shankar, Karthik

    2016-06-01

    The recent dramatic increase in the power conversion efficiencies of organic-inorganic tri-halide perovskite solar cells has triggered intense research worldwide and created a paradigm shift in the photovoltaics field. It is crucial to develop a solid understanding of the photophysical processes underlying solar cell operation in order to both further improve the photovoltaic performance of perovskite solar cells as well as to exploit the broader optoelectronic applications of the tri-halide perovskites. In this short review, we summarize the main research findings about the binding energy of excitons in tri-halide perovskite materials and find that a value in the range of 2-22 meV at room temperature would be a safe estimate. Spontaneous free carrier generation is the dominant process taking place directly after photoexcitation in organic-inorganic tri-halide perovskites at room temperature, which eliminates the exciton diffusion bottleneck present in organic solar cells and constitutes a major contributing factor to the high photovoltaic performance of this material. PMID:27427650

  20. Promotion of Organic Reactions by Ultrasound: Coupling of Alkyl and Aryl Halides in the Presence of Lithium Metal and Ultrasound.

    ERIC Educational Resources Information Center

    Lash, Timothy D.; Berry, Donna

    1985-01-01

    Experiments involving the coupling of alkyl and aryl halides in the presence of lithium metal and ultrasound are described. The experiments illustrate classical Wurtz and Fittig reactions in addition to being a convenient application of organic sonochemistry. (JN)

  1. Energetics and dynamics in organic-inorganic halide perovskite photovoltaics and light emitters.

    PubMed

    Sum, Tze Chien; Chen, Shi; Xing, Guichuan; Liu, Xinfeng; Wu, Bo

    2015-08-28

    The rapid transcendence of organic-inorganic metal halide perovskite solar cells to above the 20% efficiency mark has captivated the broad photovoltaic community. As the efficiency race continues unabated, it is essential that fundamental studies keep pace with these developments. Further gains in device efficiencies are expected to be increasingly arduous and harder to come by. The key to driving the perovskite solar cell efficiencies towards their Shockley-Queisser limit is through a clear understanding of the interfacial energetics and dynamics between perovskites and other functional materials in nanostructured- and heterojunction-type devices. In this review, we focus on the current progress in basic characterization studies to elucidate the interfacial energetics (energy-level alignment and band bending) and dynamical processes (from the ultrafast to the ultraslow) in organic-inorganic metal halide perovskite photovoltaics and light emitters. Major findings from these studies will be distilled. Open questions and scientific challenges will also be highlighted. PMID:26234397

  2. Energetics and dynamics in organic-inorganic halide perovskite photovoltaics and light emitters

    NASA Astrophysics Data System (ADS)

    Chien Sum, Tze; Chen, Shi; Xing, Guichuan; Liu, Xinfeng; Wu, Bo

    2015-08-01

    The rapid transcendence of organic-inorganic metal halide perovskite solar cells to above the 20% efficiency mark has captivated the broad photovoltaic community. As the efficiency race continues unabated, it is essential that fundamental studies keep pace with these developments. Further gains in device efficiencies are expected to be increasingly arduous and harder to come by. The key to driving the perovskite solar cell efficiencies towards their Shockley-Queisser limit is through a clear understanding of the interfacial energetics and dynamics between perovskites and other functional materials in nanostructured- and heterojunction-type devices. In this review, we focus on the current progress in basic characterization studies to elucidate the interfacial energetics (energy-level alignment and band bending) and dynamical processes (from the ultrafast to the ultraslow) in organic-inorganic metal halide perovskite photovoltaics and light emitters. Major findings from these studies will be distilled. Open questions and scientific challenges will also be highlighted.

  3. Trihalomethane and nonpurgeable total organic-halide formation potentials of the Mississippi river

    USGS Publications Warehouse

    Rathbun, R.E.

    1996-01-01

    Trihalomethane and nonpurgeable total organic-hallide formation potentials were determined for water samples from 12 sites along the Mississippi River from Minneapolis, MN, to New Orleans, LA, for the summer and fall of 1991 and the spring of 1992. The formation potentials increased with distance upstream, approximately paralleling the increase of the dissolved organic- carbon concentration. The pH and the dissolved organic-carbon and free- chlorine concentrations were significant variables in the prediction of the formation potentials. The trihalomethane formation potential increased as the pH increased, whereas the nonpurgeable total organic-halide formation potential decreased. All formation potentials increased as the dissolved organic-carbon and free-chlorine concentrations increased, with the dissolved organic-carbon concentration having a much greater effect.

  4. Size-Dependent Photon Emission from Organometal Halide Perovskite Nanocrystals Embedded in an Organic Matrix

    PubMed Central

    2015-01-01

    In recent years, organometal halide perovskite materials have attracted significant research interest in the field of optoelectronics. Here, we introduce a simple and low-temperature route for the formation of self-assembled perovskite nanocrystals in a solid organic matrix. We demonstrate that the size and photoluminescence peak of the perovskite nanocrystals can be tuned by varying the concentration of perovskite in the matrix material. The physical origin of the blue shift of the perovskite nanocrystals’ emission compared to its bulk phase is also discussed. PMID:25949773

  5. Inorganic UV absorbers for the photostabilisation of wood-clearcoating systems: Comparison with organic UV absorbers

    NASA Astrophysics Data System (ADS)

    Aloui, F.; Ahajji, A.; Irmouli, Y.; George, B.; Charrier, B.; Merlin, A.

    2007-02-01

    Inorganic UV absorbers which are widely used today were originally designed neither as a UV blocker in coatings applications, nor for wood protection. In recent years however, there has been extensive interest in these compounds, especially with regard to their properties as a UV blocker in coating applications. In this work, we carried out a comparative study to look into some inorganic and organic UV absorbers used in wood coating applications. The aim of this study is to determine the photostabilisation performances of each type of UV absorbers, to seek possible synergies and the influences of different wood species. We have also searched to find eventual correlation between these performances and the influence of UV absorbers on the film properties. Our study has compared the performances of the following UV absorbers: hombitec RM 300, hombitec RM 400 from the Sachtleben Company; transparent yellow and red iron oxides from Sayerlack as inorganic UV absorbers; organic UV absorbers Tinuvin 1130 and Tinuvin 5151 from Ciba Company. The study was carried out on three wood species: Abies grandis, tauari and European oak. The environmental constraints (in particular the limitation of the emission of volatile organic compounds VOCs) directed our choice towards aqueous formulations marketed by the Sayerlack Arch Coatings Company. The results obtained after 800 h of dry ageing showed that the Tinuvins and the hombitecs present better wood photostabilisations. On the other hand in wet ageing, with the hombitec, there are appearances of some cracks and an increase in the roughness of the surface. This phenomenon is absent when the Tinuvins are used. With regard to these results, the thermomechanical analyses relating to the follow-up of the change of the glass transition temperature ( Tg) of the various coating systems, show a different behaviour between the two types of absorbers. However, contrary to organic UV absorbers, inorganic ones tend to increase Tg during ageing

  6. Inferring Absorbing Organic Carbon Content from AERONET Data

    NASA Technical Reports Server (NTRS)

    Arola, A.; Schuster, G.; Myhre, G.; Kazadzis, S.; Dey, S.; Tripathi, S. N.

    2011-01-01

    Black carbon, light-absorbing organic carbon (often called brown carbon) and mineral dust are the major light-absorbing aerosols. Currently the sources and formation of brown carbon aerosol in particular are not well understood. In this study we estimated globally the amount of light absorbing organic carbon and black carbon from AERONET measurements. We find that the columnar absorbing organic carbon (brown carbon) levels in biomass burning regions of South-America and Africa are relatively high (about 15-20 magnesium per square meters during biomass burning season), while the concentrations are significantly lower in urban areas in US and Europe. However, we estimated significant absorbing organic carbon amounts from the data of megacities of newly industrialized countries, particularly in India and China, showing also clear seasonality with peak values up to 30-35 magnesium per square meters during the coldest season, likely caused by the coal and biofuel burning used for heating. We also compared our retrievals with the modeled organic carbon by global Oslo CTM for several sites. Model values are higher in biomass burning regions than AERONET-based retrievals, while opposite is true in urban areas in India and China.

  7. Organic-inorganic interactions of single crystalline organolead halide perovskites studied by Raman spectroscopy.

    PubMed

    Xie, Li-Qiang; Zhang, Tai-Yang; Chen, Liang; Guo, Nanjie; Wang, Yu; Liu, Guo-Kun; Wang, Jia-Rui; Zhou, Jian-Zhang; Yan, Jia-Wei; Zhao, Yi-Xin; Mao, Bing-Wei; Tian, Zhong-Qun

    2016-07-21

    Organolead halide perovskites exhibit superior photoelectric properties, which have given rise to the perovskite-based solar cells whose power conversion efficiency has rapidly reached above 20% in the past few years. However, perovskite-based solar cells have also encountered problems such as current-voltage hysteresis and degradation under practical working conditions. Yet investigations into the intrinsic chemical nature of the perovskite material and its role on the performance of the solar cells are relatively rare. In this work, Raman spectroscopy is employed together with CASTEP calculations to investigate the organic-inorganic interactions in CH3NH3PbI3 and CH3NH3PbBr3-xClx perovskite single crystals with comparison to those having ammonic acid as the cations. For Raman measurements of CH3NH3PbI3, a low energy line of 1030 nm is used to avoid excitation of strong photoluminescence of CH3NH3PbI3. Raman spectra covering a wide range of wavenumbers are obtained, and the restricted rotation modes of CH3-NH3(+) embedded in CH3NH3PbBr3 (325 cm(-1)) are overwhelmingly stronger over the other vibrational bands of the cations. However, the band intensity diminishes dramatically in CH3NH3PbBr3-xClx and most of the bands shift towards high frequency, indicating the interaction with the halides. The details of such an interaction are further revealed by inspecting the band shift of the restricted rotation mode as well as the C-N, NH3(+) and CH3 stretching of the CH3NH3(+) as a function of Cl composition and length of the cationic ammonic acids. The results show that the CH3NH3(+) interacts with the PbX3(-) octahedral framework via the NH3(+) end through N(+)-HX hydrogen bonding whose strength can be tuned by the composition of halides but is insensitive to the size of the organic cations. Moreover, an increase of the Cl content strengthens the hydrogen bonding and thus blueshifts the C-N stretching bands. This is due to the fact that Cl is more electronegative than Br

  8. Regiodivergent Cross-Dehydrogenative Coupling of Pyridines and Benzoxazoles: Discovery of Organic Halides as Regio-Switching Oxidants.

    PubMed

    Yamada, Shuya; Murakami, Kei; Itami, Kenichiro

    2016-05-20

    Cross-dehydrogenative coupling (CDC) of two unfunctionalized heteroarenes has been recognized as an ideal transformation to synthesize privileged heterobiaryl scaffolds. However, regioselective activation and transformation of a specific set of two heterocyclic C-H bonds among other bonds have been extremely challenging. Thus, discovering a new controlling element to achieve regio-controlled and regio-divergent heterocyclic CDCs is considered crucial. In this Letter, the unprecedented use of organic halides as an oxidant to achieve the CDC reaction of pyridines and benzoxazoles with palladium catalyst is described. Moreover, the regioselectivity of the pyridine functionalization site can be controlled by the choice of organic halides. PMID:27162109

  9. A First-Principles Study on the Structural and Electronic Properties of Sn-Based Organic-Inorganic Halide Perovskites

    NASA Astrophysics Data System (ADS)

    Ma, Zi-Qian; Pan, Hui; Wong, Pak Kin

    2016-08-01

    Organic-inorganic halide perovskites have attracted increasing interest on solar-energy harvesting because of their outstanding electronic properties. In this work, we systematically investigate the structural and electronic properties of Sn-based hybrid perovskites MASnX3 and FASnX3 (X = I, Br) based on density-functional-theory calculations. We find that their electronic properties strongly depend on the organic molecules, halide atoms, and structures. We show that there is a general rule to predict the band gap of the Sn-based hybrid perovskite: its band gap increases as the size of halide atom decreases as well as that of organic molecule increase. The band gap of high temperature phase (cubic structure) is smaller than that of low temperature phase (orthorhombic structure). The band gap of tetragonal structure (medium-temperature phase) may be larger or smaller than that of cubic phase, depending on the orientation of the molecule. Tunable band gap within a range of 0.73-1.53 eV can be achieved by choosing halide atom and organic molecule, and controlling structure. We further show that carrier effective mass also reduces as the size of halide atom increases and that of molecule decreases. By comparing with Pb-based hybrid perovskites, the Sn-based systems show enhanced visible-light absorption and carrier mobility due to narrowed band gap and reduced carrier effective mass. These Sn-based organic-inorganic halide perovskites may find applications in solar energy harvesting with improved performance.

  10. Photo-induced halide redistribution in organic-inorganic perovskite films

    NASA Astrophysics Data System (ADS)

    Dequilettes, Dane W.; Zhang, Wei; Burlakov, Victor M.; Graham, Daniel J.; Leijtens, Tomas; Osherov, Anna; Bulović, Vladimir; Snaith, Henry J.; Ginger, David S.; Stranks, Samuel D.

    2016-05-01

    Organic-inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced `brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. Our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance.

  11. Photo-induced halide redistribution in organic-inorganic perovskite films.

    PubMed

    deQuilettes, Dane W; Zhang, Wei; Burlakov, Victor M; Graham, Daniel J; Leijtens, Tomas; Osherov, Anna; Bulović, Vladimir; Snaith, Henry J; Ginger, David S; Stranks, Samuel D

    2016-01-01

    Organic-inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced 'brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. Our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance. PMID:27216703

  12. Hydrophobic Organic Hole Transporters for Improved Moisture Resistance in Metal Halide Perovskite Solar Cells.

    PubMed

    Leijtens, Tomas; Giovenzana, Tommaso; Habisreutinger, Severin N; Tinkham, Jonathan S; Noel, Nakita K; Kamino, Brett A; Sadoughi, Golnaz; Sellinger, Alan; Snaith, Henry J

    2016-03-01

    Solar cells based on organic-inorganic perovskite semiconductor materials have recently made rapid improvements in performance, with the best cells performing at over 20% efficiency. With such rapid progress, questions such as cost and solar cell stability are becoming increasingly important to address if this new technology is to reach commercial deployment. The moisture sensitivity of commonly used organic-inorganic metal halide perovskites has especially raised concerns. Here, we demonstrate that the hygroscopic lithium salt commonly used as a dopant for the hole transport material in perovskite solar cells makes the top layer of the devices hydrophilic and causes the solar cells to rapidly degrade in the presence of moisture. By using novel, low cost, and hydrophobic hole transporters in conjunction with a doping method incorporating a preoxidized salt of the respective hole transporters, we are able to prepare efficient perovskite solar cells with greatly enhanced water resistance. PMID:26859777

  13. Fluorescence spectroscopy: considerations for highly absorbing dissolved organic matter samples

    NASA Astrophysics Data System (ADS)

    Simone, B. E.; Miller, M.; McKnight, D. M.

    2009-12-01

    Fluorescence spectroscopy is a robust method for characterizing organic matter (OM). However, proper collection and correction of spectra are necessary to provide useful data. One important correction is the inner-filter correction, which primarily accounts for the inner-filter effect by adjusting for the wavelength dependent attenuation of emitted light by the solution prior to detection by the fluorometer. The most commonly used correction is based on an assumption that light is emitted at the center of the pathlength. Thus, the inner-filter effect is more pronounced in highly absorbing samples, and has the potential to skew the fluorescence spectra. For this study, the terrestrially derived Suwannee River fulvic acid (SRFA) and microbially derived Pony Lake fulvic acid (PLFA), from the International Humic Substances Society (IHSS), were diluted to incremental absorbances at a wavelength of 254 nm from 0.05 to 1.0 at pH 4 and 7. Three dimensional fluorescence spectra were measured and modeled with the Cory and McKnight (2005) parallel factor analysis (PARAFAC) model which resolves the fluorescence spectra into 13 components, including quinone-like and protein-like components. In the absence of inner-filter effects, plots of absorbance vs. loadings should be linear. Using the data from absorbance of 0.05 to 0.3, where the inner-filter affect is least pronounced, a linear regression was created and used as a baseline to predict component loadings at higher absorbance values in the absence of inner-filter effects. Results indicate that at absorbance values greater than 0.3, the commonly-used inner-filter correction is not able to remove the inner-filter effect. Therefore, in order to obtain reliable component loadings and correctly interpret the spectra, samples should be diluted to absorbance values less than 0.3 at 254 nm prior to collection of three dimensional fluorescence scans. The recommendation of a maximum absorbance of 0.3 agrees with the results of a

  14. Click chemistry from organic halides, diazonium salts and anilines in water catalysed by copper nanoparticles on activated carbon.

    PubMed

    Alonso, Francisco; Moglie, Yanina; Radivoy, Gabriel; Yus, Miguel

    2011-09-21

    An easy-to-prepare, reusable and versatile catalyst consisting of oxidised copper nanoparticles on activated carbon has been fully characterised and found to effectively promote the multicomponent synthesis of 1,2,3-triazoles from organic halides, diazonium salts, and aromatic amines in water at a low copper loading. PMID:21789331

  15. Integrated Photoelectrolysis of Water Implemented On Organic Metal Halide Perovskite Photoelectrode.

    PubMed

    Hoang, Minh Tam; Pham, Ngoc Duy; Han, Ji Hun; Gardner, James M; Oh, Ilwhan

    2016-05-18

    Herein we report on integrated photoelectrolysis of water employing organic metal halide (OMH) perovskite material. Generic OMH perovskite material and device architecture are highly susceptible to degradation by moisture and water. We found that decomposition of perovskite devices proceeds by water ingress through pinholes in upper layers and is strongly affected by applied bias/light and electrolyte pH. It was also found that a pinhole-free hole transport layer (HTL) could significantly enhance the stability of the perovskite photoelectrode, thereby extending the photoelectrode lifetime to several tens of minutes, which is an unprecedented record-long operation. Furthermore, a carbon nanotube (CNT)/polymer composite layer was developed that can effectively protect the underlying perovskite layer from electrolyte molecules. PMID:27120406

  16. Iron-catalysed cross-coupling of organolithium compounds with organic halides

    PubMed Central

    Jia, Zhenhua; Liu, Qiang; Peng, Xiao-Shui; Wong, Henry N. C.

    2016-01-01

    In past decades, catalytic cross-coupling reactions between organic halides and organometallic reagents to construct carbon–carbon bond have achieved a tremendous progress. However, organolithium reagents have rarely been used in cross-coupling reactions, due mainly to their high reactivity. Another limitation of this transformation using organolithium reagents is how to control reactivity with excellent selectivity. Although palladium catalysis has been applied in this field recently, the development of an approach to replace catalytic systems of noble metals with nonprecious metals is currently in high demand. Herein, we report an efficient synthetic protocol involving iron-catalysed cross-coupling reactions employing organolithium compounds as key coupling partners to unite aryl, alkyl and benzyl fragments and also disclose an efficient iron-catalysed release-capture ethylene coupling with isopropyllithium. PMID:26847602

  17. DFT +U Modeling of Hole Polarons in Organic Lead Halide Perovskites

    NASA Astrophysics Data System (ADS)

    Welch, Eric; Erhart, Paul; Scolfaro, Luisa; Zakhidov, Alex

    Due to the ever present drive towards improved efficiencies in solar cell technology, new and improved materials are emerging rapidly. Organic halide perovskites are a promising prospect, yet a fundamental understanding of the organic perovskite structure and electronic properties is missing. Particularly, explanations of certain physical phenomena, specifically a low recombination rate and high mobility of charge carriers still remain controversial. We theoretically investigate possible formation of hole polarons adopting methodology used for oxide perovskites. The perovskite studied here is the ABX3structure, with A being an organic cation, B lead and C a halogen; the combinations studied allow for A1,xA2 , 1 - xBX1,xX2 , 3 - xwhere the alloy convention is used to show mixtures of the organic cations and/or the halogens. Two organic cations, methylammonium and formamidinium, and three halogens, iodine, chlorine and bromine are studied. Electronic structures and polaron behavior is studied through first principle density functional theory (DFT) calculations using the Vienna Ab Initio Simulation Package (VASP). Local density approximation (LDA) pseudopotentials are used and a +U Hubbard correction of 8 eV is added; this method was shown to work with oxide perovskites. It is shown that a localized state is realized with the Hubbard correction in systems with an electron removed, residing in the band gap of each different structure. Thus, hole polarons are expected to be seen in these perovskites.

  18. Impact of the organic halide salt on final perovskite composition for photovoltaic applications

    SciTech Connect

    Moore, David T.; Sai, Hiroaki; Wee Tan, Kwan; Estroff, Lara A.; Wiesner, Ulrich

    2014-08-01

    The methylammonium lead halide perovskites have shown significant promise as a low-cost, second generation, photovoltaic material. Despite recent advances, however, there are still a number of fundamental aspects of their formation as well as their physical and electronic behavior that are not well understood. In this letter we explore the mechanism by which these materials crystallize by testing the outcome of each of the reagent halide salts. We find that components of both salts, lead halide and methylammonium halide, are relatively mobile and can be readily exchanged during the crystallization process when the reaction is carried out in solution or in the solid state. We exploit this fact by showing that the perovskite structure is formed even when the lead salt's anion is a non-halide, leading to lower annealing temperature and time requirements for film formation. Studies into these behaviors may ultimately lead to improved processing conditions for photovoltaic films.

  19. Silver-halide/organic-composite structures: Toward materials with multiple photographic functionalities

    SciTech Connect

    Bringley, Joseph F. . E-mail: joseph.bringley@kodak.com; Rajeswaran, Manju; Olson, Leif P.; Liebert, Nancy M.

    2005-10-15

    We report the synthesis and structure of the novel silver-halide-based organic-inorganic hybrids Ag{sub 2}Br{sub 6}(PPD){sub 2}, Ag{sub 2}Br{sub 6}(CD-2){sub 2}.H{sub 2}O, Ag{sub 2}Br{sub 4}(TMBD), and Ag{sub 2}I{sub 6}(CD-2){sub 2}.H{sub 2}O. 1,4-phenylenediammonium hexabromodiargentate(I) [Ag{sub 2}Br{sub 6}(PPD){sub 2}] crystals are monoclinic (P2{sub 1}/n), with unit-cell dimensions, a=10.1915(3)A, b=7.7562(2)A, c=12.4340(5)A and {beta}=93.109(1){sup o}. N,N-diethyl-2-methyl-1,4-benzenediammonium hexabromodiargentate(I) monohydrate [Ag{sub 2}Br{sub 6}(CD-2){sub 2}.H{sub 2}O] crystals are monoclinic (space group P2{sub 1}/c) with a=10.8434(2)A, b=11.4293(2)A, c=14.3729(1)A, and {beta}=96.153(1){sup o}. N,N,N',N'-tetramethyl-1,4-benzenediammonium tetrabromodiargentate(I) [Ag{sub 2}Br{sub 4}(TMBD)] crystals are orthorhombic (space group Pbcn) with a=17.0030(6)A, b=6.6163(2)A, and c=15.9762(6)A. N,N-diethyl-2-methyl-1,4-benzenediammonium hexaiododiargentate(I) monohydrate, [Ag{sub 2}I{sub 6}(CD-2){sub 2}.H{sub 2}O], are monoclinic (C2/c), with unit-cell dimensions, a=21.4691(4)A, b=12.1411(2)A, c=14.3102(2)A, and {beta}=98.657(1){sup o}. The novel structures are members of a class of silver-halide-based organic-inorganic hybrids based upon the assembly of [Ag{sub a}X{sub b}]{sup n-} clusters and protonated organoamines in aqueous mineral acids. The clusters display short intracluster Ag-Ag distances, and computational methods are used to evaluate intracluster Ag-Ag bonding. The diverse stoichiometries and cluster connectivities observed suggest a rich compositional and structural chemistry based upon the general assembly method. We have extended the methodology to include a silver-halide-organoamonium chemistry in which the organic moiety is chosen to serve a specific photographic function and demonstrate the first examples of such materials. The methodology allows for the direct assembly of [Ag{sub a}X{sub b}]{sup n-} clusters with commercial photographic color

  20. Organic-inorganic hybrid lead halide perovskites for optoelectronic and electronic applications.

    PubMed

    Zhao, Yixin; Zhu, Kai

    2016-02-01

    Organic and inorganic hybrid perovskites (e.g., CH(3)NH(3)PbI(3)), with advantages of facile processing, tunable bandgaps, and superior charge-transfer properties, have emerged as a new class of revolutionary optoelectronic semiconductors promising for various applications. Perovskite solar cells constructed with a variety of configurations have demonstrated unprecedented progress in efficiency, reaching about 20% from multiple groups after only several years of active research. A key to this success is the development of various solution-synthesis and film-deposition techniques for controlling the morphology and composition of hybrid perovskites. The rapid progress in material synthesis and device fabrication has also promoted the development of other optoelectronic applications including light-emitting diodes, photodetectors, and transistors. Both experimental and theoretical investigations on organic-inorganic hybrid perovskites have enabled some critical fundamental understandings of this material system. Recent studies have also demonstrated progress in addressing the potential stability issue, which has been identified as a main challenge for future research on halide perovskites. Here, we review recent progress on hybrid perovskites including basic chemical and crystal structures, chemical synthesis of bulk/nanocrystals and thin films with their chemical and physical properties, device configurations, operation principles for various optoelectronic applications (with a focus on solar cells), and photophysics of charge-carrier dynamics. We also discuss the importance of further understanding of the fundamental properties of hybrid perovskites, especially those related to chemical and structural stabilities. PMID:26645733

  1. Optical tomograph optimized for tumor detection inside highly absorbent organs

    NASA Astrophysics Data System (ADS)

    Boutet, Jérôme; Koenig, Anne; Hervé, Lionel; Berger, Michel; Dinten, Jean-Marc; Josserand, Véronique; Coll, Jean-Luc

    2011-05-01

    This paper presents a tomograph for small animal fluorescence imaging. The compact and cost-effective system described in this article was designed to address the problem of tumor detection inside highly absorbent heterogeneous organs, such as lungs. To validate the tomograph's ability to detect cancerous nodules inside lungs, in vivo tumor growth was studied on seven cancerous mice bearing murine mammary tumors marked with Alexa Fluor 700. They were successively imaged 10, 12, and 14 days after the primary tumor implantation. The fluorescence maps were compared over this time period. As expected, the reconstructed fluorescence increases with the tumor growth stage.

  2. Porphyrin Based Near Infrared-Absorbing Materials for Organic Photovoltaics

    NASA Astrophysics Data System (ADS)

    Zhong, Qiwen

    The conservation and transformation of energy is essential to the survival of mankind, and thus concerns every modern society. Solar energy, as an everlasting source of energy, holds one of the key solutions to some of the most urgent problems the world now faces, such as global warming and the oil crisis. Advances in technologies utilizing clean, abundant solar energy, could be the steering wheel of our societies. Solar cells, one of the major advances in converting solar energy into electricity, are now capturing people's interest all over the globe. While solar cells have been commercially available for many years, the manufacturing of solar cells is quite expensive, limiting their broad based implementation. The cost of solar cell based electricity is 15-50 cents per kilowatt hour (¢/kwh), depending on the type of solar cell, compared to 0.7 ¢/kwh for fossil fuel based electricity. Clearly, decreasing the cost of electricity from solar cells is critical for their wide spread deployment. This will require a decrease in the cost of light absorbing materials and material processing used in fabricating the cells. Organic photovoltaics (OPVs) utilize organic materials such as polymers and small molecules. These devices have the advantage of being flexible and lower cost than conventional solar cells built from inorganic semiconductors (e.g. silicon). The low cost of OPVs is tied to lower materials and fabrication costs of organic cells. However, the current power conversion efficiencies of OPVs are still below 15%, while convention crystalline Si cells have efficiencies of 20-25%. A key limitation in OPVs today is their inability to utilize the near infrared (NIR) portion of the solar spectrum. This part of the spectrum comprises nearly half of the energy in sunlight that could be used to make electricity. The first and foremost step in conversion solar energy conversion is the absorption of light, which nature has provided us optimal model of, which is

  3. Charge-Carrier Dynamics in Organic-Inorganic Metal Halide Perovskites.

    PubMed

    Herz, Laura M

    2016-05-27

    Hybrid organic-inorganic metal halide perovskites have recently emerged as exciting new light-harvesting and charge-transporting materials for efficient photovoltaic devices. Yet knowledge of the nature of the photogenerated excitations and their subsequent dynamics is only just emerging. This article reviews the current state of the field, focusing first on a description of the crystal and electronic band structure that give rise to the strong optical transitions that enable light harvesting. An overview is presented of the numerous experimental approaches toward determining values for exciton binding energies, which appear to be small (a few milli-electron volts to a few tens of milli-electron volts) and depend significantly on temperature because of associated changes in the dielectric function. Experimental evidence for charge-carrier relaxation dynamics within the first few picoseconds after excitation is discussed in terms of thermalization, cooling, and many-body effects. Charge-carrier recombination mechanisms are reviewed, encompassing trap-assisted nonradiative recombination that is highly specific to processing conditions, radiative bimolecular (electron-hole) recombination, and nonradiative many-body (Auger) mechanisms. PMID:26980309

  4. Ultrafast time-resolved spectroscopy of lead halide perovskite films

    NASA Astrophysics Data System (ADS)

    Idowu, Mopelola A.; Yau, Sung H.; Varnavski, Oleg; Goodson, Theodore

    2015-09-01

    Recently, lead halide perovskites which are organic-inorganic hybrid structures, have been discovered to be highly efficient as light absorbers. Herein, we show the investigation of the excited state dynamics and emission properties of non-stoichiometric precursor formed lead halide perovskites grown by interdiffusion method using steady-state and time-resolved spectroscopic measurements. The influence of the different ratios of the non-stoichiometric precursor solution was examined. The observed photoluminescence properties were correlated with the femtosecond transient absorption measurements.

  5. Photochemical aging of light-absorbing secondary organic aerosol material.

    PubMed

    Sareen, Neha; Moussa, Samar G; McNeill, V Faye

    2013-04-11

    Dark reactions of methylglyoxal with NH4(+) in aqueous aerosols yield light-absorbing and surface-active products that can influence the physical properties of the particles. Little is known about how the product mixture and its optical properties will change due to photolysis as well as oxidative aging by O3 and OH in the atmosphere. Here, we report the results of kinetics and product studies of the photochemical aging of aerosols formed by atomizing aqueous solutions of methylglyoxal and ammonium sulfate. Experiments were performed using aerosol flow tube reactors coupled with an aerosol chemical ionization mass spectrometer (Aerosol-CIMS) for monitoring gas- and particle-phase compositions. Particles were also impacted onto quartz windows in order to assess changes in their UV-visible absorption upon oxidation. Photooxidation of the aerosols leads to the formation of small, volatile organic acids including formic acid, acetic acid, and glyoxylic acid. The atmospheric lifetime of these species during the daytime is predicted to be on the order of minutes, with photolysis being an important mechanism of degradation. The lifetime with respect to O3 oxidation was observed to be on the order of hours. O3 oxidation also leads to a net increase in light absorption by the particles due to the formation of additional carbonyl compounds. Our results are consistent with field observations of high brown carbon absorption in the early morning. PMID:23506538

  6. Methylammonium Bismuth Iodide as a Lead-Free, Stable Hybrid Organic-Inorganic Solar Absorber.

    PubMed

    Hoye, Robert L Z; Brandt, Riley E; Osherov, Anna; Stevanović, Vladan; Stranks, Samuel D; Wilson, Mark W B; Kim, Hyunho; Akey, Austin J; Perkins, John D; Kurchin, Rachel C; Poindexter, Jeremy R; Wang, Evelyn N; Bawendi, Moungi G; Bulović, Vladimir; Buonassisi, Tonio

    2016-02-18

    Methylammonium lead halide (MAPbX3 ) perovskites exhibit exceptional carrier transport properties. But their commercial deployment as solar absorbers is currently limited by their intrinsic instability in the presence of humidity and their lead content. Guided by our theoretical predictions, we explored the potential of methylammonium bismuth iodide (MBI) as a solar absorber through detailed materials characterization. We synthesized phase-pure MBI by solution and vapor processing. In contrast to MAPbX3, MBI is air stable, forming a surface layer that does not increase the recombination rate. We found that MBI luminesces at room temperature, with the vapor-processed films exhibiting superior photoluminescence (PL) decay times that are promising for photovoltaic applications. The thermodynamic, electronic, and structural features of MBI that are amenable to these properties are also present in other hybrid ternary bismuth halide compounds. Through MBI, we demonstrate a lead-free and stable alternative to MAPbX3 that has a similar electronic structure and nanosecond lifetimes. PMID:26866821

  7. Charge carrier recombination channels in the low-temperature phase of organic-inorganic lead halide perovskite thin films

    NASA Astrophysics Data System (ADS)

    Wehrenfennig, Christian; Liu, Mingzhen; Snaith, Henry J.; Johnston, Michael B.; Herz, Laura M.

    2014-08-01

    The optoelectronic properties of the mixed hybrid lead halide perovskite CH3NH3PbI3-xClx have been subject to numerous recent studies related to its extraordinary capabilities as an absorber material in thin film solar cells. While the greatest part of the current research concentrates on the behavior of the perovskite at room temperature, the observed influence of phonon-coupling and excitonic effects on charge carrier dynamics suggests that low-temperature phenomena can give valuable additional insights into the underlying physics. Here, we present a temperature-dependent study of optical absorption and photoluminescence (PL) emission of vapor-deposited CH3NH3PbI3-xClx exploring the nature of recombination channels in the room- and the low-temperature phase of the material. On cooling, we identify an up-shift of the absorption onset by about 0.1 eV at about 100 K, which is likely to correspond to the known tetragonal-to-orthorhombic transition of the pure halide CH3NH3PbI3. With further decreasing temperature, a second PL emission peak emerges in addition to the peak from the room-temperature phase. The transition on heating is found to occur at about 140 K, i.e., revealing significant hysteresis in the system. While PL decay lifetimes are found to be independent of temperature above the transition, significantly accelerated recombination is observed in the low-temperature phase. Our data suggest that small inclusions of domains adopting the room-temperature phase are responsible for this behavior rather than a spontaneous increase in the intrinsic rate constants. These observations show that even sparse lower-energy sites can have a strong impact on material performance, acting as charge recombination centres that may detrimentally affect photovoltaic performance but that may also prove useful for optoelectronic applications such as lasing by enhancing population inversion.

  8. Radiochemical synthesis of pure anhydrous metal halides

    NASA Technical Reports Server (NTRS)

    Philipp, W. H.; Marsik, S. J.; May, C. E.

    1973-01-01

    Method uses radiation chemistry as practical tool for inorganic preparations and in particular deposition of metals by irradiation of their aqueous metal salt solutions with high energy electrons. Higher valence metal halide is dissolved in organic liquid and exposed to high energy electrons. This causes metal halide to be reduced to a lower valence metal halide.

  9. Is There a Need to Discuss Atomic Orbital Overlap When Teaching Hydrogen-Halide Bond Strength and Acidity Trends in Organic Chemistry?

    ERIC Educational Resources Information Center

    Devarajan, Deepa; Gustafson, Samantha J.; Bickelhaupt, F. Matthias; Ess, Daniel H.

    2015-01-01

    Undergraduate organic chemistry textbooks and Internet websites use a variety of approaches for presenting and explaining the impact of halogen atom size on trends in bond strengths and/or acidity of hydrogen halides. In particular, several textbooks and Internet websites explain these trends by invoking decreasing orbital overlap between the…

  10. Removal of hexenuronic acid by xylanase to reduce adsorbable organic halides formation in chlorine dioxide bleaching of bagasse pulp.

    PubMed

    Nie, Shuangxi; Wang, Shuangfei; Qin, Chengrong; Yao, Shuangquan; Ebonka, Johnbull Friday; Song, Xueping; Li, Kecheng

    2015-11-01

    Xylanase-aided chlorine dioxide bleaching of bagasse pulp was investigated. The pulp was pretreated with xylanase and followed a chlorine dioxide bleaching stage. The ATR-FTIR and XPS were employed to determine the surface chemistry of the control pulp, xylanase treated and chlorine dioxide treated pulps. The hexenuronic acid (HexA) could obviously be reduced after xylanase pretreatment, and the adsorbable organic halides (AOX) were reduced after chlorine dioxide bleaching. Compared to the control pulp, AOX could be reduced by 21.4-26.6% with xylanase treatment. Chlorine dioxide demand could be reduced by 12.5-22% to achieve the same brightness. The ATR-FTIR and XPS results showed that lignin and hemicellulose (mainly HexA) were the main source for AOX formation. Xylanase pretreatment could remove HexA and expose more lignin, which decreased the chlorine dioxide demand and thus reduced formation of AOX. PMID:26263004

  11. The interaction between hybrid organic-inorganic halide perovskite and selective contacts in perovskite solar cells: an infrared spectroscopy study.

    PubMed

    Idígoras, J; Todinova, A; Sánchez-Valencia, J R; Barranco, A; Borrás, A; Anta, J A

    2016-05-11

    The interaction of hybrid organic-inorganic halide perovskite and selective contacts is crucial to get efficient, stable and hysteresis-free perovskite-based solar cells. In this report, we analyze the vibrational properties of methylammonium lead halide perovskites deposited on different substrates by infrared absorption (IR) measurements (4000-500 cm(-1)). The materials employed as substrates are not only characterized by different chemical natures (TiO2, ZnO and Al2O3), but also by different morphologies. For all of them, we have investigated the influence of these substrate properties on perovskite formation and its degradation by humidity. The effect of selective-hole contact (Spiro-OmeTad and P3HT) layers on the degradation rate by moisture has also been studied. Our IR results reveal the existence of a strong interaction between perovskite and all ZnO materials considered, evidenced by a shift of the peaks related to the N-H vibrational modes. The interaction even induces a morphological change in ZnO nanoparticles after perovskite deposition, pointing to an acid-base reaction that takes place through the NH3(+) groups of the methylammonium cation. Our IR and X-ray diffraction results also indicate that this specific interaction favors perovskite decomposition and PbI2 formation for ZnO/perovskite films subjected to humid conditions. Although no interaction is observed for TiO2, Al2O3, and the hole selective contact, the morphology and chemical nature of both contacts appear to play an important role in the rate of degradation upon exposure to moisture. PMID:27138224

  12. Hot-carrier cooling and photoinduced refractive index changes in organic-inorganic lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Price, Michael B.; Butkus, Justinas; Jellicoe, Tom C.; Sadhanala, Aditya; Briane, Anouk; Halpert, Jonathan E.; Broch, Katharina; Hodgkiss, Justin M.; Friend, Richard H.; Deschler, Felix

    2015-09-01

    Metal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ~1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a `phonon bottleneck' substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon-impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance.

  13. Hot-carrier cooling and photoinduced refractive index changes in organic-inorganic lead halide perovskites.

    PubMed

    Price, Michael B; Butkus, Justinas; Jellicoe, Tom C; Sadhanala, Aditya; Briane, Anouk; Halpert, Jonathan E; Broch, Katharina; Hodgkiss, Justin M; Friend, Richard H; Deschler, Felix

    2015-01-01

    Metal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ∼ 1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a 'phonon bottleneck' substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon-impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance. PMID:26404048

  14. Detection of Organic Compounds in Water by an Optical Absorbance Method

    PubMed Central

    Kim, Chihoon; Eom, Joo Beom; Jung, Soyoun; Ji, Taeksoo

    2016-01-01

    This paper proposes an optical method which allows determination of the organic compound concentration in water by measurement of the UV (ultraviolet) absorption at a wavelength of 250 nm~300 nm. The UV absorbance was analyzed by means of a multiple linear regression model for estimation of the total organic carbon contents in water, which showed a close correlation with the UV absorbance, demonstrating a high adjusted coefficient of determination, 0.997. The comparison of the TOC (total organic carbon) concentrations for real samples (tab water, sea, and river) calculated from the UV absorbance spectra, and those measured by a conventional TOC analyzer indicates that the higher the TOC value the better the agreement. This UV absorbance method can be easily configured for real-time monitoring water pollution, and built into a compact system applicable to industry areas. PMID:26742043

  15. Detection of Organic Compounds in Water by an Optical Absorbance Method.

    PubMed

    Kim, Chihoon; Eom, Joo Beom; Jung, Soyoun; Ji, Taeksoo

    2016-01-01

    This paper proposes an optical method which allows determination of the organic compound concentration in water by measurement of the UV (ultraviolet) absorption at a wavelength of 250 nm~300 nm. The UV absorbance was analyzed by means of a multiple linear regression model for estimation of the total organic carbon contents in water, which showed a close correlation with the UV absorbance, demonstrating a high adjusted coefficient of determination, 0.997. The comparison of the TOC (total organic carbon) concentrations for real samples (tab water, sea, and river) calculated from the UV absorbance spectra, and those measured by a conventional TOC analyzer indicates that the higher the TOC value the better the agreement. This UV absorbance method can be easily configured for real-time monitoring water pollution, and built into a compact system applicable to industry areas. PMID:26742043

  16. Quantum confinement and dielectric profiles of colloidal nanoplatelets of halide inorganic and hybrid organic-inorganic perovskites.

    PubMed

    Sapori, Daniel; Kepenekian, Mikaël; Pedesseau, Laurent; Katan, Claudine; Even, Jacky

    2016-03-28

    Quantum confinement as well as high frequency ε∞ and static εs dielectric profiles are described for nanoplatelets of halide inorganic perovskites CsPbX3 (X = I, Br, Cl) and hybrid organic-inorganic perovskites (HOP) in two-dimensional (2D) and three-dimensional (3D) structures. 3D HOP are currently being sought for their impressive photovoltaic ability. Prior to this sudden popularity, 2D HOP materials were driving intense activity in the field of optoelectronics. Such developments have been enriched by the recent ability to synthesize colloidal nanostructures of controlled sizes of 2D and 3D HOP. This raises the need to achieve a thorough description of the electronic structure and dielectric properties of these systems. In this work, we go beyond the abrupt dielectric interface model and reach the atomic scale description. We examine the influence of the nature of the halogen and of the cation on the band structure and dielectric constants. Similarly, we survey the effect of dimensionality and shape of the perovskite. In agreement with recent experimental results, we show an increase of the band gap and a decrease of ε∞ when the size of a nanoplatelet reduces. By inspecting 2D HOP, we find that it cannot be described as a simple superposition of independent inorganic and organic layers. Finally, the dramatic impact of ionic contributions on the dielectric constant εs is analysed. PMID:26705549

  17. Revealing the role of organic cations in hybrid halide perovskite CH3NH3PbI3

    PubMed Central

    Motta, Carlo; El-Mellouhi, Fedwa; Kais, Sabre; Tabet, Nouar; Alharbi, Fahhad; Sanvito, Stefano

    2015-01-01

    The hybrid halide perovskite CH3NH3PbI3 has enabled solar cells to reach an efficiency of about 20%, demonstrating a pace for improvements with no precedents in the solar energy arena. Despite such explosive progress, the microscopic origin behind the success of such material is still debated, with the role played by the organic cations in the light-harvesting process remaining unclear. Here van der Waals-corrected density functional theory calculations reveal that the orientation of the organic molecules plays a fundamental role in determining the material electronic properties. For instance, if CH3NH3 orients along a (011)-like direction, the PbI6 octahedral cage will distort and the bandgap will become indirect. Our results suggest that molecular rotations, with the consequent dynamical change of the band structure, might be at the origin of the slow carrier recombination and the superior conversion efficiency of CH3NH3PbI3. PMID:25912782

  18. Effect of cuprous halide interlayers on the device performance of ZnPc/C{sub 60} organic solar cells

    SciTech Connect

    Lee, Jinho; Park, Dasom; Heo, Ilsu; Yim, Sanggyu

    2014-10-15

    Highlights: • Effect of CuX interlayers on subsequently deposited films and devices was studied. • CuI is the most effective for the performance of ZnPc/C{sub 60}-based solar cells. • Results were related to the molecular geometry of ZnPc and HOMO level of interlayers. - Abstract: The effect of various cuprous halide (CuX) interlayers introduced between a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) layer and zinc phthalocyanine (ZnPc) layer on the physical properties of the ZnPc thin films and device performances of ZnPc/C{sub 60}-based small-molecule organic solar cells was studied. Strong substrate–molecule interaction between the CuX and ZnPc partly converted surface-perpendicular stacking geometry of ZnPc molecules into surface-parallel one. This flat-lying geometry led to an enhancement in electronic absorption and charge transport within the ZnPc films. As a result, the overall power conversion efficiency of the cell with CuI interlayer increased by ∼37%. In the case of the cells with CuBr and CuCl interlayer, however, the enhancement in device performances was limited because of the reduced conversion of the molecular geometry and increased energy barrier for hole extraction due to the low highest occupied molecular orbital level of the interlayer.

  19. Why are organotin hydride reductions of organic halides so frequently retarded? Kinetic studies, analyses, and a few remedies.

    PubMed

    Ingold, K U; Bowry, Vincent W

    2015-02-01

    Kinetic data for reduction of organic halides (RX) by tri-n-butylstannane (SnH) reveal a serious flaw in the current view of the kinetic radical chain: the tacit but unproven assumption that the speed of reaction is determined by the slowest propagation step. Our results show this is rarely true for reductive chains and that the observed rate is in fact controlled by unseen side-reactions of propagating R(•) and Sn(•) radicals with the solvent (notably, benzene!) or solvent impurities (e.g., trace benzophenone dryness indicator in THF) or, crucially, with allylic-CH and conjugated unsaturated groups in substrates and products. Most R(•) and/or Sn(•) radicals are therefore converted into relatively inert delocalized species A(•) and/or B(•) that inhibit the chain. Retardation in the degraded chain is given by a simple sum of terms, each being the ratio of the chain-transfer rate divided by the rate of chain-return. The model kinetic equation is linear and easy to ratify, interpret, and apply: to calculate retarding rate constants, optimize reaction conditions, and identify additives or "remedies" that repair the chain and accelerate reaction. The present work is thus expected to have a helpful impact on the practice and design of SnH radical chain based (and related) syntheses. PMID:25545111

  20. Quantum confinement and dielectric profiles of colloidal nanoplatelets of halide inorganic and hybrid organic-inorganic perovskites

    NASA Astrophysics Data System (ADS)

    Sapori, Daniel; Kepenekian, Mikaël; Pedesseau, Laurent; Katan, Claudine; Even, Jacky

    2016-03-01

    Quantum confinement as well as high frequency ε∞ and static εs dielectric profiles are described for nanoplatelets of halide inorganic perovskites CsPbX3 (X = I, Br, Cl) and hybrid organic-inorganic perovskites (HOP) in two-dimensional (2D) and three-dimensional (3D) structures. 3D HOP are currently being sought for their impressive photovoltaic ability. Prior to this sudden popularity, 2D HOP materials were driving intense activity in the field of optoelectronics. Such developments have been enriched by the recent ability to synthesize colloidal nanostructures of controlled sizes of 2D and 3D HOP. This raises the need to achieve a thorough description of the electronic structure and dielectric properties of these systems. In this work, we go beyond the abrupt dielectric interface model and reach the atomic scale description. We examine the influence of the nature of the halogen and of the cation on the band structure and dielectric constants. Similarly, we survey the effect of dimensionality and shape of the perovskite. In agreement with recent experimental results, we show an increase of the band gap and a decrease of ε∞ when the size of a nanoplatelet reduces. By inspecting 2D HOP, we find that it cannot be described as a simple superposition of independent inorganic and organic layers. Finally, the dramatic impact of ionic contributions on the dielectric constant εs is analysed.Quantum confinement as well as high frequency ε∞ and static εs dielectric profiles are described for nanoplatelets of halide inorganic perovskites CsPbX3 (X = I, Br, Cl) and hybrid organic-inorganic perovskites (HOP) in two-dimensional (2D) and three-dimensional (3D) structures. 3D HOP are currently being sought for their impressive photovoltaic ability. Prior to this sudden popularity, 2D HOP materials were driving intense activity in the field of optoelectronics. Such developments have been enriched by the recent ability to synthesize colloidal nanostructures of controlled

  1. Applicability of Fluorescence and Absorbance Spectroscopy to Estimate Organic Pollution in Rivers

    PubMed Central

    Knapik, Heloise Garcia; Fernandes, Cristovão Vicente Scapulatempo; de Azevedo, Júlio Cesar Rodrigues; do Amaral Porto, Monica Ferreira

    2014-01-01

    Abstract This article explores the applicability of fluorescence and absorbance spectroscopy for estimating organic pollution in polluted rivers. The relationship between absorbance, fluorescence intensity, dissolved organic carbon, biochemical oxygen demand (BOD), chemical oxygen demand (COD), and other water quality parameters were used to characterize and identify the origin and the spatial variability of the organic pollution in a highly polluted watershed. Analyses were performed for the Iguassu River, located in southern Brazil, with area about 2,700 km2 and ∼3 million inhabitants. Samples were collect at six monitoring sites covering 107 km of the main river. BOD, COD, nitrogen, and phosphorus concentration indicates a high input of sewage to the river. Specific absorbance at 254 and 285 nm (SUVA254 and A285/COD) did not show significant variation between sites monitored, indicating the presence of both dissolved compounds found in domestic effluents and humic and fulvic compounds derived from allochthonous organic matter. Correlations between BOD and tryptophan-like fluorescence peak (peak T2, r=0.7560, and peak T1, r=0.6949) and tyrosine-like fluorescence peak (peak B, r=0.7321) indicated the presence of labile organic matter and thus confirmed the presence of sewage in the river. Results showed that fluorescence and absorbance spectroscopy provide useful information on pollution in rivers from critical watersheds and together are a robust method that is simpler and more rapid than traditional methods employed by regulatory agencies. PMID:25469076

  2. Spatially separated charge densities of electrons and holes in organic-inorganic halide perovskites

    SciTech Connect

    Li, Dan; Liang, Chunjun E-mail: zhqhe@bjtu.edu.cn; Zhang, Huimin; You, Fangtian; He, Zhiqun E-mail: zhqhe@bjtu.edu.cn; Zhang, Chunxiu

    2015-02-21

    Solution-processable methylammonium lead trihalide perovskites exhibit remarkable high-absorption and low-loss properties for solar energy conversion. Calculation from density functional theory indicates the presence of non-equivalent halogen atoms in the unit cell because of the specific orientation of the organic cation. Considering the 〈100〉 orientation as an example, I{sub 1}, one of the halogen atoms, differs from the other iodine atoms (I{sub 2} and I{sub 3}) in terms of its interaction with the organic cation. The valance-band-maximum (VBM) and conduction-band-minimum (CBM) states are derived mainly from 5p orbital of I{sub 1} atom and 6p orbital of Pb atom, respectively. The spatially separated charge densities of the electrons and holes justify the low recombination rate of the pure iodide perovskite. Chlorine substitution further strengthens the unique position of the I{sub 1} atom, leading to more localized charge density around the I{sub 1} atom and less charge density around the other atoms at the VBM state. The less overlap of charge densities between the VBM and CBM states explains the relatively lower carrier recombination rate of the iodine-chlorine mixed perovskite. Chlorine substitution significantly reduces the effective mass at a direction perpendicular to the Pb-Cl bond and organic axis, enhancing the carrier transport property of the mixed perovskite in this direction.

  3. DEVELOP NEW TOTAL ORGANIC CARBON/SPECIFIC UV ABSORBANCE METHOD WITH EXPANDED QUALITY CONTROL

    EPA Science Inventory

    The purpose of this project is to provide a total organic carbon (TOC)/specific ultraviolet absorbance (SUVA) method that will be used by the Office of Ground Water and Drinking Water (OGWDW) to support monitoring requirements of the Stage 2 Disinfectant/Disinfection By-products ...

  4. Removal of fluorescence and ultraviolet absorbance of dissolved organic matter in reclaimed water by solar light.

    PubMed

    Wu, Qianyuan; Li, Chao; Wang, Wenlong; He, Tao; Hu, Hongying; Du, Ye; Wang, Ting

    2016-05-01

    Storing reclaimed water in lakes is a widely used method of accommodating changes in the consumption of reclaimed water during wastewater reclamation and reuse. Solar light serves as an important function in degrading pollutants during storage, and its effect on dissolved organic matter (DOM) was investigated in this study. Solar light significantly decreased the UV254 absorbance and fluorescence (FLU) intensity of reclaimed water. However, its effect on the dissolved organic carbon (DOC) value of reclaimed water was very limited. The decrease in the UV254 absorbance intensity and FLU excitation-emission matrix regional integration volume (FLU volume) of reclaimed water during solar light irradiation was fit with pseudo-first order reaction kinetics. The decrease of UV254 absorbance was much slower than that of the FLU volume. Ultraviolet light in solar light had a key role in decreasing the UV254 absorbance and FLU intensity during solar light irradiation. The light fluence-based removal kinetic constants of the UV254 and FLU intensity were independent of light intensity. The peaks of the UV254 absorbance and FLU intensity with an apparent molecular weight (AMW) of 100Da to 2000Da decreased after solar irradiation, whereas the DOC value of the major peaks did not significantly change. PMID:27155416

  5. Effect of halide ions and carbonates on organic contaminant degradation by hydroxyl radical-based advanced oxidation processes in saline waters.

    PubMed

    Grebel, Janel E; Pignatello, Joseph J; Mitch, William A

    2010-09-01

    Advanced oxidation processes (AOPs) generating nonselective hydroxyl radicals (HO*) provide a broad-spectrum contaminant destruction option for the decontamination of waters. Halide ions are scavengers of HO* during AOP treatment, such that treatment of saline waters would be anticipated to be ineffective. However, HO* scavenging by halides converts HO* to radical reactive halogen species (RHS) that participate in contaminant destruction but react more selectively with electron-rich organic compounds. The effects of Cl-, Br-, and carbonates (H2CO3+HCO3-+CO3(2-)) on the UV/H2O2 treatment of model compounds in saline waters were evaluated. For single target organic contaminants, the impact of these constituents on contaminant destruction rate suppression at circumneutral pH followed the order Br->carbonates>Cl-. Traces of Br- in the NaCl stock had a greater effect than Cl- itself. Kinetic modeling of phenol destruction demonstrated that RHS contributed significantly to phenol destruction, mitigating the impact of HO* scavenging. The extent of treatment efficiency reduction in the presence of halides varied dramatically among different target organic compounds. Destruction of contaminants containing electron-poor reaction centers in seawater was nearly halted, while 17beta-estradiol removal declined by only 3%. Treatment of mixtures of contaminants with each other and with natural organic matter (NOM) was evaluated. Although NOM served as an oxidant scavenger, conversion of nonselective HO* to selective radicals due to the presence of anions enhanced the efficiency of electron-rich contaminant removal in saline waters by focusing the oxidizing power of the system away from the NOM toward the target contaminant. Despite the importance of contaminant oxidation by halogen radicals, the formation of halogenated byproducts was minimal. PMID:20681567

  6. Dipole-driven self-organization of zwitterionic molecules on alkali halide surfaces.

    PubMed

    Nony, Laurent; Bocquet, Franck; Para, Franck; Chérioux, Frédéric; Duverger, Eric; Palmino, Frank; Luzet, Vincent; Loppacher, Christian

    2012-01-01

    We investigated the adsorption of 4-methoxy-4'-(3-sulfonatopropyl)stilbazolium (MSPS) on different ionic (001) crystal surfaces by means of noncontact atomic force microscopy. MSPS is a zwitterionic molecule with a strong electric dipole moment. When deposited onto the substrates at room temperature, MSPS diffuses to step edges and defect sites and forms disordered assemblies of molecules. Subsequent annealing induces two different processes: First, at high coverage, the molecules assemble into a well-organized quadratic lattice, which is perfectly aligned with the <110> directions of the substrate surface (i.e., rows of equal charges) and which produces a Moiré pattern due to coincidences with the substrate lattice constant. Second, at low coverage, we observe step edges decorated with MSPS molecules that run along the <110> direction. These polar steps most probably minimize the surface energy as they counterbalance the molecular dipole by presenting oppositely charged ions on the rearranged step edge. PMID:22497002

  7. Dipole-driven self-organization of zwitterionic molecules on alkali halide surfaces

    PubMed Central

    Nony, Laurent; Bocquet, Franck; Para, Franck; Chérioux, Frédéric; Duverger, Eric; Palmino, Frank; Luzet, Vincent

    2012-01-01

    Summary We investigated the adsorption of 4-methoxy-4′-(3-sulfonatopropyl)stilbazolium (MSPS) on different ionic (001) crystal surfaces by means of noncontact atomic force microscopy. MSPS is a zwitterionic molecule with a strong electric dipole moment. When deposited onto the substrates at room temperature, MSPS diffuses to step edges and defect sites and forms disordered assemblies of molecules. Subsequent annealing induces two different processes: First, at high coverage, the molecules assemble into a well-organized quadratic lattice, which is perfectly aligned with the <110> directions of the substrate surface (i.e., rows of equal charges) and which produces a Moiré pattern due to coincidences with the substrate lattice constant. Second, at low coverage, we observe step edges decorated with MSPS molecules that run along the <110> direction. These polar steps most probably minimize the surface energy as they counterbalance the molecular dipole by presenting oppositely charged ions on the rearranged step edge. PMID:22497002

  8. Structural tunability and switchable exciton emission in inorganic-organic hybrids with mixed halides

    SciTech Connect

    Ahmad, Shahab; Vijaya Prakash, G.; Baumberg, Jeremy J.

    2013-12-21

    Room-temperature tunable excitonic photoluminescence is demonstrated in alloy-tuned layered Inorganic-Organic (IO) hybrids, (C{sub 12}H{sub 25}NH{sub 3}){sub 2}PbI{sub 4(1−y)}Br{sub 4y} (y = 0 to 1). These perovskite IO hybrids adopt structures with alternating stacks of low-dimensional inorganic and organic layers, considered to be naturally self-assembled multiple quantum wells. These systems resemble stacked monolayer 2D semiconductors since no interlayer coupling exists. Thin films of IO hybrids exhibit sharp and strong photoluminescence (PL) at room-temperature due to stable excitons formed within the low-dimensional inorganic layers. Systematic variation in the observed exciton PL from 510 nm to 350 nm as the alloy composition is changed, is attributed to the structural readjustment of crystal packing upon increase of the Br content in the Pb-I inorganic network. The energy separation between exciton absorption and PL is attributed to the modified exciton density of states and diffusion of excitons from relatively higher energy states corresponding to bromine rich sites towards the lower energy iodine sites. Apart from compositional fluctuations, these excitons show remarkable reversible flips at temperature-induced phase transitions. All the results are successfully correlated with thermal and structural studies. Such structural engineering flexibility in these hybrids allows selective tuning of desirable exciton properties within suitable operating temperature ranges. Such wide-range PL tunability and reversible exciton switching in these novel IO hybrids paves the way to potential applications in new generation of optoelectronic devices.

  9. Zero-dipole molecular organic cations in mixed organic-inorganic halide perovskites: possible chemical solution for the reported anomalous hysteresis in the current-voltage curve measurements

    NASA Astrophysics Data System (ADS)

    Giorgi, Giacomo; Yamashita, Koichi

    2015-11-01

    Starting from a brief description of the main architectures characterizing the novel solar technology of perovskite-based solar cells, we focus our attention on the anomalous hysteresis experimentally found to affect the measurement of the current-voltage curve of such devices. This detrimental effect, associated with slow dynamic reorganization processes, depends on several parameters; among them, the scan rate of the measurements, the architecture of the cell, and the perovskite deposition rate are crucial. Even if a conclusive explanation of the origin of the hysteresis has not been provided so far, several experimental findings ascribe its origin to ionic migration at an applied bias and dielectric polarization that occurs in the perovskite layer. Consistently, a dipole-moment-reduced cation such as formamidinium ion is experimentally reported to quantitatively reduce the hysteresis from perovskite-based devices. By means of a density-functional theory-based set of calculations, we have predicted and characterized guanidinium ion (GA = +[C(NH2)3], a zero-dipole moment cation by symmetry)-based organic-inorganic halide perovskite’s structural and electronic properties, speculating that such a cation and the alloys it may form with other organic cations can represent a possible chemical solution for the puzzling issue of the hysteresis.

  10. Zero-dipole molecular organic cations in mixed organic-inorganic halide perovskites: possible chemical solution for the reported anomalous hysteresis in the current-voltage curve measurements.

    PubMed

    Giorgi, Giacomo; Yamashita, Koichi

    2015-11-01

    Starting from a brief description of the main architectures characterizing the novel solar technology of perovskite-based solar cells, we focus our attention on the anomalous hysteresis experimentally found to affect the measurement of the current-voltage curve of such devices. This detrimental effect, associated with slow dynamic reorganization processes, depends on several parameters; among them, the scan rate of the measurements, the architecture of the cell, and the perovskite deposition rate are crucial. Even if a conclusive explanation of the origin of the hysteresis has not been provided so far, several experimental findings ascribe its origin to ionic migration at an applied bias and dielectric polarization that occurs in the perovskite layer. Consistently, a dipole-moment-reduced cation such as formamidinium ion is experimentally reported to quantitatively reduce the hysteresis from perovskite-based devices. By means of a density-functional theory-based set of calculations, we have predicted and characterized guanidinium ion (GA = (+)[C(NH2)3], a zero-dipole moment cation by symmetry)-based organic-inorganic halide perovskite's structural and electronic properties, speculating that such a cation and the alloys it may form with other organic cations can represent a possible chemical solution for the puzzling issue of the hysteresis. PMID:26468971

  11. Lipophilic polyelectrolyte gels as super-absorbent polymers for nonpolar organic solvents

    NASA Astrophysics Data System (ADS)

    Ono, Toshikazu; Sugimoto, Takahiro; Shinkai, Seiji; Sada, Kazuki

    2007-06-01

    Polyelectrolyte gels that are known as super-absorbent polymers swell and absorb water up to several hundred times their dried weights and have become ubiquitous and indispensable materials in many applications. Their superior swelling abilities originate from the electrostatic repulsion between the charges on the polymer chains and the osmotic imbalance between the interior and exterior of the gels. However, no super-absorbent polymers for volatile organic compounds (VOCs), and especially for nonpolar organic solvents (ɛ<10) have been reported, because common polyelectrolyte gels collapse in such solvents owing to the formation of a higher number of aggregates of ions and ion pairs. Here, we report that a novel class of polyelectrolyte gels bearing tetra-alkylammonium tetraphenylborate as a lipophilic and bulky ionic group swell in some nonpolar organic solvents up to 500 times their dry size. Dissociation of the ionic groups even in low-dielectric media (3<ɛ<10) enhances the swelling ability by expansion of the polymer networks. This expands the potential of polyelectrolytes that have been used only in aqueous solutions or highly polar solvents, and provides soft materials that swell in a variety of media. These materials could find applications as protective barriers for VOCs spilled in the environment and as absorbents for waste oil.

  12. Lead-free solid-state organic-inorganic halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Hao, Feng; Stoumpos, Constantinos C.; Cao, Duyen Hanh; Chang, Robert P. H.; Kanatzidis, Mercouri G.

    2014-06-01

    Lead-free solution-processed solid-state photovoltaic devices based on methylammonium tin iodide (CH3NH3SnI3) perovskite semiconductor as the light harvester are reported. Featuring an optical bandgap of 1.3 eV, the CH3NH3SnI3 perovskite material can be incorporated into devices with the organic hole-transport layer spiro-OMeTAD and show an absorption onset at 950 nm, which is significantly redshifted compared with the benchmark CH3NH3PbI3 counterpart (1.55 eV). Bandgap engineering was implemented by chemical substitution in the form of CH3NH3SnI3-xBrx solid solutions, which can be controllably tuned to cover much of the visible spectrum, thus enabling the realization of lead-free solar cells with an initial power conversion efficiency of 5.73% under simulated full sunlight. Further efficiency enhancements are expected following optimization and a better fundamental understanding of the internal electron dynamics and corresponding interfacial engineering. The reported CH3NH3SnI3-xBrx perovskite solar cells represent a step towards the realization of low-cost, environmentally friendly solid-state solar cells.

  13. Mesoporous silicate MCM-41 containing organic ultraviolet ray absorbents: Preparation, photostability and in vitro release

    NASA Astrophysics Data System (ADS)

    Ambrogi, V.; Perioli, L.; Marmottini, F.; Latterini, L.; Rossi, C.; Costantino, U.

    2007-05-01

    The mesoporous silicate MCM-41 was studied for its properties to adsorb and to influence the photostability and the release of three organic ultraviolet (UV) ray absorbents, namely benzophenone-3 (B3), benzophenone-2 (B2) and p-aminobenzoic acid (PABA). MCM-41 microcrystals have been loaded with the UV absorbents obtaining a good loading w/w percentage. The loaded samples have been characterized by chemical and thermal analyses, X-ray diffraction, N2 adsorption isotherms. Photochemical studies demonstrated that the UV-shielding properties of B2 were maintained whereas in other cases a small reduction of sunscreen protection range was noticed. B3 and B2 release from loaded MCM-41 formulations were studied and compared to those obtained from formulations containing free UV ray absorbent; no remarkable differences were observed in the release profiles.

  14. Uncertainties of organ-absorbed doses to patients from 18f-choline

    NASA Astrophysics Data System (ADS)

    Li, W. B.; Janzen, T.; Zankl, M.; Giussani, A.; Hoeschen, C.

    2011-03-01

    Radiation doses of radiopharmaceuticals to patients in nuclear medicine are, as the standard method, estimated by the administered activity, medical imaging (e.g. PET imaging), compartmental modeling and Monte Carlo simulation of radiation with reference digital human phantoms. However, in each of the contributing terms, individual uncertainty due to measurement techniques, patient variability and computation methods may propagate to the uncertainties of the calculated organ doses to the individual patient. To evaluate the overall uncertainties and the quality assurance of internal absorbed doses, a method was developed within the framework of the MADEIRA Project (Minimizing Activity and Dose with Enhanced Image quality by Radiopharmaceutical Administrations) to quantitatively analyze the uncertainties in each component of the organ absorbed doses after administration of 18F-choline to prostate cancer patients undergoing nuclear medicine diagnostics. First, on the basis of the organ PET and CT images of the patients as well as blood and urine samples, a model structure of 18F-choline was developed and the uncertainties of the model parameters were determined. Second, the model parameter values were sampled and biokinetic modeling using these sampled parameter values were performed. Third, the uncertainties of the new specific absorbed fraction (SAF) values derived with different phantoms representing individual patients were presented. Finally, the uncertainties of absorbed doses to the patients were calculated by applying the ICRP/ICRU adult male reference computational phantom. In addition to the uncertainty analysis, the sensitivity of the model parameters on the organ PET images and absorbed doses was indicated by coupling the model input and output using regression and partial correlation analysis. The results showed that the uncertainty factors of absorbed dose to patients are in most cases less than a factor of 2 without taking into account the uncertainties

  15. Kinetic and electrochemical studies of the oxidative addition of demanding organic halides to Pd(0): the efficiency of polyphosphane ligands in low palladium loading cross-couplings decrypted.

    PubMed

    Zinovyeva, Veronika A; Mom, Sophal; Fournier, Sophie; Devillers, Charles H; Cattey, Hélène; Doucet, Henri; Hierso, Jean-Cyrille; Lucas, Dominique

    2013-10-21

    Oxidative addition (OA) of organic halides to palladium(0) species is a fundamental reaction step which initiates the C-C bond formation catalytic processes typical of Pd(0)/Pd(II) chemistry. The use of structurally congested polyphosphane ligands in palladium-catalyzed C-C bond formation has generated very high turnover numbers (TONs) in topical reactions such as Heck, Suzuki, Sonogashira couplings, and direct sp(2)C-H functionalization. Herein, the OA of aryl bromides to Pd(0) complexes stabilized by ferrocenylpolyphosphane ligands L1 (tetraphosphane), L2 (triphosphane), and L3 (diphosphane) is considered. The investigation of kinetic constants for the addition of Ph-Br to Pd(0) intermediates (generated by electrochemical reduction of Pd(II) complexes coordinated by L1-L3) is reported. Thus, in the OA of halides to the Pd(0) complex coordinated by L1 the series of rate constants kapp is found (mol(-1) L s(-1)): kapp(Ph-Br) = 0.48 > kapp(ClCH2-Cl) = 0.25 ≫ kapp(p-MeC6H4-Br) = 0.08 ≈ kapp(o-MeC6H4-Br) = 0.07 ≫ kapp(Ph-Cl). Kinetic measurements clarify the influence that the presence of four, three, or two phosphorus atoms in the coordination sphere of Pd has on OA. The presence of supplementary phosphorus atoms in L1 and L2 unambiguously stabilizes Pd(0) species and thus slows down the OA of Ph-Br to Pd(0) of about 2 orders of magnitude compared to the diphosphane L3. The electrosynthesis of the complexes resulting from the OA of organic halides to [Pd(0)/L] is easily performed and show the concurrent OA to Pd(0) of the sp(3)C-Cl bond of dichloromethane solvent. The resulting unstable Pd/alkyl complex is characterized by NMR and single crystal X-ray structure. We additionally observed the perfect stereoselectivity of the OA reactions which is induced by the tetraphosphane ligand L1. Altogether, a clearer picture of the general effects of congested polydentate ligands on the OA of organic halides to Pd(0) is given. PMID:24107007

  16. Metal-organic frameworks reactivate deceased diatoms to be efficient CO(2) absorbents.

    PubMed

    Liu, Dingxin; Gu, Jiajun; Liu, Qinglei; Tan, Yongwen; Li, Zhuo; Zhang, Wang; Su, Yishi; Li, Wuxia; Cui, Ajuan; Gu, Changzhi; Zhang, Di

    2014-02-26

    Diatomite combined with certain metal-organic frameworks (MOFs) is shown to be an effective CO2 absorbent, although diatomite alone is regarded as inert with respect to CO2 absorption. This finding opens the prospect of reactivating millions of tons of diatomite for CO2 absorption. It also shows for the first time that diatom frustules can act as CO2 buffers, an important link in a successive biological CO2 concentration mechanism chain that impacts on global warming. PMID:24285587

  17. The Silver Halides

    ERIC Educational Resources Information Center

    Sahyun, M. R. V.

    1977-01-01

    Illustrates the type of fractional bonding for solid silver halides. Treats the silver halides as electron excess compounds, and develops a model of a localized bonding unit that may be iterated in three dimensions to describe the bulk phase. (MLH)

  18. A Strained Disilane-Promoted Carboxylation of Organic Halides with CO2 under Transition-Metal-Free Conditions.

    PubMed

    Mita, Tsuyoshi; Suga, Kenta; Sato, Kaori; Sato, Yoshihiro

    2015-11-01

    By using a strained four-membered ring disilane (3,4-benzo-1,1,2,2-tetraethyldisilacyclobutene) and CsF, a wide range of aryl, alkenyl, alkynyl, benzyl, allyl, and alkyl halides was successfully carboxylated under an ambient CO2 atmosphere (CO2 balloon) at room temperature within 2 h. In this carboxylation, a highly reactive silyl anion, which is generated from the disilane and CsF, is a key to facilitating the formation of a carbanion equivalent. The resulting anionic species can be trapped with CO2 to produce carboxylic acids with high efficiency. PMID:26451945

  19. Quantifying and correcting the impacts of freezing samples on dissolved organic matter absorbance

    NASA Astrophysics Data System (ADS)

    Griffin, C. G.; McClelland, J. W.; Frey, K. E.; Holmes, R. M.

    2012-12-01

    The use of optical measurements as proxies for organic matter concentration and composition has become increasingly popular in recent years. Absorbance of chromophoric dissolved organic matter (CDOM) can be used to estimate concentrations of dissolved organic carbon (DOC), as a qualitative assessment of dissolved organic matter (DOM) average molecular weight and is often used to calibrate satellite remote sensing of organic matter. However, there is evidence that preservation of samples can lead to significant changes in CDOM absorbance spectra. Freezing is a popular means of preservation, but can result in flocculation of DOM when samples are thawed for analysis. We hypothesize that the particles generated as a result of a freeze/thaw cycle lead to increasing absorption in visible wavelengths (400-800 nm). Yet, absorbance in the UV spectra should remain similar to original values. These hypotheses are tested on CDOM spectra collected from two large Arctic watersheds (the Mackenzie and Yukon rivers) and four smaller Texas watersheds (the Colorado, Guadalupe, Nueces and San Antonio rivers). In addition, we experiment with additional filtering and sonication to correct for flocculation from frozen samples. Preliminary data show that short wavelengths are relatively well preserved (200-300 nm). However, CDOM absorption changes unpredictably from 350-450 nm, the wavelengths most commonly used to estimate DOC. Absorption coefficients tend to be higher in these wavelengths after a freeze/thaw cycle, but the magnitude of this increase varies. Some of these impacts can be corrected for with sonication. For instance, when comparing experimental treatments to initial absorption at 365 nm from Mackenzie River samples, R2 increases from 0.60 to 0.79 for samples undergoing one freeze/thaw cycle to those that were also sonicated. Regardless of treatment, however, no spectral slopes were well preserved after a freeze/thaw cycle. These results reinforce earlier work that it is

  20. Surface-active and Light-absorbing Secondary Organic Aerosol (SOA) Material

    NASA Astrophysics Data System (ADS)

    McNeill, V. F.; Sareen, N.; Schwier, A. N.; Shapiro, E. L.

    2009-12-01

    We have observed the formation of light-absorbing, high-molecular-weight, and surface-active organics from methylgyloxal interacting with ammonium salts in aqueous aerosol mimics. Mixtures of methylglyoxal and glyoxal also form light-absorbing products and exhibit surface tension depression with a Langmuir-like dependence on initial methylglyoxal concentration. We used chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol-CIMS) to characterize the product species. The results are consistent with aldol condensation products, carbon-nitrogen species, sulfur-containing compounds, and oligomeric species up to 759 amu. These observations have potentially significant implications for our understanding of the effects of SOA on climate, since a) SOA are typically treated as non-absorbing in climate models, and b) surface tension depression in aqueous aerosols by SOA material may result in increased cloud condensation nucleus (CCN) activity. Furthermore, surface film formation could affect aerosol heterogeneous chemistry. We will also discuss aerosol flow tube O3 oxidation experiments designed to determine the atmospheric lifetimes of the observed product compounds.

  1. Estimating the Absorbed Dose to Critical Organs During Dual X-ray Absorptiometry

    PubMed Central

    Sharafi, A A; Larijani, B; Mokhlesian, N; Hasanzadeh, H

    2008-01-01

    Objective The purpose of this study is to estimate a patient's organ dose (effective dose) during performance of dual X-ray absorptiometry by using the correlations derived from the surface dose and the depth doses in an anthropomorphic phantom. Materials and Methods An anthropomorphic phantom was designed and TLDs (Thermoluminescent Dosimeters) were placed at the surface and these were also inserted at different depths of the thyroid and uterus of the anthropomorphic phantom. The absorbed doses were measured on the phantom for the spine and femur scan modes. The correlation coefficients and regression functions between the absorbed surface dose and the depth dose were determined. The derived correlation was then applied for 40 women patients to estimate the depth doses to the thyroid and uterus. Results There was a correlation between the surface dose and depth dose of the thyroid and uterus in both scan modes. For the women's dosimetry, the average surface doses of the thyroid and uterus were 1.88 µGy and 1.81 µGy, respectively. Also, the scan center dose in the women was 5.70 µGy. There was correlation between the thyroid and uterus surface doses, and the scan center dose. Conclusion We concluded that the effective dose to the patient's critical organs during dual X-ray absorptiometry can be estimated by the correlation derived from phantom dosimetry. PMID:18385556

  2. Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts.

    PubMed

    Poelma, Saemi O; Burnett, G Leslie; Discekici, Emre H; Mattson, Kaila M; Treat, Nicolas J; Luo, Yingdong; Hudson, Zachary M; Shankel, Shelby L; Clark, Paul G; Kramer, John W; Hawker, Craig J; Read de Alaniz, Javier

    2016-08-19

    Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity. PMID:27276418

  3. Organic solar cells with graded absorber layers processed from nanoparticle dispersions

    NASA Astrophysics Data System (ADS)

    Gärtner, Stefan; Reich, Stefan; Bruns, Michael; Czolk, Jens; Colsmann, Alexander

    2016-03-01

    The fabrication of organic solar cells with advanced multi-layer architectures from solution is often limited by the choice of solvents since most organic semiconductors dissolve in the same aromatic agents. In this work, we investigate multi-pass deposition of organic semiconductors from eco-friendly ethanol dispersion. Once applied, the nanoparticles are insoluble in the deposition agent, allowing for the application of further nanoparticulate layers and hence for building poly(3-hexylthiophene-2,5-diyl):indene-C60 bisadduct absorber layers with vertically graded polymer and conversely graded fullerene concentration. Upon thermal annealing, we observe some degrees of polymer/fullerene interdiffusion by means of X-ray photoelectron spectroscopy and Kelvin probe force microscopy. Replacing the common bulk-heterojunction by such a graded photo-active layer yields an enhanced fill factor of the solar cell due to an improved charge carrier extraction, and consequently an overall power conversion efficiency beyond 4%. Wet processing of such advanced device architectures paves the way for a versatile, eco-friendly and industrially feasible future fabrication of organic solar cells with advanced multi-layer architectures.

  4. Organic solar cells with graded absorber layers processed from nanoparticle dispersions.

    PubMed

    Gärtner, Stefan; Reich, Stefan; Bruns, Michael; Czolk, Jens; Colsmann, Alexander

    2016-03-28

    The fabrication of organic solar cells with advanced multi-layer architectures from solution is often limited by the choice of solvents since most organic semiconductors dissolve in the same aromatic agents. In this work, we investigate multi-pass deposition of organic semiconductors from eco-friendly ethanol dispersion. Once applied, the nanoparticles are insoluble in the deposition agent, allowing for the application of further nanoparticulate layers and hence for building poly(3-hexylthiophene-2,5-diyl):indene-C60 bisadduct absorber layers with vertically graded polymer and conversely graded fullerene concentration. Upon thermal annealing, we observe some degrees of polymer/fullerene interdiffusion by means of X-ray photoelectron spectroscopy and Kelvin probe force microscopy. Replacing the common bulk-heterojunction by such a graded photo-active layer yields an enhanced fill factor of the solar cell due to an improved charge carrier extraction, and consequently an overall power conversion efficiency beyond 4%. Wet processing of such advanced device architectures paves the way for a versatile, eco-friendly and industrially feasible future fabrication of organic solar cells with advanced multi-layer architectures. PMID:26952692

  5. Light-absorbing secondary organic material formed by glyoxal in aqueous aerosol mimics

    NASA Astrophysics Data System (ADS)

    Shapiro, E. L.; Szprengiel, J.; Sareen, N.; Jen, C. N.; Giordano, M. R.; McNeill, V. F.

    2009-01-01

    Light-absorbing and high-molecular-weight secondary organic products were observed to result from the reaction of glyoxal in mildly acidic (pH=4) aqueous inorganic salt solutions mimicking aqueous tropospheric aerosol particles. High-molecular-weight (500-600 amu) products were observed when ammonium sulfate ((NH4)2SO4) or sodium chloride (NaCl) was present in the aqueous phase. The products formed in the (NH4)2SO4 solutions absorb light at UV and visible wavelengths. Substantial absorption at 300-400 nm develops within two hours, and absorption between 400-600 nm develops within days. Pendant drop tensiometry measurements show that the products are not surface-active. The experimental results along with ab initio predictions of the UV/Vis absorption of potential products suggest that an aldol condensation mechanism is active in the glyoxal-(NH4)2SO4system, resulting in the formation of pi-conjugated products. If similar products are formed in atmospheric aerosol particles, they could change the optical properties of the seed aerosol over its lifetime.

  6. Polarity and oxidation level of visible absorbers in model organic aerosol

    NASA Astrophysics Data System (ADS)

    Rifkha Kameel, F.; Lee, S. H.; Hoffmann, M. R.; Colussi, A. J.

    2014-05-01

    How to parametrize the absorptivity of organic aerosols in atmospheric radiative models remains uncertain. Here we report that the λ = 400 nm absorbers in model aerosol mixtures elute as weakly polar species in reversed-phase chromatography. Typical among them, the m/z = 269 (C12H13O7-, O/C = 0.58) isomers detected by mass spectrometry possess Cdbnd O groups linked by Cdbnd C bridges. More polar species, such as the m/z = 289 (C11H13O9-, O/C = 0.82) polyacids, are instead colorless. On this basis we argue that visible absorptivity, which develops from extended conjugation among chromophores, may not increase monotonically with oxidation level.

  7. Fingerprinting Dissolved Organic Carbon (DOC) Sources with Specific UV Absorbance (SUVA) and Fluorescence

    NASA Astrophysics Data System (ADS)

    van Verseveld, W. J.; Lajtha, K.; McDonnell, J. J.

    2007-12-01

    DOC is an important water quality constituent because it is an important food source for stream biota, it plays a significant role in metal toxicity and transport, and protects aquatic organisms by absorbing visible and UV light. However, sources of stream DOC and changes in DOC quality at storm and seasonal scales remain poorly understood. We characterized DOC concentrations and SUVA (as an indicator of aromaticity) at the plot, hillslope and catchment scale during and between five storm events over the period Fall 2004 until Spring 2005, in WS10, H.J. Andrews, Oregon, USA. This study site has hillslopes that issue directly into the stream. This enabled us to compare a trenched hillslope response to the stream response without the influence of a riparian zone. The main result of this study was that SUVA in addition to DOC was needed to fingerprint sources of DOC. Stream water and lateral subsurface flow showed a clockwise DOC and SUVA hysteresis pattern. Both organic horizon water and transient groundwater were characterized by high DOC concentrations and SUVA values, while DOC concentrations and SUVA values in soil water decreased with depth in the soil profile. This indicates transient groundwater was an important contributor to high DOC concentrations and SUVA values during storm events. During the falling limb of the hydrograph deep soil water and seepage groundwater based on SUVA values contributed significantly to lateral subsurface flow and stream water. Preliminary results showed that fluorescence of stream water and lateral subsurface flow continuously measured with a fluorometer was significantly related to UV-absorbance during a December storm event. Finally, SUVA of lateral subsurface flow was lower than SUVA of stream water at the seasonal scale, indicating a difference in mixing of water sources at the hillslope and catchment scale. Overall, our results show that SUVA and fluorescence are useful tracers for fingerprinting DOC sources.

  8. Mechanism of Charge Transfer and Recombination Dynamics in Organo Metal Halide Perovskites and Organic Electrodes, PCBM, and Spiro-OMeTAD: Role of Dark Carriers.

    PubMed

    Ponseca, Carlito S; Hutter, Eline M; Piatkowski, Piotr; Cohen, Boiko; Pascher, Torbjörn; Douhal, Abderrazzak; Yartsev, Arkady; Sundström, Villy; Savenije, Tom J

    2015-12-30

    Despite the unprecedented interest in organic-inorganic metal halide perovskite solar cells, quantitative information on the charge transfer dynamics into selective electrodes is still lacking. In this paper, we report the time scales and mechanisms of electron and hole injection and recombination dynamics at organic PCBM and Spiro-OMeTAD electrode interfaces. On the one hand, hole transfer is complete on the subpicosecond time scale in MAPbI3/Spiro-OMeTAD, and its recombination rate is similar to that in neat MAPbI3. This was found to be due to a high concentration of dark charges, i.e., holes brought about by unintentional p-type doping of MAPbI3. Hence, the total concentration of holes in the perovskite is hardly affected by optical excitation, which manifested as similar decay kinetics. On the other hand, the decay of the photoinduced conductivity in MAPbI3/PCBM is on the time scale of hundreds of picoseconds to several nanoseconds, due to electron injection into PCBM and electron-hole recombination at the interface occurring at similar rates. These results highlight the importance of understanding the role of dark carriers in deconvoluting the complex photophysical processes in these materials. Moreover, optimizing the preparation processes wherein undesired doping is minimized could prompt the use of organic molecules as a more viable electrode substitute for perovskite solar cell devices. PMID:26636183

  9. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    PubMed

    Chen, Kun; Tüysüz, Harun

    2015-11-01

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. PMID:26376773

  10. Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber

    NASA Astrophysics Data System (ADS)

    Stranks, Samuel; Eperon, Giles; Grancini, Giulia; Menelaou, Christopher; Alcocer, Marcelo; Leijtens, Tomas; Herz, Laura; Petrozza, Annamaria; Snaith, Henry

    2014-03-01

    Organic-inorganic perovskites have shown promise as high-performance absorbers in solar cells, first as a coating on a mesoporous metal oxide scaffold and more recently as a solid layer in planar heterojunction architectures. Here, we report transient absorption and photoluminescence-quenching measurements to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide (CH3NH3PbI3-xClx) and triiodide (CH3NH3PbI3) perovskite absorbers. We found that the diffusion lengths are greater than 1 micrometer in the mixed halide perovskite, which is an order of magnitude greater than the absorption depth. In contrast, the triiodide absorber has electron-hole diffusion lengths of order 100 nanometers. Finally, we fabricated solution-processed thin-film planar heterojunction devices, achieving power conversion efficiencies of over 12% using the mixed halide absorber but only 4% with the triiodide perovskite. Our results show that the long diffusion lengths justify the high efficiency of planar heterojunction perovskite solar cells, and identify a critical parameter to optimize for future perovskite absorber development.

  11. Multi-target determination of organic ultraviolet absorbents in organism tissues by ultrasonic assisted extraction and ultra-high performance liquid chromatography-tandem mass spectrometry.

    PubMed

    Peng, Xianzhi; Jin, Jiabin; Wang, Chunwei; Ou, Weihui; Tang, Caiming

    2015-03-01

    A sensitive and reliable method was developed for multi-target determination of 13 most widely used organic ultraviolet (UV) absorbents (including UV filters and UV stabilizers) in aquatic organism tissues. The organic UV absorbents were extracted using ultrasonic-assisted extraction, purified via gel permeation chromatography coupled with silica gel column chromatography, and determined by ultra-high performance liquid chromatography-tandem mass spectrometry. Recoveries of the UV absorbents from organism tissues mostly ranged from 70% to 120% from fish filet with satisfactory reproducibility. Method quantification limits were 0.003-1.0ngg(-1) dry weight (dw) except for 2-ethylhexyl 4-methoxycinnamate. This method has been applied to analysis of the UV absorbents in wild and farmed aquatic organisms collected from the Pearl River Estuary, South China. 2-Hydroxy-4-methoxybenzophenone and UV-P were frequently detected in both wild and farmed marine organisms at low ngg(-1)dw. 3-(4-Methylbenzylidene)camphor and most of the benzotriazole UV stabilizers were also frequently detected in maricultured fish. Octocrylene and 2-ethylhexyl 4-methoxycinnamate were not detected in any sample. This work lays basis for in-depth study about bioaccumulation and biomagnification of the UV absorbents in marine environment. PMID:25637008

  12. Predicting trace organic compound breakthrough in granular activated carbon using fluorescence and UV absorbance as surrogates.

    PubMed

    Anumol, Tarun; Sgroi, Massimiliano; Park, Minkyu; Roccaro, Paolo; Snyder, Shane A

    2015-06-01

    This study investigated the applicability of bulk organic parameters like dissolved organic carbon (DOC), UV absorbance at 254 nm (UV254), and total fluorescence (TF) to act as surrogates in predicting trace organic compound (TOrC) removal by granular activated carbon in water reuse applications. Using rapid small-scale column testing, empirical linear correlations for thirteen TOrCs were determined with DOC, UV254, and TF in four wastewater effluents. Linear correlations (R(2) > 0.7) were obtained for eight TOrCs in each water quality in the UV254 model, while ten TOrCs had R(2) > 0.7 in the TF model. Conversely, DOC was shown to be a poor surrogate for TOrC breakthrough prediction. When the data from all four water qualities was combined, good linear correlations were still obtained with TF having higher R(2) than UV254 especially for TOrCs with log Dow>1. Excellent linear relationship (R(2) > 0.9) between log Dow and the removal of TOrC at 0% surrogate removal (y-intercept) were obtained for the five neutral TOrCs tested in this study. Positively charged TOrCs had enhanced removals due to electrostatic interactions with negatively charged GAC that caused them to deviate from removals that would be expected with their log Dow. Application of the empirical linear correlation models to full-scale samples provided good results for six of seven TOrCs (except meprobamate) tested when comparing predicted TOrC removal by UV254 and TF with actual removals for GAC in all the five samples tested. Surrogate predictions using UV254 and TF provide valuable tools for rapid or on-line monitoring of GAC performance and can result in cost savings by extended GAC run times as compared to using DOC breakthrough to trigger regeneration or replacement. PMID:25792436

  13. Optical Properties of Moderately-Absorbing Organic and Mixed Organic/Inorganic Particles at Very High Humidities

    SciTech Connect

    Bond, Tami C; Rood, Mark J; Brem, Benjamin T; Mena-Gonzalez, Francisco C; Chen, Yanju

    2012-04-16

    Relative humidity (RH) affects the water content of an aerosol, altering its ability to scatter and absorb light, which is important for aerosol effects on climate and visibility. This project involves in situ measurement and modeling of aerosol optical properties including absorption, scattering and extinction at three visible wavelengths (467, 530, 660 nm), for organic carbon (OC) generated by pyrolysis of biomass, ammonium sulfate and sodium chloride, and their mixtures at controlled RH conditions. Novel components of this project include investigation of: (1) Changes in all three of these optical properties at scanned RH conditions; (2) Optical properties at RH values up to 95%, which are usually extrapolated instead of measured; and (3) Examination of aerosols generated by the pyrolysis of wood, which is representative of primary atmospheric organic carbon, and its mixture with inorganic aerosol. Scattering and extinction values were used to determine light absorption by difference and single scattering albedo values. Extensive instrumentation development and benchmarking with independently measured and modeled values were used to obtain and evaluate these new results. The single scattering albedo value for a dry absorbing polystyrene microsphere benchmark agreed within 0.02 (absolute value) with independently published results at 530 nm. Light absorption by a nigrosin (sample light-absorbing) benchmark increased by a factor of 1.24 +/-0.06 at all wavelengths as RH increased from 38 to 95%. Closure modeling with Mie theory was able to reproduce this increase with the linear volume average (LVA) refractive index mixing rule for this water soluble compound. Absorption by biomass OC aerosol increased by a factor of 2.1 +/- 0.7 and 2.3 +/- 1.2 between 32 and 95% RH at 467 nm and 530 nm, but there was no detectable absorption at 660 nm. Additionally, the spectral dependence of absorption by OC that was observed with filter measurements was confirmed qualitatively

  14. Direct measurement of the exciton binding energy and effective masses for charge carriers in organic-inorganic tri-halide perovskites

    NASA Astrophysics Data System (ADS)

    Miyata, Atsuhiko; Mitioglu, Anatolie; Plochocka, Paulina; Portugall, Oliver; Wang, Jacob Tse-Wei; Stranks, Samuel D.; Snaith, Henry J.; Nicholas, Robin J.

    2015-07-01

    Solar cells based on the organic-inorganic tri-halide perovskite family of materials have shown significant progress recently, offering the prospect of low-cost solar energy from devices that are very simple to process. Fundamental to understanding the operation of these devices is the exciton binding energy, which has proved both difficult to measure directly and controversial. We demonstrate that by using very high magnetic fields it is possible to make an accurate and direct spectroscopic measurement of the exciton binding energy, which we find to be only 16 meV at low temperatures, over three times smaller than has been previously assumed. In the room-temperature phase we show that the binding energy falls to even smaller values of only a few millielectronvolts, which explains their excellent device performance as being due to spontaneous free-carrier generation following light absorption. Additionally, we determine the excitonic reduced effective mass to be 0.104me (where me is the electron mass), significantly smaller than previously estimated experimentally but in good agreement with recent calculations. Our work provides crucial information about the photophysics of these materials, which will in turn allow improved optoelectronic device operation and better understanding of their electronic properties.

  15. Optical properties and structural phase transitions of lead-halide based inorganic-organic 3D and 2D perovskite semiconductors under high pressure

    NASA Astrophysics Data System (ADS)

    Matsuishi, K.; Ishihara, T.; Onari, S.; Chang, Y. H.; Park, C. H.

    2004-11-01

    Optical absorption, photoluminescence and Raman scattering of lead-halide based inorganic-organic perovskite semiconductors were measured under quasi-hydrostatic pressure at room temperature. For the 3D perovskite semiconductor, (CH3NH3)PbBr3, the free exciton photoluminescence band exhibits red-shifts with pressure, and jumps to a higher energy by 0.07 eV at 0.8 GPa, which is associated with a phase transition from a cubic to an orthorhombic structure confirmed by Raman scattering. Above the phase transition pressure, the exciton band shows blue-shifts with further increasing pressure, and eventually disappears above 4.7 GPa. The results are compared with those for the 2D perovskite semiconductor, (C4H9NH3)2PbI4. First principles pseudopotential calculations were performed to investigate changes in octahedral distortion and electronic band structures with pressure. The calculations have explained the origins of the intriguing changes in the electronic states with pressure in view of bonding characters between atomic orbitals in octahedra.

  16. Evaluation of UV-permeability and photo-oxidisability of organic ultraviolet radiation-absorbing coatings

    NASA Astrophysics Data System (ADS)

    Li, Neng; Chen, Yuhe; Bao, Yongjie; Zhang, Zeqian; Wu, Zaixing; Chen, Zhangmin

    2015-03-01

    Enhancing the durability of the coatings used on bamboo products is essential for increasing their use in outdoor environments. In this study, we investigated organic UV radiation-absorbing coatings for use on bamboo surfaces. The degree of resistance of the coatings, which contained 2-(2-hydroxy-3-tert-butyl-5-methyl-phenyl)-5-chlorinated benzotriazole (BTZ-1), to UV radiation degradation was determined through spectroscopic analysis. The critical BTZ-1 loading amount was determined by analysing the spectroscopic data. Fourier transform infrared spectroscopy was used to elucidate the relationship between the degree of photooxidation of the coatings and their BTZ-1 concentration. The experimental results showed that the coatings provided a high degree of shielding from UV radiation. The critical loading amount was determined to be 1.82 ± 0.05 g BTZ-1/m2. The coatings formed using the formulations that contained 3 and 5 wt% BTZ-1 exhibited the lowest degree of photooxidation after exposure to UV radiation.

  17. Lithography-Free Broadband Ultrathin-Film Absorbers with Gap-Plasmon Resonance for Organic Photovoltaics.

    PubMed

    Choi, Minjung; Kang, Gumin; Shin, Dongheok; Barange, Nilesh; Lee, Chang-Won; Ko, Doo-Hyun; Kim, Kyoungsik

    2016-05-25

    Strategies to confine electromagnetic field within ultrathin film emerge as essential technologies for applications from thin-film solar cells to imaging and sensing devices. We demonstrate a lithography-free, low-cost, large-scale method to realize broadband ultrathi-film metal-dielectric-metal (MDM) absorbers, by exploiting gap-plasmon resonances for strongly confined electromagnetic field. A two-steps method, first organizing Au nanoparticles via thermal dewetting and then transferring the nanoparticles to a spacer-reflector substrate, is used to achieve broader absorption bandwidth by manipulating geometric shapes of the top metallic layer into hemiellipsoids. A fast-deposited nominal Au film, instead of a conventional slow one, is employed in the Ostwald ripening process to attain hemiellipsoidal nanoparticles. A polymer supported transferring step allows a wider range of dewetting temperature to manipulate the nanoparticles' shape. By incorporating circularity with ImageJ software, the geometries of hemiellipsoidal nanoparticles are quantitatively characterized. Controlling the top geometry of MDM structure from hemisphere to hemiellipsoid increases the average absorption at 500-900 nm from 23.1% to 43.5% in the ultrathin film and full width at half-maximum of 132-324 nm, which is consistently explained by finite-difference time-domain simulation. The structural advantages of our scheme are easily applicable to thin-film photovoltaic devices because metal electrodes can act as metal reflectors and semiconductor layers as dielectric spacers. PMID:27160410

  18. Estimation of Organ Absorbed Doses in Patients from 99mTc-diphosphonate Using the Data of MIRDose Software

    PubMed Central

    Shahbazi-Gahrouei, Daryoush; Cheki, Mohsen; Moslehi, Masoud

    2012-01-01

    The purpose of this study was to compare estimation of radiation absorbed doses to patients following bone scans with technetium-99m-labeled methylene diphosphonate (MDP) with the estimates given in MIRDose software. In this study, each patient was injected 25 mCi of 99mTc-MDP. Whole-body images from thirty patients were acquired by gamma camera at 10, 60, 90, 180 minutes after 99mTc-MDP injection. To determine the amount of activity in each organ, conjugate view method was applied on images. MIRD equation was then used to estimate absorbed doses in different organs of patients. At the end, absorbed dose values obtained in this study were compared with the data of MIRDose software. The absorbed doses per unit of injected activity (mGy/MBq × 10–4) for liver, kidneys, bladder wall and spleen were 3.86 ± 1.1, 38.73 ± 4.7, 4.16 ± 1.8 and 3.91 ± 1.3, respectively. The results of this study may be useful to estimate the amount of activity that can be administered to the patient and also showed that methods used in the study for absorbed dose calculation is in good agreement with the data of MIRDose software and it is possible to use by a clinician. PMID:23724374

  19. Secondary organic material formed by methylglyoxal in aqueous aerosol mimics - Part 1: Surface tension depression and light-absorbing products

    NASA Astrophysics Data System (ADS)

    Schwier, A. N.; Shapiro, E. L.; Sareen, N.; McNeill, V. F.

    2009-07-01

    We show that methylglyoxal forms light-absorbing secondary organic material in aqueous ammonium sulfate and ammonium nitrate solutions mimicking tropospheric aerosol particles. The light-absorbing products form on the order of minutes, and solution composition continues to change over several days. The results suggest an aldol condensation pathway involving the participation of the ammonium ion. Aqueous solutions of methylglyoxal, with and without inorganic salts, exhibit surface tension depression. Methylglyoxal uptake could potentially change the optical properties, climate effects, and heterogeneous chemistry of the seed aerosol over its lifetime.

  20. Analysis of the Body Distribution of Absorbed Dose in the Organs of Three Species of Fish from Sepetiba Bay

    SciTech Connect

    Pereira, Wagner de S; Kelecom, Alphonse; Santos Gouvea, Rita de Cassia dos; Azevedo Py Junior, Delcy de

    2008-08-07

    The body distribution of Polonium-210 in three fishes from the Sepetiba Bay (Macrodon ancylodon, Micropogonias furnieri and Mugil curema) has been studied under the approach of the Department of Energy of the United States of America (DOE) that set the limit of absorbed dose rate in biota equal to 3.5x10{sup 3} {mu}Gy/y, and that also established the relation between dose rate (D) and radionuclide concentration (c) on a fish muscle fresh weight basis, as follows: D = 5.05 ExNxC, assuming that the radionuclide distribution is homogenous among organs. Two hypotheses were tested here, using statistical tools: 1) is the body distribution of absorbed dose homogenous among organs? and 2) is the body distribution of absorbed dose identical among studied fishes? It was concluded, as expected, that the distribution among organs is heterogeneous; but, unexpectedly, that the three fishes display identical body distribution pattern, although they belong to different trophic levels. Hence, concerning absorbed dose calculation, the statement that data distribution is homogenous must be understood merely as an approximation, at least in the case of Polonium-210.

  1. Near-IR absorbing phthalocyanine derivatives as materials for organic solar cells

    NASA Astrophysics Data System (ADS)

    Mayukh, Mayank

    2011-12-01

    Phthalocyanines (Pcs) are highly conjugated synthetic porphyrin analogs that exhibit high extinction coefficients and hole mobilities, and strong pi-pi interactions. We have developed a general method for the synthesis of peripherally functionalized Pc chromophores using 'click' chemistry, wherein an alkynyl substituted Pc is reacted with an azide, providing an elegant route to the creation of a library of numerous Pcs. We have also developed a simple route to the synthesis of tri- and tetravalent metal Pc derivatives such as titanyl phthalocyanine (TiO Pc) involving solvent-free conditions. Solvent-free conditions are environmentally friendly and industrially economical, and in the present context effectively eliminate the formation of non-metallated phthalocyanine (H 2Pc), a side product often seen in other routes that interferes with their purification. We have also prepared and characterized thin-films of some of these Pcs, TiOPcs in particular, wherein we have developed an easy route to various TiO Pc polymorphs exhibiting different near-IR sensitivities via spin-coating whose optical properties are reminiscent of Phase-I and Phase-II polymorphs of the unmodified TiOPc. Phase-II is particularly interesting as it is photoelectrically active in the near-IR region with a Q-band maximum at ca. 890 nm. We have also fabricated and characterized organic solar cells in both planar heterojunction (PHJ) and bulk heterojunction (BHJ) architectures based on one of these materials, which exhibited good near-IR photoactivity with the absorption spectrum extending up to 1 micrometer in the near-IR. The incident and absorbed photon to current efficiency (IPCE and APCE) spectra showed contributions from the TiOPc in the near-IR region with local maxima around 680 nm and 920 nm, corresponding to the Frenkel and the charge-transfer (CT) bands of the TiOPc, respectively.

  2. Photoinduced electron transfer double fragmentation. An oxygen-mediated radical chain process in the cofragmentation of aminopinacol donors with organic halides

    SciTech Connect

    Chen, L.; Farahat, M.S.; Gan, H.; Whitten, D.G.; Farid, S. |

    1995-06-14

    We reprot an investigation in which excited states of amino pinacols 1-3 are reacted with the halides CCl{sub 4}, benzyl bromide, and p-cyanobenzyl bromide. Interesting results from this study include the finding that low-to-moderate quantum efficiencies for reaction are observed when the reactions are carried out under degassed conditions, indicating that the halide radical anions must survive long enough within the initial ion pair formed in the quenching step to undergo considerable return electron transfer. More strikingly we find that for certain pinacol-halide combinations reaction in aerared solutions leads to much higher efficiencies, which can be attributed to a chain reaction involving oxygen capture of a primary radical product. 25 refs., 1 fig., 1 tab.

  3. Mixed-Halide CH3 NH3 PbI3-x Xx (X=Cl, Br, I) Perovskites: Vapor-Assisted Solution Deposition and Application as Solar Cell Absorbers.

    PubMed

    Sedighi, Rahime; Tajabadi, Fariba; Shahbazi, Saeed; Gholipour, Somayeh; Taghavinia, Nima

    2016-08-01

    There have been recent reports on the formation of single-halide perovskites, CH3 NH3 PbX3 (X=Cl, Br, I), by means of vapor-assisted solution processing. Herein, the successful formation of mixed-halide perovskites (CH3 NH3 PbI3-x Xx ) by means of a vapor-assisted solution method at ambient atmosphere is reported. The perovskite films are synthesized by exposing PbI2 film to CH3 NH3 X (X=I, Br, or Cl) vapor. The prepared perovskite films have uniform surfaces with good coverage, as confirmed by SEM images. The inclusion of chlorine and bromine into the structure leads to a lower temperature and shorter reaction time for optimum perovskite film formation. In the case of CH3 NH3 PbI3-x Clx , the optimum reaction temperature is reduced to 100 °C, and the resulting phases are CH3 NH3 PbI3 (with trace Cl) and CH3 NH3 PbCl3 with a ratio of about 2:1. In the case of CH3 NH3 PbI3-x Brx , single-phase CH3 NH3 PbI2 Br is formed in a considerably shorter reaction time than that of CH3 NH3 PbI3 . The mesostructured perovskite solar cells based on CH3 NH3 PbI3 films show the best optimal power conversion efficiency of 13.5 %, whereas for CH3 NH3 PbI3-x Clx and CH3 NH3 PbI3-x Brx the best recorded efficiencies are 11.6 and 10.5 %, respectively. PMID:27124622

  4. Moving Towards a Technical Specification for Fluorescence Excitation-Emission Mapping and Absorbance Analysis of Colored Dissolved Organic Matter

    NASA Astrophysics Data System (ADS)

    Gilmore, A. M.

    2010-12-01

    Colored dissolved organic matter (CDOM) measurements with fluorescence and absorbance are important for evaluating a wide variety natural and industrial water sources. However, uncertainties and ambiguities continue to be propagated regarding interpretation of CDOM spectral data due to the variety of instruments, sampling chemistry conditions and types of analysis algorithms. Recent efforts have focused on standardization and interlaboratory comparisons of CDOM samples with respect to preparation, spectroscopic evaluation and mathematical analysis. This study deals with correlating absorbance and fluorescence data measured with the same sample to minimize interlaboratory variation. The theoretical significance of true simultaneous acquisition of the corrected (NIST Traceable) absorbance spectrum and fluorescence excitation spectral profile and excitation emission map is discussed as a means to provide the least ambiguous spectral data. Key issues considered are the variations introduced by ‘serial’ acquisitions of absorbance and fluorescence data. Variation can be caused by the different light-exposure history (especially UV) in the instruments, dissolved oxygen content associated with temperature changes and oxidation kinetics of the CDOM and in many cases concentration- and pH-related changes associated with diluting and pH buffering of the CDOM sample, respectively. Concentration changes in CDOM can be associated with optical anomalies including self-quenching and -absorption which systematically alter the fluorescence spectrum. Clearly, monitoring the absorbance and fluorescence simultaneously would deal with the above sampling variations and facilitate correcting the absorbance based fluorescence anomalies. The proposed method(s) described will be discussed in view of their potential to serve as the basis for an international technical specification in terms of the optical instrument and sampling conditions for CDOM analysis and reporting.

  5. Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon

    USGS Publications Warehouse

    Weishaar, J.L.; Aiken, G.R.; Bergamaschi, B.A.; Fram, M.S.; Fujii, R.; Mopper, K.

    2003-01-01

    Specific UV absorbance (SUVA) is defined as the UV absorbance of a water sample at a given wavelength normalized for dissolved organic carbon (DOC) concentration. Our data indicate that SUVA, determined at 254 nm, is strongly correlated with percent aromaticity as determined by 13C NMR for 13 organic matter isolates obtained from a variety of aquatic environments. SUVA, therefore, is shown to be a useful parameter for estimating the dissolved aromatic carbon content in aquatic systems. Experiments involving the reactivity of DOC with chlorine and tetramethylammonium hydroxide (TMAH), however, show a wide range of reactivity for samples with similar SUVA values. These results indicate that, while SUVA measurements are good predictors of general chemical characteristics of DOC, they do not provide information about reactivity of DOC derived from different types of source materials. Sample pH, nitrate, and iron were found to influence SUVA measurements.

  6. Multi-pulse LIBDE of fused silica at different thicknesses of the organic absorber layer

    NASA Astrophysics Data System (ADS)

    Pan, Yunxiang; Ehrhardt, Martin; Lorenz, Pierre; Han, Bing; Hopp, Bela; Vass, Csaba; Ni, Xiaowu; Zimmer, Klaus

    2015-12-01

    Laser-induced etching techniques feature several unique characteristics that enable ultraprecise machining of transparent materials. However, LIBDE (laser-induced back side dry etching) and LIBWE (laser-induced back side wet etching) are preferentially studied due to experimental feasibilities either using a very thin or a bulk absorber at the rear side of the transparent material. This study aims to fill the gap by examining the thickness dependence of the absorbing material. Multi-pulse-LIBDE (MP-LIBDE) of fused silica using different thick photoresist absorber layers (dL = 0.2-11.7 μm) was performed with a KrF excimer laser (λ = 248 nm, tp ≈ 20 ns). The influence of several experimental parameters, such as laser fluence, pulse number, film thickness, on the ablation morphology and the etching rate were investigated. Especially at moderate fluences (F = 0.7-1.5 J/cm2) MP-LIBDE and LIBWE show several similar process characteristics such as the etching rate dependence on the laser fluence and the pulse number with a typical etching rate of approx. 12 nm at 1 J/cm2. However, the specific etching rate values depend on the absorber layer thickness, for instance. The morphology of the etched surface is smooth with a roughness of below 5 nm rms. Further, the modification of the surface has been observed and will be discussed in relation to the multi-pulse laser etching mechanism.

  7. An environment-friendly and multi-functional absorbent from chitosan for organic pollutants and heavy metal ion.

    PubMed

    Li, Ang; Lin, Runjun; Lin, Chong; He, Bianyang; Zheng, Tingting; Lu, Lingbin; Cao, Yang

    2016-09-01

    Developing environment-friendly green absorbents for disposal of wastewater remains to be studied. In this paper, the cross-linked chitosan aerogel (CsA) as an environment-friendly absorbent was obtained by a simple method involving cross-linked process and freeze drying technique. Compared with conventional absorbents, the porous chitosan aerogel was provided with unique properties such as low density (0.0283g/cm(3)), high porosity (97.98%) and outstanding adsorption performance. The chitosan aerogel also displayed good reusability and excellent elasticity with a maximal thickness recovery up to 96.8% of the original thickness. The as-prepared absorbent exhibited preferable adsorption capacities for crude oil, diesel and copper ion (41.07g/g, 31.07g/g and 21.38mg/g, respectively). The aerogel can collect a wide range of organic solvents and oils with absorption capacities up to 40 times their own weight, depending on the density and viscosity of the liquids. The adsorption capacity for heavy metal ion was also considerable and the maximum adsorption capacity (qm) of the aerogel for copper ion was 35.08mg/g according to Langmuir isotherm model. Consequently, the chitosan aerogel with versatile adsorption properties has a good potential for wastewater treatment in environmental application. PMID:27185140

  8. Accurate spectral response measurements of a complementary absorbing organic tandem cell with fill factor exceeding the subcells

    SciTech Connect

    Cheyns, David; Kim, Minjae; Verreet, Bregt; Rand, Barry P.

    2014-03-03

    Single heterojunction organic photovoltaic cells based on co-evaporated donor–acceptor layers with power conversion efficiencies (η) above 5.5% are demonstrated, using either high (1.8 eV) or low (1.4 eV) optical gap materials. The high energy absorbing cell utilizes a high fullerene-C{sub 70} content, in combination with a high mobility amorphous donor, while the low energy absorbing cell consists of a donor–acceptor molecule paired with C{sub 60} as the acceptor. The integration of the two cells in an optimized tandem configuration leads to η =7.2%, verified by external quantum efficiency measurements of the subcells. Notably, the fill-factor of the tandem stack is higher than either one of the sub-cells.

  9. Method for absorbing hydrogen using an oxidation resisant organic hydrogen getter

    DOEpatents

    Shepodd, Timothy J.; Buffleben, George M.

    2009-02-03

    A composition for removing hydrogen from an atmosphere, comprising a mixture of a polyphenyl ether and a hydrogenation catalyst, preferably a precious metal catalyst, and most preferably platinum, is disclosed. This composition is stable in the presence of oxygen, will not polymerize or degrade upon exposure to temperatures in excess of 200.degree. C., or prolonged exposure to temperatures in the range of 100-300.degree. C. Moreover, these novel hydrogen getter materials can be used to efficiently remove hydrogen from mixtures of hydrogen/inert gas (e.g., He, Ar, N.sub.2), hydrogen/ammonia atmospheres, such as may be encountered in heat exchangers, and hydrogen/carbon dioxide atmospheres. Water vapor and common atmospheric gases have no adverse effect on the ability of these getter materials to absorb hydrogen.

  10. Two Dimensional Organometal Halide Perovskite Nanorods with Tunable Optical Properties.

    PubMed

    Aharon, Sigalit; Etgar, Lioz

    2016-05-11

    Organo-metal halide perovskite is an efficient light harvester in photovoltaic solar cells. Organometal halide perovskite is used mainly in its "bulk" form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halide perovskite, as well as the nanoscale properties. In this paper, we present facile low-temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g., octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. The 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light-emitting diodes, lasing, solar cells, and sensors. PMID:27089497

  11. Process for oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Lyke, Stephen E.

    1992-01-01

    An improved process for generating an elemental halogen selected from chlorine, bromine or iodine, from a corresponding hydrogen halide by absorbing a molten salt mixture, which includes sulfur, alkali metals and oxygen with a sulfur to metal molar ratio between 0.9 and 1.1 and includes a dissolved oxygen compound capable of reacting with hydrogen halide to produce elemental halogen, into a porous, relatively inert substrate to produce a substrate-supported salt mixture. Thereafter, the substrate-supported salt mixture is contacted (stage 1) with a hydrogen halide while maintaining the substrate-supported salt mixture during the contacting at an elevated temperature sufficient to sustain a reaction between the oxygen compound and the hydrogen halide to produce a gaseous elemental halogen product. This is followed by purging the substrate-supported salt mixture with steam (stage 2) thereby recovering any unreacted hydrogen halide and additional elemental halogen for recycle to stage 1. The dissolved oxygen compound is regenerated in a high temperature (stage 3) and an optical intermediate temperature stage (stage 4) by contacting the substrate-supported salt mixture with a gas containing oxygen whereby the dissolved oxygen compound in the substrate-supported salt mixture is regenerated by being oxidized to a higher valence state.

  12. Inorganic-organic solar cells based on quaternary sulfide as absorber materials.

    PubMed

    Hong, Tiantian; Liu, Zhifeng; Yan, Weiguo; Liu, Junqi; Zhang, Xueqi

    2015-12-14

    We report a novel promising quaternary sulfide (CuAgInS) to serve as a semiconductor sensitizer material in the photoelectrochemical field. In this study, CuAgInS (CAIS) sulfide sensitized ZnO nanorods were fabricated on ITO substrates through a facile and low-cost hydrothermal chemical method and applied on photoanodes for solar cells for the first time. The component and stoichiometry were key factors in determining the photoelectric performance of CAIS sulfide, which were controlled by modulating their reaction time. ZnO/Cu0.7Ag0.3InS2 nanoarrays exhibit an enhanced optical and photoelectric performance and the power conversion efficiency of ITO/ZnO/Cu0.7Ag0.3InS2/P3HT/Pt solid-state solar cell was up to 1.80%. The remarkable performance stems from improved electron transfer, a higher efficiency of light-harvesting and appropriate band gap alignment at the interface of the ZnO/Cu0.7Ag0.3InS2 NTs. The research indicates that CAIS as an absorbing material has enormous potential in solar cell systems. PMID:26553746

  13. Optimization of UV absorptivity of layered double hydroxide by intercalating organic UV-absorbent molecules.

    PubMed

    Mohsin, Sumaiyah Megat Nabil; Hussein, Mohd Zobir; Sarijo, Siti Halimah; Fakurazi, Sharida; Arulselvan, Palanisamy; Taufiq-Yap, Yun Hin

    2014-08-01

    Intercalation of Zn/Al layered double hydroxide (LDH) with benzophenone 9 (B9), a strong ultraviolet (UV) absorber, had been carried out by two different routes; co-precipitation and ion exchange method. Powder X-ray diffraction (PXRD) patterns of co-precipitated (ZB9C) and ion exchanged product (ZB91) showed basal spacing of 15.9 angstrom and 16.6 angstrom, respectively, as a result of the intercalation of B9 anions into the lamellae spaces of LDH. Intercalation was further confirmed by Fourier transform infrared spectra (FTIR), carbon, hydrogen, nitrogen and sulfur (CHNS) and thermogravimetric and differential thermogravimetric (TGA/DTG) studies. UV-vis absorption properties of the nanocomposite was investigated with diffuse reflectance UV-visible spectrometer and showed broader UV absorption range. Furthermore, stability of sunscreen molecules in LDH interlayer space was tested in deionized water, artificial sea water and skin pH condition to show slow deintercalation and high retention in host. Cytotoxicity study of the synthesized nanocomposites on human dermal fibroblast (HDF) cells shows no significant cytotoxicity after 24 h exposure for test concentrations up to 25 microg/mL. PMID:25016649

  14. On the Boiling Points of the Alkyl Halides.

    ERIC Educational Resources Information Center

    Correia, John

    1988-01-01

    Discusses the variety of explanations in organic chemistry textbooks of a physical property of organic compounds. Focuses on those concepts explaining attractive forces between molecules. Concludes that induction interactions play a major role in alkyl halides and other polar organic molecules and should be given wider exposure in chemistry texts.…

  15. Transparent Organic Photodetector using a Near-Infrared Absorbing Cyanine Dye

    PubMed Central

    Zhang, Hui; Jenatsch, Sandra; De Jonghe, Jelissa; Nüesch, Frank; Steim, Roland; Véron, Anna C.; Hany, Roland

    2015-01-01

    Organic photodetectors are interesting for low cost, large area optical sensing applications. Combining organic semiconductors with discrete absorption bands outside the visible wavelength range with transparent and conductive electrodes allows for the fabrication of visibly transparent photodetectors. Visibly transparent photodetectors can have far reaching impact in a number of areas including smart displays, window-integrated electronic circuits and sensors. Here, we demonstrate a near-infrared sensitive, visibly transparent organic photodetector with a very high average visible transmittance of 68.9%. The transmitted light of the photodetector under solar irradiation exhibits excellent transparency colour perception and rendering capabilities. At a wavelength of 850 nm and at −1 V bias, the photoconversion efficiency is 17% and the specific detectivity is 1012 Jones. Large area photodetectors with an area of 1.6 cm2 are demonstrated. PMID:25803320

  16. Study of two-photon excitation spectra of organic compounds absorbing in the UV region

    SciTech Connect

    Babenko, V A; Sychev, Andrei A

    2004-12-31

    A method is proposed for recording two-photon excitation (TPE) spectra of organic compounds with the help of picosecond pulses from a dye laser tunable in the range from 550 to 640 nm. The TPE spectra are obtained for organic scintillators and drugs: paraterphenyl in liquid and solid phases, stilbene single crystal and Streptocid powder, having a one-photon absorption band in the region from 270 to 350 nm. It is shown that the vibronic structure in the TPE spectra of these compounds is independent of their aggregate state and is an individual characteristic of each of the compounds. (active media)

  17. PREPARATION OF HALIDES OF PLUTONIUM

    DOEpatents

    Garner, C.S.; Johns, I.B.

    1958-09-01

    A dry chemical method is described for preparing plutonium halides, which consists in contacting plutonyl nitrate with dry gaseous HCl or HF at an elevated temperature. The addition to the reaction gas of a small quantity of an oxidizing gas or a reducing gas will cause formation of the tetra- or tri-halide of plutonium as desired.

  18. Application of high-resolution spectral absorbance measurements to determine dissolved organic carbon concentration in remote areas

    NASA Astrophysics Data System (ADS)

    Avagyan, Armine; Runkle, Benjamin R. K.; Kutzbach, Lars

    2014-09-01

    Accurate quantification of dissolved organic carbon (DOC) in surface and soil pore waters is crucial for understanding changes in water resources under the influence of climate and land use changes. Sampling and laboratory analysis of DOC content at a sufficient temporal frequency are especially difficult to achieve for natural DOC sources like the extensive boreal and arctic mire landscapes due to their remoteness. Therefore, the goals of this paper are (1) to investigate the performance of a portable, high-resolution ultraviolet-visible light spectroscopic method for determining the DOC content of surface and soil pore water samples from a boreal mire complex and (2) to compare the spectroscopic method with other DOC measurement techniques, e.g., the wet heated persulfate oxidation method and a laboratory, expulsion-based spectrophotometric method and (3) to assess different multivariate models that relate absorbance measurements with DOC contents. The study indicates that high-resolution spectroscopic measurements provide a simple, robust and non-destructive method for measuring DOC content. These measurements are of short duration (<1 min) and the sample analysis is portable, rendering this method particularly advantageous for in situ investigations at remote field locations. The study also demonstrates that if absorbances at specific wavelengths are used as proxies for DOC concentration, it is recommended to create site-specific calibration models that include more than one wavelength to achieve the optimal accuracy of the proxy-based DOC quantification.

  19. Seasonal variations in the light-absorbing properties of water-soluble and insoluble organic aerosols in Seoul, Korea

    NASA Astrophysics Data System (ADS)

    Kim, Hwajin; Kim, Jin Young; Jin, Hyoun Cher; Lee, Ji Yi; Lee, Se Pyo

    2016-03-01

    The spectral properties of light-absorbing organic aerosol extractions were investigated using 24-h average fine particulate matter (PM2.5) measurements from October 2012 to September 2013 in Seoul, Korea. The light-absorption spectra of water and methanol extracts exhibited strong evidence of brown carbon with Absorption Angstrom Exponent (AAE; fitted between 300 and 700 nm) ranges of 5.84-9.17 and 4.08-5.75, with averages of 7.23 ± 1.58 and 5.05 ± 0.67, respectively. The light absorption of both extracts at 365 nm (Abs365), which is typically used as a proxy for brown carbon (BrC), displayed strong seasonal variations and was well correlated with both water-soluble organic carbon (WSOC; r = 0.81) and organic carbon (OC; r = 0.85), indicating that both primary and secondary organics were sources of BrC in this region. Normalizing the Abs365 of water and methanol extracts to the mass of WSOC and OC yielded average solution mass absorption efficiency (MAE365) of 0.28-1.18 and 0.44-1.45 m2 g-1 C, respectively. MAE365 in Korea were in the same range or slightly lower than those in China, however, despite the same ranges, the seasonal variations were different, suggesting that the sources of light absorbers could be different. Combining the AAE, Abs365, and MAE365 of both extracts and a detailed chemical speciation of filter extracts identified the compounds responsible for the temporal variations of BrC in Korea. During summer, secondary organic aerosol (SOA), photochemically generated from anthropogenic emissions, was the major source; however, during winter, long range transported organics or transported BrC seem to be a source of BrC in Korea, a downwind site of China, where severe smog and BrC were observed during this season. Biomass burning was also an important source; however, unlike in previous studies, where it was identified as a major source during winter, here, it contributed during the whole year. Although many of its properties, sources, and potential

  20. Adsorption on Alkali Halides.

    NASA Astrophysics Data System (ADS)

    Urzua Duran, Gilberto Antonio

    1995-01-01

    Using a variety of interionic potentials, I have computed the configurations of adsorbed alkali halides monomers on the (001) surface of selected alkali halides crystals. In the majority of cases studied it is found that the monomer adsorbs perpendicular to the surface with the cation sitting nearly on top of the surface anion. In about ten percent of the cases though the monomer adsorbs tilted from the vertical. In these cases the ion that is closer to the surface can be the cation or the anion. The effect of polarization forces is found to be important. In order to discuss the effects of surface retaxation with adsorbates, I have evaluated the surface relaxation of the alkali halide crystals, using a shell model for the interionic forces. It is found that surface relaxation and rumpling are generally small, especially when the van der Waals forces are included. A theory of the effect of substrate vibrations on the binding of an adsorbed atom is developed. At T = 0 the binding energy is D_0-E, where D_0 is the surface well depth (classical binding energy) and E is the quantum correction. For several simple models, it is found that E is surprisingly model-independent. We compare D _0-E with the binding energies to a rigid substrate, D_0-E_{rs}, and to a vibrationally averaged substrate, D _0-E_{va}. We prove that E_{va}>=q E>=q E_ {rs} and that similar relations hold at finite temperature for the free energy of binding. In most cases E_{rs} is better than E_{va} as an approximation to E.

  1. Halide laser glasses

    SciTech Connect

    Weber, M.J.

    1982-01-14

    Energy storage and energy extraction are of prime importance for efficient laser action and are affected by the line strengths and linewidths of optical transitions, excited-state lifetimes, nonradiative decay processes, spectroscopic inhomogeneities, nonlinear refractive index, and damage threshold. These properties are all host dependent. To illustrate this, the spectroscopic properties of Nd/sup 3 +/ have been measured in numerous oxide, oxyhalide, and halide glasses. A table summarizes the reported ranges of stimulated emission cross sections, peak wavelengths, linewidths, and radiative lifetimes associated with the /sup 4/F/sub 3/2/ ..-->.. /sup 4/I/sub 11/2/ lasing transition.

  2. Measurement of absorbed doses in organs of medical staff at (18)F-FDG pet examination.

    PubMed

    Fujibuchi, Toshioh; Iimori, Takashi; Isobe, Tomonori; Masuda, Yoshitada; Uchida, Yoshitaka; Matsubayashi, Fumiyasu; Sakae, Takeji

    2010-01-01

    In this study, the organ doses were measured using a human- body phantom simulating a medical staff member, and we considered an effective method for decreasing exposure to staff in positron emission tomography examinations. A fluorescence glass dosimeter was arranged for measurements in various organs. Regarding exposure, the average ratio of the dose at 100 cm from the source to the dose at 30 cm was 0.35. The ratio of the dose at 100 cm with a 3 cm lead shield to the dose at 100 cm with no shielding device was 0.01. To reduce the radiation exposure effectively, medical staff members should inform the patient of the details of the examination in advance, reduce the contact time with the patient during the examination, and maximize their distance from the patient when contact is necessary. PMID:20821099

  3. Synthesis and characterization of a sphere-like modified chitosan and acrylate resin composite for organics absorbency

    NASA Astrophysics Data System (ADS)

    Xin, S. S.; Wang, Y. H.; Li, Q. R.; Zhang, Q.; Wang, X. P.

    2015-07-01

    In this study, the chitosan (deacetylation degree >95%) was modified with vinyltriethoxysilane (A151) and became hydrophobic. The modified chitosan and acrylate resin composite can be synthesized by butyl methacrylate (BMA), butyl acrylate (BA), poly vinyl alcoho(PVA), N,N’-methylene bisacrylamide (MBA), benzoyl peroxide (BPO), and ethyl acetate under microwave irradiation. The optimal synthetic condition was as follows: the molar ratio of BA and BMA was 1.5:1, the dosage of ethyl acetate, PVA, MBA, BPO and modified chitosan were 50 wt.%, 10 wt.%, 1.5 wt.%, 2.0 wt.% and 1.0 wt.% of monomers, respectively. The adsorption capacity of the composite for CHCl3 and CCl4 were approximate to 53 g/g and 44 g/g, respectively. The organics absorbency and regeneration of the samples were also tested, and the samples were characterized by analysis of the scanning electron microscope and simultaneous thermo gravimetric/differential thermal.

  4. Method 415.3, Rev. 1.2: Determination of Total Organic Carbon and Specific UV Absorbance at 254 nm in Source Water and Drinking Water

    EPA Science Inventory

    This method provides procedures for the determination of total organic carbon (TOC), dissolved organic carbon (DOC), and UV absorption at 254 nm (UVA) in source waters and drinking waters. The DOC and UVA determinations are used in the calculation of the Specific UV Absorbance (S...

  5. A new carboxyl-copper-organic framework and its excellent selective absorbability for proteins

    SciTech Connect

    Yang, Linyan; Xin, Liangliang; Gu, Wen; Tian, Jinlei; Liao, Shengyun; Du, Peiyao; Tong, Yuzhang; Zhang, Yanping; Lv, Rui; Wang, Jingyao; Liu, Xin

    2014-10-15

    One-pot solvothermal treatments of CuCl{sub 2}·2H{sub 2}O, H{sub 2}L (5-(3-methyl-5-(pyridin-4-yl)-4H-1,2,4-triazol-4-yl) isophthalic acid) and Sm(NO{sub 3}){sub 3}·6H{sub 2}O in water yielded a rare carboxyl-copper-organic framework, [Cu(HL)]{sub n}·nH{sub 2}O (1). The existence of carboxyl groups in compound 1 may be due to the interference of Sm(NO{sub 3}){sub 3}·6H{sub 2}O at the relatively high temperature and autogenous pressure of the reaction. Compound 1 has been characterized by single-crystal X-ray diffraction, PXRD, IR, and elemental analysis. Compound 1 is a 3D coordination polymer, and an xfe-4-Fddd, (4{sup 2}.6.8{sup 3}) topology in 1 is created. In addition, the optical properties have been investigated. Rhodamine B dyeing experiments exhibited that there were residual carboxyl groups on the surface of compound 1. UV–vis results showed that more lysozyme was adsorbed onto the surface of compound 1 than BSA at pH 7.4. At the same time, XPS spectra were also investigated to verify the results. - Graphical abstract: One-pot solvothermal treatments of CuCl{sub 2}·2H{sub 2}O, H2L (5-(3-methyl-5-(pyridin-4-yl)-4H-1, 2, 4-triazol-4-yl) isophthalic acid) and Sm(NO{sub 3}){sub 3}·6H{sub 2}O in water yielded a rare carboxyl-copper-organic framework, [Cu(HL)]n·nH{sub 2}O (1). The existence of carboxyl groups in compound 1 may be due to the interference of Sm(NO{sub 3}){sub 3}·6H{sub 2}O at the relatively high temperature and autogenous pressure of the reaction. Compound 1 has been characterized by single-crystal X-ray diffraction, XRPD, IR, and elemental analysis. Compound 1 is a 3D coordination polymer, and an xfe-4-Fddd, (4{sup 2}.6.8{sup 3}) topology in 1 is created. In addition, the optical properties have been investigated. Rhodamine B dyeing experiments exhibited that there were residual carboxyl groups on the surface of compound 1. UV-vis results showed that more lysozyme was adsorbed onto the surface of compound 1 than that of BSA at pH 7

  6. Simultaneous trace determination of nine organic UV-absorbing compounds (UV filters) in environmental samples.

    PubMed

    Zenker, Armin; Schmutz, Hansruedi; Fent, Karl

    2008-08-15

    A new sensitive method has been successfully developed and validated for the simultaneous determination and quantification of nine estrogenic UV filters (benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-4, 4,4-dihydroxybenzophenone, ethyl-4-aminobenzoate, 2-ethyl-hexyl-4-trimethoxycinnamate, 3-(4-methylbenzylidene)-camphor, 3-benzylidene-camphor) in different environmental matrices. After optimisation of extraction conditions for the best recovery of polar to lipophilic compounds from fish tissue and a subsequent lipid clean-up in HPLC, fish extraction recoveries exceeded 72% for all nine UV filters. Identification and quantification of compounds was performed for lipophilic UV filters with gas chromatography-electroionisation-mass spectrometry and for polar and mid-polar compounds with liquid chromatography coupled to electrospray ionisation mass spectrometry. Instrumental detection limits (IDL) varied between 5 and 260 pg injected and method detection limits (MDL) were in the low ng/g lipids range for all test compounds. The described analytical methods are shown to be useful to screen for estrogenic UV filters in environmental samples such as fish and polar organic chemical integrative samplers. PMID:18632108

  7. A new carboxyl-copper-organic framework and its excellent selective absorbability for proteins

    NASA Astrophysics Data System (ADS)

    Yang, Linyan; Xin, Liangliang; Gu, Wen; Tian, Jinlei; Liao, Shengyun; Du, Peiyao; Tong, Yuzhang; Zhang, Yanping; Lv, Rui; Wang, Jingyao; Liu, Xin

    2014-10-01

    One-pot solvothermal treatments of CuCl2·2H2O, H2L (5-(3-methyl-5-(pyridin-4-yl)-4H-1,2,4-triazol-4-yl) isophthalic acid) and Sm(NO3)3·6H2O in water yielded a rare carboxyl-copper-organic framework, [Cu(HL)]n·nH2O (1). The existence of carboxyl groups in compound 1 may be due to the interference of Sm(NO3)3·6H2O at the relatively high temperature and autogenous pressure of the reaction. Compound 1 has been characterized by single-crystal X-ray diffraction, PXRD, IR, and elemental analysis. Compound 1 is a 3D coordination polymer, and an xfe-4-Fddd, (42.6.83) topology in 1 is created. In addition, the optical properties have been investigated. Rhodamine B dyeing experiments exhibited that there were residual carboxyl groups on the surface of compound 1. UV-vis results showed that more lysozyme was adsorbed onto the surface of compound 1 than BSA at pH 7.4. At the same time, XPS spectra were also investigated to verify the results.

  8. Systematic analysis of the unique band gap modulation of mixed halide perovskites.

    PubMed

    Kim, Jongseob; Lee, Sung-Hoon; Chung, Choong-Heui; Hong, Ki-Ha

    2016-02-14

    Solar cells based on organic-inorganic hybrid metal halide perovskites have been proven to be one of the most promising candidates for the next generation thin film photovoltaic cells. Mixing Br or Cl into I-based perovskites has been frequently tried to enhance the cell efficiency and stability. One of the advantages of mixed halides is the modulation of band gap by controlling the composition of the incorporated halides. However, the reported band gap transition behavior has not been resolved yet. Here a theoretical model is presented to understand the electronic structure variation of metal mixed-halide perovskites through hybrid density functional theory. Comparative calculations in this work suggest that the band gap correction including spin-orbit interaction is essential to describe the band gap changes of mixed halides. In our model, both the lattice variation and the orbital interactions between metal and halides play key roles to determine band gap changes and band alignments of mixed halides. It is also presented that the band gap of mixed halide thin films can be significantly affected by the distribution of halide composition. PMID:26791587

  9. Filter-free integrated sensor array based on luminescence and absorbance measurements using ring-shaped organic photodiodes.

    PubMed

    Abel, Tobias; Sagmeister, Martin; Lamprecht, Bernhard; Kraker, Elke; Köstler, Stefan; Ungerböck, Birgit; Mayr, Torsten

    2012-12-01

    An optical waveguiding sensor array featuring monolithically integrated organic photodiodes as integrated photo-detector, which simplifies the readout system by minimizing the required parts, is presented. The necessity of any optical filters becomes redundant due to the proposed platform geometry, which discriminates between excitation light and sensing signal. The sensor array is capable of measuring luminescence or absorption, and both sensing geometries are based on the identical substrate. It is demonstrated that background light is virtually non-existent. All sensing and waveguide layers, as well as in- and out-coupling elements are assembled by conventional screen-printing techniques. Organic photodiodes are integrated by layer-by-layer vacuum deposition onto glass or common polymer foils. The universal and simple applicability of this sensor chip is demonstrated by sensing schemes for four different analytes. Relative humidity, oxygen, and carbon dioxide are measured in gas phase using luminescence-based sensor schemes; the latter two analytes are also measured by absorbance-based sensor schemes. Furthermore, oxygen and pH in aqueous media were enabled. The consistency of calibration characteristics extending over different sensor chips is verified. PMID:22706404

  10. Enhancing the carrier thermalization time in organometallic perovskites by halide mixing.

    PubMed

    Madjet, Mohamed El-Amine; Akimov, Alexey V; El-Mellouhi, Fadwa; Berdiyorov, Golibjon R; Ashhab, Sahel; Tabet, Nouar; Kais, Sabre

    2016-02-21

    Hybrid metal-organic halide perovskites have recently attracted a great deal of attention because of their interesting electronic, optical and transport properties, which make them promising materials for high-performance, low-cost solar cells. Fundamental understanding of the formation mechanisms and dynamics of photoinduced charge carriers is essential for improving the performance of perovskite solar cell devices. For example, a significant amount of absorbed solar energy is lost as a result of carrier thermalization. This energy could be harnessed by extracting hot carriers before they cool down to the band edges. Although such hot carrier collection is experimentally challenging, theoretical investigations based on time-dependent methods can guide future experimental research by providing insights into the thermalization process. Here, we perform ab initio nonadiabatic molecular dynamics simulations to study non-radiative relaxation dynamics of charge carriers in hybrid halide perovskites. We find that the carrier relaxation time can be considerably increased by mixing halogen atoms in the perovskite materials. These findings show that simple approaches could be adopted to slow down the thermalization process of hot carriers in perovskite materials. PMID:26812955

  11. A Bismuth-Halide Double Perovskite with Long Carrier Recombination Lifetime for Photovoltaic Applications.

    PubMed

    Slavney, Adam H; Hu, Te; Lindenberg, Aaron M; Karunadasa, Hemamala I

    2016-02-24

    Despite the remarkable rise in efficiencies of solar cells containing the lead-halide perovskite absorbers RPbX3 (R = organic cation; X = Br(-) or I(-)), the toxicity of lead remains a concern for the large-scale implementation of this technology. This has spurred the search for lead-free materials with similar optoelectronic properties. Here, we use the double-perovskite structure to incorporate nontoxic Bi(3+) into the perovskite lattice in Cs2AgBiBr6 (1). The solid shows a long room-temperature fundamental photoluminescence (PL) lifetime of ca. 660 ns, which is very encouraging for photovoltaic applications. Comparison between single-crystal and powder PL decay curves of 1 suggests inherently high defect tolerance. The material has an indirect bandgap of 1.95 eV, suited for a tandem solar cell. Furthermore, 1 is significantly more heat and moisture stable compared to (MA)PbI3. The extremely promising optical and physical properties of 1 shown here motivate further exploration of both inorganic and hybrid halide double perovskites for photovoltaics and other optoelectronics. PMID:26853379

  12. Heat capacity of molten halides.

    PubMed

    Redkin, Alexander A; Zaikov, Yurii P; Korzun, Iraida V; Reznitskikh, Olga G; Yaroslavtseva, Tatiana V; Kumkov, Sergey I

    2015-01-15

    The heat capacities of molten salts are very important for their practical use. Experimental investigation of this property is challenging because of the high temperatures involved and the corrosive nature of these materials. It is preferable to combine experimental investigations with empirical relationships, which allows for the evaluation of the heat capacity of molten salt mixtures. The isobaric molar heat capacities of all molten alkali and alkaline-earth halides were found to be constant for each group of salts. The value depends on the number of atoms in the salt, and the molar heat capacity per atom is constant for all molten halide salts with the exception of the lithium halides. The molar heat capacities of molten halides do not change when the anions are changed. PMID:25530462

  13. Absorbed Radiation Dose in Radiosensitive Organs Using 64- and 320-Row Multidetector Computed Tomography: A Comparative Study

    PubMed Central

    Khan, Atif N.; Nikolic, Boris; Khan, Mohammad K.; Kang, Jian; Khosa, Faisal

    2014-01-01

    Aim. To determine absorbed radiation dose (ARD) in radiosensitive organs during prospective and full phase dose modulation using ECG-gated MDCTA scanner under 64- and 320-row detector modes. Methods. Female phantom was used to measure organ radiation dose. Five DP-3 radiation detectors were used to measure ARD to lungs, breast, and thyroid using the Aquilion ONE scanner in 64- and 320-row modes using both prospective and dose modulation in full phase acquisition. Five measurements were made using three tube voltages: 100, 120, and 135 kVp at 400 mA at heart rate (HR) of 60 and 75 bpm for each protocol. Mean acquisition was recorded in milligrays (mGy). Results. Mean ARD was less for 320-row versus 64-row mode for each imaging protocol. Prospective EKG-gated imaging protocol resulted in a statistically lower ARD using 320-row versus 64-row modes for midbreast (6.728 versus 19.687 mGy, P < 0.001), lung (6.102 versus 21.841 mGy, P < 0.001), and thyroid gland (0.208 versus 0.913 mGy; P < 0.001). Retrospective imaging using 320- versus 64-row modes showed lower ARD for midbreast (10.839 versus 43.169 mGy, P < 0.001), lung (8.848 versus 47.877 mGy, P < 0.001), and thyroid gland (0.057 versus 2.091 mGy; P < 0.001). ARD reduction was observed at lower kVp and heart rate. Conclusions. Dose reduction to radiosensitive organs is achieved using 320-row compared to 64-row modes for both prospective and retrospective gating, whereas 64-row mode is equivalent to the same model 64-row MDCT scanner. PMID:25170427

  14. Formation of nitrogen- and sulfur-containing light-absorbing compounds accelerated by evaporation of water from secondary organic aerosols

    NASA Astrophysics Data System (ADS)

    Nguyen, Tran B.; Lee, Paula B.; Updyke, Katelyn M.; Bones, David L.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey A.

    2012-01-01

    Aqueous extracts of secondary organic aerosols (SOA) generated from the ozonolysis of d-limonene were subjected to dissolution, evaporation, and re-dissolution in the presence and absence of ammonium sulfate (AS). Evaporation with AS at pH 4-9 produced chromophores that were stable with respect to hydrolysis and had a distinctive absorption band at 500 nm. Evaporation accelerated the rate of chromophore formation by at least three orders of magnitude compared to the reaction in aqueous solution, which produced similar compounds. Absorption spectroscopy and high-resolution nanospray desorption electrospray ionization (nano-DESI) mass spectrometry experiments suggested that the molar fraction of the chromophores was small (<2%), and that they contained nitrogen atoms. Although the colored products represented only a small fraction of SOA, their large extinction coefficients (>105 L mol-1 cm-1 at 500 nm) increased the effective mass absorption coefficient of the residual organics in excess of 103 cm2 g-1 - a dramatic effect on the optical properties from minor constituents. Evaporation of SOA extracts in the absence of AS resulted in the production of colored compounds only when the SOA extract was acidified to pH ˜ 2 with sulfuric acid. These chromophores were produced by acid-catalyzed aldol condensation, followed by a conversion into organosulfates. The presence of organosulfates was confirmed by high resolution mass spectrometry experiments. Results of this study suggest that evaporation of cloud or fog droplets containing dissolved organics leads to significant modification of the molecular composition and serves as a potentially important source of light-absorbing compounds.

  15. Formation of Nitrogen- and Sulfur-Containing Light-Absorbing Compounds Accelerated by Evaporation of Water from Secondary Organic Aerosols

    SciTech Connect

    Nguyen, Tran B.; Lee, Paula B.; Updyke, Katelyn M.; Bones, David L.; Laskin, Julia; Laskin, Alexander; Nizkorodov, Sergey

    2012-01-14

    Aqueous extracts of secondary organic aerosols (SOA) generated from the ozonolysis of dlimonene were subjected to dissolution, evaporation, and re-dissolution in the presence and absence of ammonium sulfate (AS). Evaporation with AS at pH 4-9 produced chromophores that were stable with respect to hydrolysis and had a distinctive absorption band at 500 nm. Evaporation accelerated the rate of chromophore formation by at least three orders of magnitude compared to the reaction in aqueous solution, which produced similar compounds. Absorption spectroscopy and high-resolution nanospray desorption electrospray ionization (nano-DESI) mass spectrometry experiments suggested that the molar fraction of the chromophores was small (< 2%), and that they contained nitrogen atoms. Although the colored products represented only a small fraction of SOA, their large extinction coefficients (>10{sup 5} L mol{sup -1} cm{sup -1} at 500 nm) increased the effective mass absorption coefficient of the residual organics in excess of 10{sup 3} cm{sup 2} g{sup -1} - a dramatic effect on the optical properties from minor constituents. Evaporation of SOA extracts in the absence of AS resulted in the production of colored compounds only when the SOA extract was acidified to pH {approx} 2 with sulfuric acid. These chromophores were produced by acid-catalyzed aldol condensation, followed by a conversion into organosulfates. The presence of organosulfates was confirmed by high resolution mass spectrometry experiments. Results of this study suggest that evaporation of cloud or fog droplets containing dissolved organics leads to significant modification of the molecular composition and serves as a potentially important source of light-absorbing compounds.

  16. Chemical characteristics and light-absorbing property of water-soluble organic carbon in Beijing: Biomass burning contributions

    NASA Astrophysics Data System (ADS)

    Yan, Caiqing; Zheng, Mei; Sullivan, Amy P.; Bosch, Carme; Desyaterik, Yury; Andersson, August; Li, Xiaoying; Guo, Xiaoshuang; Zhou, Tian; Gustafsson, Örjan; Collett, Jeffrey L.

    2015-11-01

    Emissions from biomass burning contribute significantly to water-soluble organic carbon (WSOC) and light-absorbing organic carbon (brown carbon). Ambient atmospheric samples were collected at an urban site in Beijing during winter and summer, along with source samples from residential crop straw burning. Carbonaceous aerosol species, including organic carbon (OC), elemental carbon (EC), WSOC and multiple saccharides as well as water-soluble potassium (K+) in PM2.5 (fine particulate matter with size less than 2.5 μm) were measured. Chemical signatures of atmospheric aerosols in Beijing during winter and summer days with significant biomass burning influence were identified. Meanwhile, light absorption by WSOC was measured and quantitatively compared to EC at ground level. The results from this study indicated that levoglucosan exhibited consistently high concentrations (209 ± 145 ng m-3) in winter. Ratios of levoglucosan/mannosan (L/M) and levoglucosan/galacosan (L/G) indicated that residential biofuel use is an important source of biomass burning aerosol in winter in Beijing. Light absorption coefficient per unit ambient WSOC mass calculated at 365 nm is approximately 1.54 ± 0.16 m2 g-1 in winter and 0.73 ± 0.15 m2 g-1 in summer. Biomass burning derived WSOC accounted for 23 ± 7% and 16 ± 7% of total WSOC mass, and contributed to 17 ± 4% and 19 ± 5% of total WSOC light absorption in winter and summer, respectively. It is noteworthy that, up to 30% of total WSOC light absorption was attributed to biomass burning in significant biomass-burning-impacted summer day. Near-surface light absorption (over the range 300-400 nm) by WSOC was about ∼40% of that by EC in winter and ∼25% in summer.

  17. METHOD OF PREPARING METAL HALIDES

    DOEpatents

    Hendrickson, A.V.

    1958-11-18

    The conversion of plutonium halides from plutonium peroxide can be done by washing the peroxide with hydrogen peroxide, drying the peroxide, passing a dry gaseous hydrohalide over the surface of the peroxide at a temperature of about lOO icient laborato C until the reaction rate has stabillzed, and then ralsing the reaction temperature to between 400 and 600 icient laborato C until the conversion to plutonium halide is substantially complete.

  18. Approaching Bulk Carrier Dynamics in Organo-Halide Perovskite Nanocrystalline Films by Surface Passivation.

    PubMed

    Stewart, Robert J; Grieco, Christopher; Larsen, Alec V; Maier, Joshua J; Asbury, John B

    2016-04-01

    The electronic properties of organo-halide perovskite absorbers described in the literature have been closely associated with their morphologies and processing conditions. However, the underlying origins of this dependence remain unclear. A combination of inorganic synthesis, surface chemistry, and time-resolved photoluminescence spectroscopy was used to show that charge recombination centers in organo-halide perovskites are almost exclusively localized on the surfaces of the crystals rather than in the bulk. Passivation of these surface defects causes average charge carrier lifetimes in nanocrystalline thin films to approach the bulk limit reported for single-crystal organo-halide perovskites. These findings indicate that the charge carrier lifetimes of perovskites are correlated with their thin-film processing conditions and morphologies through the influence these have on the surface chemistry of the nanocrystals. Therefore, surface passivation may provide a means to decouple the electronic properties of organo-halide perovskites from their thin-film processing conditions and corresponding morphologies. PMID:26966792

  19. Making and Breaking of Lead Halide Perovskites.

    PubMed

    Manser, Joseph S; Saidaminov, Makhsud I; Christians, Jeffrey A; Bakr, Osman M; Kamat, Prashant V

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  20. Sense or no-sense of the sum parameter for water soluble "adsorbable organic halogens" (AOX) and "absorbed organic halogens" (AOX-S18) for the assessment of organohalogens in sludges and sediments.

    PubMed

    Müller, German

    2003-07-01

    "AOX" is the abbreviation of the sum parameter for water soluble "adsorbable organic halogens" in which 'A' stands for adsorbable, 'O' for organic and 'X' for the halogens chlorine, bromine and iodine. After the introduction of the AOX in 1976, this parameter has been correctly used for "real" AOX constituents (DDT and its metabolites, PCBs, etc.) but also misused for non-adsorbable adsorbed OX-compounds, mostly high molecular organohalogens in plants and even to inorganic compounds being neither organic nor adsorbable. The question of natural "Adsorbable Organic Halogens" (AOX) formed by living organisms and/or during natural abiogenic processes has been definitively solved by the known existence of already more than 3650 organohalogen compounds, amongst them the highly reactive, cancerogenic vinyl chloride (VC). The extension of the AOX to AOX-S18 for Sludges and Sediments, in which A stands for adsorbed (not for adsorbable) is questionable. It includes the most important water insoluble technical organochlorine product: polyvinyl chloride, PVC. In addition to organic halogens it also includes inorganic, mineralogenic halides, incorporated mainly in the crystal lattice of fine grained phyllosilicates, the typical clay minerals (kaolinite, montmorillonite, illite and chlorite) which are main constituents of sediments and sedimentary rocks representing the major part of the sedimentary cover of the earth. Other phyllosilicates, biotite and muscovite, major constituents of granites and many metamorphic rocks (gneiss and mica schist) will also contribute to the AOX-S18 especially in soils as result of weathering processes. Since chlorine is incorporated into the mineral structure and, as a consequence, not soluble by the nitric acid analytical step (pH 0.5) of the S18 determination, it will account to the AOX-S18 in the final charcoal combustion step at temperatures >950 degrees C. After heavy rainfalls sewage sludge composition is strongly influenced by

  1. Actinide halide complexes

    DOEpatents

    Avens, L.R.; Zwick, B.D.; Sattelberger, A.P.; Clark, D.L.; Watkin, J.G.

    1992-11-24

    A compound is described of the formula MX[sub n]L[sub m] wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands. A compound of the formula MX[sub n] wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds are described including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant.

  2. Actinide halide complexes

    DOEpatents

    Avens, Larry R.; Zwick, Bill D.; Sattelberger, Alfred P.; Clark, David L.; Watkin, John G.

    1992-01-01

    A compound of the formula MX.sub.n L.sub.m wherein M is a metal atom selected from the group consisting of thorium, plutonium, neptunium or americium, X is a halide atom, n is an integer selected from the group of three or four, L is a coordinating ligand selected from the group consisting of aprotic Lewis bases having an oxygen-, nitrogen-, sulfur-, or phosphorus-donor, and m is an integer selected from the group of three or four for monodentate ligands or is the integer two for bidentate ligands, where the sum of n+m equals seven or eight for monodentate ligands or five or six for bidentate ligands, a compound of the formula MX.sub.n wherein M, X, and n are as previously defined, and a process of preparing such actinide metal compounds including admixing the actinide metal in an aprotic Lewis base as a coordinating solvent in the presence of a halogen-containing oxidant, are provided.

  3. Semiempirical and DFT Investigations of the Dissociation of Alkyl Halides

    ERIC Educational Resources Information Center

    Waas, Jack R.

    2006-01-01

    Enthalpy changes corresponding to the gas phase heats of dissociation of 12 organic halides were calculated using two semiempirical methods, the Hartree-Fock method, and two DFT methods. These calculated values were compared to experimental values where possible. All five methods agreed generally with the expected empirically known trends in the…

  4. Preparation of cerium halide solvate complexes

    DOEpatents

    Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

    2013-08-06

    Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

  5. In situ aerosol optics in Reno, NV, USA during and after the summer 2008 California wildfires and the influence of absorbing and non-absorbing organic coatings on spectral light absorption

    NASA Astrophysics Data System (ADS)

    Gyawali, M.; Arnott, W. P.; Lewis, K.; Moosmüller, H.

    2009-10-01

    Hundreds of wildfires in Northern California were sparked by lightning during the summer of 2008, resulting in downwind smoke for the months of June and July. Comparisons are reported for aerosol optics measurements in Reno, Nevada made during the very smoky month of July and the relatively clean month of August. Photoacoustic instruments equipped with integrating nephelometers were used to measure aerosol light scattering and absorption coefficients at wavelengths of 405 nm and 870 nm, revealing a strong variation of aerosol light absorption with wavelength. Insight on fuels burned is gleaned from comparison of Ångström exponents of absorption (AEA) versus single scattering albedo (SSA) of the ambient measurements with laboratory biomass smoke measurements for many fuels. Measurements during the month of August, which were largely unaffected by fire smoke, exhibit surprisingly low AEA for aerosol light absorption when the SSA is highest, again likely as a consequence of the underappreciated wavelength dependence of aerosol light absorption by particles coated with non-absorbing organic and inorganic matter. Coated sphere calculations were used to show that AEA as large as 1.6 are possible for wood smoke even with non-absorbing organic coatings on black carbon cores, suggesting care be exercised when diagnosing AEA.

  6. High-Dose 131I-Tositumomab (Anti-CD20) Radioimmunotherapy for Non-Hodgkin's Lymphoma: Adjusting Radiation Absorbed Dose to Actual Organ Volumes

    SciTech Connect

    Rajendran, Joseph G.; Fisher, Darrell R.; Gopal, A K.; Durack, L. D.; Press, O. W.; Eary, Janet F.

    2004-06-01

    Radioimmunotherapy (RIT) using 131I-tositumomab has been used successfully to treat relapsed or refractory B-cell non-Hodgin's lymphoma (NHL). Our approach to treatment planning has been to determine limits on radiation absorbed close to critical nonhematopoietic organs. This study demonstrates the feasibility of using CT to adjust for actual organ volumes in calculating organ-specific absorbed dose estimates. Methods: Records of 84 patients who underwent biodistribution studies after a trace-labeled infusion of 131I-tositumomab for RIT (January 1990 and April 2003) were reviewed. Serial planar -camera images and whole-body Nal probe counts were obtained to estimate 131I-antibody source-organ residence times as recommended by the MIRD Committee. The source-organ residence times for standard man or woman were adjusted by the ratio of the MIRD phantom organ mass to the CT-derived organ mass. Results: The mean radiation absorbed doses (in mGy/MBq) for our data using the MIRD model were lungs= 1.67; liver= 1.03; kidneys= 1.08; spleen= 2.67; and whole body= 0.3; and for CT volume-adjusted organ volumes (in mGy/MBq) were lungs= 1.30; liver= 0.92; kidneys= 0.76; spleen= 1.40; and whole body= 0.22. We determined the following correlation coefficients between the 2 methods for the various organs; lungs, 0.49; (P= 0.0001); liver, 0.64 (P= 0.004); kidneys, 0.45 (P= 0.0001), for the residence times. For therapy, patients received mean 131I administered activities of 19.2 GBq (520 mCi) after adjustment for CT-derived organ mass compared with 16.0 GBq (433 mCi) that would otherwise have been given had therapy been based only using standard MIRD organ volumes--a statistically significant difference (P= 0.0001). Conclusion: We observed large variations in organ masses among our patients. Our treatments were planned to deliver the maximally tolerated radiation dose to the dose-limiting normal organ. This work provides a simplified method for calculating patient-specific radiation

  7. A 3D Monte Carlo Method for Estimation of Patient-specific Internal Organs Absorbed Dose for (99m)Tc-hynic-Tyr(3)-octreotide Imaging.

    PubMed

    Momennezhad, Mehdi; Nasseri, Shahrokh; Zakavi, Seyed Rasoul; Parach, Ali Asghar; Ghorbani, Mahdi; Asl, Ruhollah Ghahraman

    2016-01-01

    Single-photon emission computed tomography (SPECT)-based tracers are easily available and more widely used than positron emission tomography (PET)-based tracers, and SPECT imaging still remains the most prevalent nuclear medicine imaging modality worldwide. The aim of this study is to implement an image-based Monte Carlo method for patient-specific three-dimensional (3D) absorbed dose calculation in patients after injection of (99m)Tc-hydrazinonicotinamide (hynic)-Tyr(3)-octreotide as a SPECT radiotracer. (99m)Tc patient-specific S values and the absorbed doses were calculated with GATE code for each source-target organ pair in four patients who were imaged for suspected neuroendocrine tumors. Each patient underwent multiple whole-body planar scans as well as SPECT imaging over a period of 1-24 h after intravenous injection of (99m)hynic-Tyr(3)-octreotide. The patient-specific S values calculated by GATE Monte Carlo code and the corresponding S values obtained by MIRDOSE program differed within 4.3% on an average for self-irradiation, and differed within 69.6% on an average for cross-irradiation. However, the agreement between total organ doses calculated by GATE code and MIRDOSE program for all patients was reasonably well (percentage difference was about 4.6% on an average). Normal and tumor absorbed doses calculated with GATE were slightly higher than those calculated with MIRDOSE program. The average ratio of GATE absorbed doses to MIRDOSE was 1.07 ± 0.11 (ranging from 0.94 to 1.36). According to the results, it is proposed that when cross-organ irradiation is dominant, a comprehensive approach such as GATE Monte Carlo dosimetry be used since it provides more reliable dosimetric results. PMID:27134562

  8. A 3D Monte Carlo Method for Estimation of Patient-specific Internal Organs Absorbed Dose for 99mTc-hynic-Tyr3-octreotide Imaging

    PubMed Central

    Momennezhad, Mehdi; Nasseri, Shahrokh; Zakavi, Seyed Rasoul; Parach, Ali Asghar; Ghorbani, Mahdi; Asl, Ruhollah Ghahraman

    2016-01-01

    Single-photon emission computed tomography (SPECT)-based tracers are easily available and more widely used than positron emission tomography (PET)-based tracers, and SPECT imaging still remains the most prevalent nuclear medicine imaging modality worldwide. The aim of this study is to implement an image-based Monte Carlo method for patient-specific three-dimensional (3D) absorbed dose calculation in patients after injection of 99mTc-hydrazinonicotinamide (hynic)-Tyr3-octreotide as a SPECT radiotracer. 99mTc patient-specific S values and the absorbed doses were calculated with GATE code for each source-target organ pair in four patients who were imaged for suspected neuroendocrine tumors. Each patient underwent multiple whole-body planar scans as well as SPECT imaging over a period of 1-24 h after intravenous injection of 99mhynic-Tyr3-octreotide. The patient-specific S values calculated by GATE Monte Carlo code and the corresponding S values obtained by MIRDOSE program differed within 4.3% on an average for self-irradiation, and differed within 69.6% on an average for cross-irradiation. However, the agreement between total organ doses calculated by GATE code and MIRDOSE program for all patients was reasonably well (percentage difference was about 4.6% on an average). Normal and tumor absorbed doses calculated with GATE were slightly higher than those calculated with MIRDOSE program. The average ratio of GATE absorbed doses to MIRDOSE was 1.07 ± 0.11 (ranging from 0.94 to 1.36). According to the results, it is proposed that when cross-organ irradiation is dominant, a comprehensive approach such as GATE Monte Carlo dosimetry be used since it provides more reliable dosimetric results. PMID:27134562

  9. Atomic structure of metal-halide perovskites from first principles: The chicken-and-egg paradox of the organic-inorganic interaction

    NASA Astrophysics Data System (ADS)

    Li, Jingrui; Rinke, Patrick

    2016-07-01

    We have studied the prototype hybrid organic-inorganic perovskite CH3NH3PbI3 and its three close relatives, CH3NH3SnI3 ,CH3NH3PbCl3 , and CsPbI3, using relativistic density function theory. The long-range van der Waals (vdW) interactions were incorporated into the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional using the Tkatchenko-Scheffler pairwise scheme. Our results reveal that hydrogen bonding, which is well described by the PBE functional, plays a decisive role for the structural parameters of these systems, including the position and orientation of the organic cation as well as the deformation of the inorganic framework. The magnitude of the inorganic-framework deformation depends sensitively on the orientation of the organic cation, and directly influences the stability of the hybrid perovskites. Our results suggest that the organic and the inorganic components complement each other; the low symmetry of the organic cation is the origin of the inorganic-framework deformation, which then aids the overall stabilization of the hybrid perovskite structure. This stabilization is indirectly affected by vdW interactions, which lead to smaller unit-cell volumes than in PBE and therefore modulate the interaction between the organic cation and the inorganic framework. The vdW-induced lattice-constant corrections are system dependent and lead to PBE+vdW lattice constants in good agreement with experiment. Further insight is gained by analyzing the vdW contributions. In all iodide-based hybrid perovskites, the interaction between the organic cation and the iodide anions provides the largest lattice-constant change, followed by iodine-iodine and the organic cation—heavy-metal cation interaction. These corrections follow an almost linear dependence on the lattice constant within the range considered in our study and are therefore approximately additive.

  10. Development of Halide and Oxy-Halides for Isotopic Separations

    SciTech Connect

    Leigh R. Martin; Aaron T. Johnson; Jana Pfeiffer; Martha R. Finck

    2014-10-01

    The goal of this project was to synthesize a volatile form of Np for introduction into mass spectrometers at INL. Volatile solids of the 5f elements are typically those of the halides (e.g. UF6), however fluorine is highly corrosive to the sensitive internal components of the mass separator, and the other volatile halides exist as several different stable isotopes in nature. However, iodide is both mono-isotopic and volatile, and as such presents an avenue for creation of a form of Np suitable for introduction into the mass separator. To accomplish this goal, the technical work in the project sought to establish a novel synthetic route for the conversion NpO2+ (dissolved in nitric acid) to NpI3 and NpI4.

  11. Resonance Raman spectra of organic molecules absorbed on inorganic semiconducting surfaces: Contribution from both localized intramolecular excitation and intermolecular charge transfer excitation

    SciTech Connect

    Ye, ChuanXiang; Zhao, Yi E-mail: liangwz@xmu.edu.cn; Liang, WanZhen E-mail: liangwz@xmu.edu.cn

    2015-10-21

    The time-dependent correlation function approach for the calculations of absorption and resonance Raman spectra (RRS) of organic molecules absorbed on semiconductor surfaces [Y. Zhao and W. Z. Liang, J. Chem. Phys. 135, 044108 (2011)] is extended to include the contribution of the intermolecular charge transfer (CT) excitation from the absorbers to the semiconducting nanoparticles. The results demonstrate that the bidirectionally interfacial CT significantly modifies the spectral line shapes. Although the intermolecular CT excitation makes the absorption spectra red shift slightly, it essentially changes the relative intensities of mode-specific RRS and causes the oscillation behavior of surface enhanced Raman spectra with respect to interfacial electronic couplings. Furthermore, the constructive and destructive interferences of RRS from the localized molecular excitation and CT excitation are observed with respect to the electronic coupling and the bottom position of conductor band. The interferences are determined by both excitation pathways and bidirectionally interfacial CT.

  12. Sound Absorbers

    NASA Astrophysics Data System (ADS)

    Fuchs, H. V.; Möser, M.

    Sound absorption indicates the transformation of sound energy into heat. It is, for instance, employed to design the acoustics in rooms. The noise emitted by machinery and plants shall be reduced before arriving at a workplace; auditoria such as lecture rooms or concert halls require a certain reverberation time. Such design goals are realised by installing absorbing components at the walls with well-defined absorption characteristics, which are adjusted for corresponding demands. Sound absorbers also play an important role in acoustic capsules, ducts and screens to avoid sound immission from noise intensive environments into the neighbourhood.

  13. Absorbed Radiation Dose in Radiosensitive Organs During Coronary CT Angiography Using 320-MDCT: Effect of Maximum Tube Voltage and Heart Rate Variations

    PubMed Central

    Nikolic, Boris; Khosa, Faisal; Lin, Pei-Jan Paul; Khan, Atif N.; Sarwar, Sheryar; Yam, Chun-Shan; Court, Laurence E.; Raptopoulos, Vassilios; Clouse, Melvin E.

    2012-01-01

    OBJECTIVE The purpose of this article is to estimate the absorbed radiation dose in radiosensitive organs during coronary MDCT angiography using 320-MDCT and to determine the effects of tube voltage variation and heart rate (HR) control on absorbed radiation dose. MATERIALS AND METHODS Semiconductor field effect transistor detectors were used to measure absorbed radiation doses for the thyroid, midbreast, breast, and midlung in an anthropomorphic phantom at 100, 120, and 135 kVp at two different HRs of 60 and 75 beats per minute (bpm) with a scan field of view of 320 mm, 400 mA, 320 × 0.5 mm detectors, and 160 mm collimator width (160 mm range). The paired Student’s t test was used for data evaluation. RESULTS At 60 bpm, absorbed radiation doses for 100, 120, and 135 kVp were 13.41 ± 3.59, 21.7 ± 4.12, and 29.28 ± 5.17 mGy, respectively, for midbreast; 11.76 ± 0.58, 18.86 ± 1.06, and 24.82 ± 1.45 mGy, respectively, for breast; 12.19 ± 2.59, 19.09 ± 3.12, and 26.48 ± 5.0 mGy, respectively, for lung; and 0.37 ± 0.14, 0.69 ± 0.14, and 0.92 ± 0.2 mGy, respectively, for thyroid. Corresponding absorbed radiation doses for 75 bpm were 38.34 ± 2.02, 59.72 ± 3.13, and 77.8 ± 3.67 mGy for midbreast; 26.2 ± 1.74, 44 ± 1.11, and 52.84 ± 4.07 mGy for breast; 38.02 ± 1.58, 58.89 ± 1.68, and 78 ± 2.93 mGy for lung; and 0.79 ± 0.233, 1.04 ± 0.18, and 2.24 ± 0.52 mGy for thyroid. Absorbed radiation dose changes were significant for all organs for both tube voltage reductions as well as for HR control from 75 to 60 bpm at all tube voltage settings (p < 0.05). The absorbed radiation doses for the calcium score protocol were 11.2 ± 1.4 mGy for midbreast, 9.12 ± 0.48 mGy for breast, 10.36 ± 1.3 mGy for lung, and 0.4 ± 0.05 mGy for thyroid. CONCLUSION CT angiography with 320-MDCT scanners results in absorbed radiation doses in radiosensitive organs that compare favorably to those previously reported. Significant dose reductions can be achieved by tube

  14. 40 CFR 721.4095 - Quaternary ammonium alkyltherpropyl trialkylamine halides.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... trialkylamine halides. 721.4095 Section 721.4095 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.4095 Quaternary ammonium alkyltherpropyl trialkylamine halides. (a... generically as quaternary ammonium alkyltherpropyl trialkylamine halides (PMNs...

  15. TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

    DOEpatents

    Fried, S.

    1951-03-20

    Halides of transuranic elements are prepared by contacting with aluminum and a halogen, or with an aluminum halide, a transuranic metal oxide, oxyhalide, halide, or mixture thereof at an elevated temperature.

  16. Degradation and mineralization of organic UV absorber compound 2-phenylbenzimidazole-5-sulfonic acid (PBSA) using UV-254nm/H2O2.

    PubMed

    Abdelraheem, Wael H M; He, Xuexiang; Duan, Xiaodi; Dionysiou, Dionysios D

    2015-01-23

    Various studies have revealed the non-biodegradable and endocrine disrupting properties of sulfonated organic UV absorbers, directing people's attention toward their risks on ecological and human health and hence their removal from water. In this study, UV-254nm/H2O2 advanced oxidation process (AOP) was investigated for degrading a model UV absorber compound 2-phenylbenzimidazole-5-sulfonic acid (PBSA) and a structurally similar compound 1H-benzimidazole-2-sulfonic acid (BSA), with a specific focus on their mineralization. At 4.0mM [H2O2]0, a complete removal of 40.0μM parent PBSA and 25% decrease in TOC were achieved with 190min of UV irradiation; SO4(2-) was formed and reached its maximum level while the release of nitrogen as NH4(+) was much lower (around 50%) at 190min. Sulfate removal was strongly enhanced by increasing [H2O2]0 in the range of 0-4.0mM, with slight inhibition in 4.0-12.0mM. Faster and earlier ammonia formation was observed at higher [H2O2]0. The presence of Br(-) slowed down the degradation and mineralization of both compounds while a negligible effect on the degradation was observed in the presence of Cl(-). Our study provides important technical and fundamental results on the HO based degradation and mineralization of SO3H and N-containing UV absorber compounds. PMID:25123523

  17. Computational Investigations for Undergraduate Organic Chemistry: Modeling Markovnikov and anti-Markovnikov Reactions for the Formation of Alkyl Halides and Alcohols

    NASA Astrophysics Data System (ADS)

    Hessley, Rita K.

    2000-06-01

    Early in sophomore-level organic chemistry students are introduced to reaction mechanisms, and it is at this stage when they tend to become convinced that memorization is the skill they need to hone in order to succeed. This paper describes how the early introduction of molecular modeling for the study of reaction mechanisms leading to alcohols from alkenes can increase students' involvement in their own learning and can effectively challenge their misapprehension about memorization. It describes the use of modeling to emphasize structure-reactivity relationships rather than focusing on reagents, and tries to show that the use of molecular modeling is well suited for classroom and laboratory use as well as to assist students' study. Particularly in an educational setting that stresses collaborative or interactive learning, the methodology described here can be rewarding for teachers and students alike.

  18. Color Bricks: Building Highly Organized and Strongly Absorbing Multicomponent Arrays of Terpyridyl Perylenes on Metal Oxide Surfaces.

    PubMed

    Sariola-Leikas, Essi; Ahmed, Zafar; Vivo, Paola; Ojanperä, Anniina; Lahtonen, Kimmo; Saari, Jesse; Valden, Mika; Lemmetyinen, Helge; Efimov, Alexander

    2016-01-22

    Terpyridine-substituted perylenes containing cyclic anhydrides in the peri position were synthesized. The anhydride group served as an anchor for assembly of the terpyridyl-crowned chromophores as monomolecular layers on metal oxide surfaces. Further coordination with Zn(2+) ions allowed for layer-by-layer formation of supramolecular assemblies of perylene imides on the solid substrates. With properly selected anchor and linker molecules it was possible to build high quality structures of greater than ten successive layers by a simple and straightforward procedure. The prepared films were stable and had a broad spectral coverage and high absorbance. To demonstrate their potential use, the synthesized dyes were employed in solid-state dye-sensitized solar cells, and electron injection from the perylene antennas to titanium dioxide was observed. PMID:26632758

  19. Application of three-coordinate copper(I) complexes with halide ligands in organic light-emitting diodes that exhibit delayed fluorescence.

    PubMed

    Osawa, Masahisa; Hoshino, Mikio; Hashimoto, Masashi; Kawata, Isao; Igawa, Satoshi; Yashima, Masataka

    2015-05-14

    A series of three-coordinate copper(I) complexes (L(Me))CuX [X = Cl (1), Br (2), I (3)], (L(Et))CuBr (4), and (L(iPr))CuBr (5) [L(Me) = 1,2-bis[bis(2-methylphenyl)phosphino]benzene, L(Et) = 1,2-bis[bis(2-ethylphenyl)phosphino]benzene, and L(iPr) = 1,2-bis[bis(2-isopropylphenyl)phosphino]benzene] exhibit efficient blue-green emission in the solid state at ambient temperature with peak wavelengths between 473 and 517 nm. The emission quantum yields were 0.38-0.95. The emission lifetimes were measured in the temperature range of 77-295 K using a nanosecond laser technique. The temperature dependence of the emission lifetimes was explained using a model with two excited states: a singlet and a triplet state. The small energy gaps (<830 cm(-1)) between the two states suggest that efficient emission from 1-5 was thermally activated delayed fluorescence (TADF). Alkyl substituents at ortho positions of peripheral phenyl groups were found to have little effect on the electronic excited states. Because the origin of the emission of complexes 2, 4, and 5 was thought to be a (σ + Br)→π* transition, photoluminescence characteristics of these complexes were dominated by the diphosphine ligands. Complexes 2, 4, and 5 had similar emission properties. Complexes 1-5 had efficient green TADF in amorphous films at 293 K with maximum emission wavelengths of 508-520 nm and quantum yields of 0.61-0.71. Organic light-emitting devices that contained complexes 1-5 and exhibited TADF exhibit bright green luminescence with current efficiencies of 55.6-69.4 cd A(-1) and maximum external quantum efficiencies of 18.6-22.5%. PMID:25470470

  20. Cohesive Energy-Lattice Constant and Bulk Modulus-Lattice Constant Relationships: Alkali Halides, Ag Halides, Tl Halides

    NASA Technical Reports Server (NTRS)

    Schlosser, Herbert

    1992-01-01

    In this note we present two expressions relating the cohesive energy, E(sub coh), and the zero pressure isothermal bulk modulus, B(sub 0), of the alkali halides. Ag halides and TI halides, with the nearest neighbor distances, d(sub nn). First, we show that the product E(sub coh)d(sub 0) within families of halide crystals with common crystal structure is to a good approximation constant, with maximum rms deviation of plus or minus 2%. Secondly, we demonstrate that within families of halide crystals with a common cation and common crystal structure the product B(sub 0)d(sup 3.5)(sub nn) is a good approximation constant, with maximum rms deviation of plus or minus 1.36%.

  1. Role of shielding in modulating the effects of solar particle events: Monte Carlo calculation of absorbed dose and DNA complex lesions in different organs

    NASA Technical Reports Server (NTRS)

    Ballarini, F.; Biaggi, M.; De Biaggi, L.; Ferrari, A.; Ottolenghi, A.; Panzarasa, A.; Paretzke, H. G.; Pelliccioni, M.; Sala, P.; Scannicchio, D.; Zankl, M.; Townsend, L. W. (Principal Investigator)

    2004-01-01

    Distributions of absorbed dose and DNA clustered damage yields in various organs and tissues following the October 1989 solar particle event (SPE) were calculated by coupling the FLUKA Monte Carlo transport code with two anthropomorphic phantoms (a mathematical model and a voxel model), with the main aim of quantifying the role of the shielding features in modulating organ doses. The phantoms, which were assumed to be in deep space, were inserted into a shielding box of variable thickness and material and were irradiated with the proton spectra of the October 1989 event. Average numbers of DNA lesions per cell in different organs were calculated by adopting a technique already tested in previous works, consisting of integrating into "condensed-history" Monte Carlo transport codes--such as FLUKA--yields of radiobiological damage, either calculated with "event-by-event" track structure simulations, or taken from experimental works available in the literature. More specifically, the yields of "Complex Lesions" (or "CL", defined and calculated as a clustered DNA damage in a previous work) per unit dose and DNA mass (CL Gy-1 Da-1) due to the various beam components, including those derived from nuclear interactions with the shielding and the human body, were integrated in FLUKA. This provided spatial distributions of CL/cell yields in different organs, as well as distributions of absorbed doses. The contributions of primary protons and secondary hadrons were calculated separately, and the simulations were repeated for values of Al shielding thickness ranging between 1 and 20 g/cm2. Slight differences were found between the two phantom types. Skin and eye lenses were found to receive larger doses with respect to internal organs; however, shielding was more effective for skin and lenses. Secondary particles arising from nuclear interactions were found to have a minor role, although their relative contribution was found to be larger for the Complex Lesions than for the

  2. Multiple-Wavelength Metal/Halide Laser

    NASA Technical Reports Server (NTRS)

    Nerheim, N. M.

    1984-01-01

    Single device produces multiple lasing lines. Laser capable of producing many lasing lines has several reservoirs of halide lasant mixed with chlorides of copper, manganese and iron. Convection-control technique possible to rapidly change from one metal halide to another at maximum energy.

  3. Hygroscopicity Evaluation of Halide Scintillators

    SciTech Connect

    Zhuravleva, M; Stand, L; Wei, H; Hobbs, C. L.; Boatner, Lynn A; Ramey, Joanne Oxendine; Burger, Arnold; Rowe, E; Bhattacharya, P.; Tupitsyn, E; Melcher, Charles L

    2014-01-01

    A collaborative study of relative hygroscopicity of anhydrous halide scintillators grown at various laboratories is presented. We have developed a technique to evaluate moisture sensitivity of both raw materials and grown crystals, in which the moisture absorption rate is measured using a gravimetric analysis. Degradation of the scintillation performance was investigated by recording gamma-ray spectra and monitoring the photopeak position, count rate and energy resolution. The accompanying physical degradation of the samples exposed to ambient atmosphere was photographically recorded as well. The results were compared with ben

  4. Quantum Size Effect in Organometal Halide Perovskite Nanoplatelets.

    PubMed

    Sichert, Jasmina A; Tong, Yu; Mutz, Niklas; Vollmer, Mathias; Fischer, Stefan; Milowska, Karolina Z; García Cortadella, Ramon; Nickel, Bert; Cardenas-Daw, Carlos; Stolarczyk, Jacek K; Urban, Alexander S; Feldmann, Jochen

    2015-10-14

    Organometal halide perovskites have recently emerged displaying a huge potential for not only photovoltaic, but also light emitting applications. Exploiting the optical properties of specifically tailored perovskite nanocrystals could greatly enhance the efficiency and functionality of applications based on this material. In this study, we investigate the quantum size effect in colloidal organometal halide perovskite nanoplatelets. By tuning the ratio of the organic cations used, we can control the thickness and consequently the photoluminescence emission of the platelets. Quantum mechanical calculations match well with the experimental values. We find that not only do the properties of the perovskite, but also those of the organic ligands play an important role. Stacking of nanoplatelets leads to the formation of minibands, further shifting the bandgap energies. In addition, we find a large exciton binding energy of up to several hundreds of meV for nanoplatelets thinner than three unit cells, partially counteracting the blueshift induced by quantum confinement. Understanding of the quantum size effects in perovskite nanoplatelets and the ability to tune them provide an additional method with which to manipulate the optical properties of organometal halide perovskites. PMID:26327242

  5. Characteristics of dissolved organic carbon revealed by ultraviolet/visible absorbance and fluorescence spectroscopy: The current status and future exploration

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Dissolved organic carbon (DOC) is an important research subject for various disciplines. The objectives of this chapter are to review and summarize recent advancement in characterization of DOC by ultraviolet/visible (UV/Vis) and fluorescence spectroscopies and to identify the information gaps for ...

  6. Getting Away from the Cookbook in the Organic Laboratory.

    ERIC Educational Resources Information Center

    Potter, Neil H.; McGrath, Thomas F.

    1989-01-01

    Discusses an organic laboratory program emphasizing individual experiments for the second semester of a two-semester course. Describes the outlines of two topics, including halide or alcohol synthesis and multistep synthesis. Provides reaction tables of alcohols and halides. (YP)

  7. Shallow halogen vacancies in halide optoelectronic materials

    DOE PAGESBeta

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VHmore » is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.« less

  8. Shallow halogen vacancies in halide optoelectronic materials

    NASA Astrophysics Data System (ADS)

    Shi, Hongliang; Du, Mao-Hua

    2014-11-01

    Halogen vacancies (VH ) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., C H3N H3Pb I3 and TlBr. Both C H3N H3Pb I3 and TlBr have been found to have shallow VH , in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., C H3N H3Pb I3 , C H3N H3Sn I3 (photovoltaic materials), TlBr, and CsPbB r3 (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of n s2 ions both play important roles in creating shallow VH in halides such as C H3N H3Pb I3 , C H3N H3Sn I3 , and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH , such as those with large cation-cation distances and low anion coordination numbers and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH . The results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  9. Cross-Electrophile Coupling of Vinyl Halides with Alkyl Halides.

    PubMed

    Johnson, Keywan A; Biswas, Soumik; Weix, Daniel J

    2016-05-23

    An improved method for the reductive coupling of aryl and vinyl bromides with alkyl halides that gave high yields for a variety of substrates at room temperature with a low (2.5 to 0.5 mol %) catalyst loading is presented. Under the optimized conditions, difficult substrates, such as unhindered alkenyl bromides, can be coupled to give the desired olefins with minimal diene formation and good stereoretention. These improved conditions also worked well for aryl bromides. For example, a gram-scale reaction was demonstrated with 0.5 mol % catalyst loading, whereas reactions at 10 mol % catalyst loading completed in as little as 20 minutes. Finally, a low-cost single-component pre-catalyst, (bpy)NiI2 (bpy=2,2'-bipyridine) that is both air- and moisture-stable over a period of months was introduced. PMID:27017436

  10. Abiotic Formation of Methyl Halides in the Terrestrial Environment

    NASA Astrophysics Data System (ADS)

    Keppler, F.

    2011-12-01

    Methyl chloride and methyl bromide are the most abundant chlorine and bromine containing organic compounds in the atmosphere. Since both compounds have relatively long tropospheric lifetimes they can effectively transport halogen atoms from the Earth's surface, where they are released, to the stratosphere and following photolytic oxidation form reactive halogen gases that lead to the chemical destruction of ozone. Methyl chloride and methyl bromide account for more than 20% of the ozone-depleting halogens delivered to the stratosphere and are predicted to grow in importance as the chlorine contribution to the stratosphere from anthropogenic CFCs decline. Today methyl chloride and methyl bromide originate mainly from natural sources with only a minor fraction considered to be of anthropogenic origin. However, until as recently as 2000 most of the methyl chloride and methyl bromide input to the atmosphere was considered to originate from the oceans, but investigations in recent years have clearly demonstrated that terrestrial sources such as biomass burning, wood-rotting fungi, coastal salt marshes, tropical vegetation and organic matter degradation must dominate the atmospheric budgets of these trace gases. However, many uncertainties still exist regarding strengths of both sources and sinks, as well as the mechanisms of formation of these naturally occurring halogenated gases. A better understanding of the atmospheric budget of both methyl chloride and methyl bromide is therefore required for reliable prediction of future ozone depletion. Biotic and abiotic methylation processes of chloride and bromide ion are considered to be the dominant pathways of formation of these methyl halides in nature. In this presentation I will focus on abiotic formation processes in the terrestrial environment and the potential parameters that control their emissions. Recent advances in our understanding of the abiotic formation pathway of methyl halides will be discussed. This will

  11. Lasing in robust cesium lead halide perovskite nanowires.

    PubMed

    Eaton, Samuel W; Lai, Minliang; Gibson, Natalie A; Wong, Andrew B; Dou, Letian; Ma, Jie; Wang, Lin-Wang; Leone, Stephen R; Yang, Peidong

    2016-02-23

    The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic-inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored and handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry-Pérot lasing occurs in CsPbBr3 nanowires with an onset of 5 μJ cm(-2) with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 10(9) excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication. PMID:26862172

  12. Mass absorption efficiency of light absorbing organic aerosols from source region of paddy-residue burning emissions in the Indo-Gangetic Plain

    NASA Astrophysics Data System (ADS)

    Srinivas, B.; Rastogi, N.; Sarin, M. M.; Singh, A.; Singh, D.

    2016-01-01

    The mass absorption efficiency (MAE) of light absorbing water-soluble organics, representing a significant fraction of brown carbon (BrC), has been studied in fine mode aerosols (PM2.5) from a source region (Patiala: 30.2 °N, 76.3 °E) of biomass burning emissions (BBEs) in the Indo-Gangetic Plain (IGP). The mass absorption coefficient of BrC at 365 nm (babs-365), assessed from absorption spectra of aqueous extracts, exhibits significant linear relationship with water-soluble organic carbon (WSOC) for day (R2 = 0.37) and night time (R2 = 0.77) samples; and slope of regression lines provides a measure of MAE of BrC (daytime: ˜0.75 m2 g-1 and night time: 1.13 m2 g-1). A close similarity in the temporal variability of babs-365 (for BrC) and K+ in all samples suggests their common source from BBEs. The babs-365 of BrC follows a power law (babs-λ ≈ λ-α; where α = angstrom exponent) and averages around 5.2 ± 2.0 M m-1 (where M = 10-6). A significant decrease in the MAE of BrC from the source region (this study) to the downwind oceanic region (over Bay of Bengal, Srinivas and Sarin, 2013) could be attributed to relative increase in the contribution of non-absorbing WSOC and/or photo-bleaching of BrC during long-range atmospheric transport. The atmospheric radiative forcing due to BrC over the study site accounts for ˜40% of that from elemental carbon (EC).

  13. Appearance of strong absorbers and fluorophores in limonene-O3 secondary organic aerosol due to NH4+-mediated chemical aging over long time scales

    NASA Astrophysics Data System (ADS)

    Bones, David L.; Henricksen, Dana K.; Mang, Stephen A.; Gonsior, Michael; Bateman, Adam P.; Nguyen, Tran B.; Cooper, William J.; Nizkorodov, Sergey A.

    2010-03-01

    This study investigated long-term chemical aging of model biogenic secondary organic aerosol (SOA) prepared from the ozonolysis of terpenes. Techniques including electrospray ionization mass spectrometry (ESI-MS), UV-visible spectroscopy, Fourier transform infrared (FTIR) spectroscopy, NMR, and three-dimensional fluorescence were used to probe the changes in chemical composition of SOA collected by impaction on substrates and also of aqueous extracts of SOA. The addition of ammonium ions or amino acids to limonene SOA reproducibly produced orange-colored species that strongly absorbed visible radiation and fluoresced at UV and visible wavelengths. Simultaneous addition of H2SO4 to the SOA aqueous extracts inhibited this color transformation. These observations suggest the existence of aging processes leading to heavily conjugated molecules containing organic nitrogen. The presence of nitrogen in the chromophores was confirmed by the dependence of the absorption and fluorescence spectra on the amino acids added. In contrast to the strong change in the absorption and fluorescence spectra, there was no significant change in the ESI-MS, FTIR, and NMR spectra, suggesting that the chromophores were minor species in the aged SOA. Aqueous extracts of aged limonene + NH4+ SOA were characterized by an effective base-e absorption coefficient of ˜3 L g-1 cm-1 at 500 nm. Assuming particulate matter concentrations typical of polluted rural air gives an upper limit of 0.2 M m-1 for the aerosol absorption coefficient due to the aged limonene oxidation products. Biogenic SOA can therefore become weakly absorbing if they undergo aging in the presence of NH4+-containing aerosol.

  14. Metal-organic framework-templated synthesis of magnetic nanoporous carbon as an efficient absorbent for enrichment of phenylurea herbicides.

    PubMed

    Liu, Xingli; Wang, Chun; Wu, Qiuhua; Wang, Zhi

    2015-04-22

    Nanoporous carbon with a high specific surface area and unique porous structure represents an attractive material as an adsorbent in analytical chemistry. In this study, a magnetic nanoporous carbon (MNC) was fabricated by direct carbonization of Co-based metal-organic framework in nitrogen atmosphere without using any additional carbon precursors. The MNC was used as an effective magnetic adsorbent for the extraction and enrichment of some phenylurea herbicides (monuron, isoproturon, diuron and buturon) in grape and bitter gourd samples prior to their determination by high performance liquid chromatography with ultraviolet detection. Several important experimental parameters that could influence the extraction efficiency were investigated and optimized. Under the optimum conditions, a good linearity was achieved in the concentration range of 1.0-100.0 ng g(-1) for monuron, diuron and buturon and 1.5-100.0 ng g(-1) for isoproturon with the correlation coefficients (r) larger than 0.9964. The limits of detection (S/N=3) of the method were in the range from 0.17 to 0.46 ng g(-1). The results indicated that the MNC material was stable and efficient adsorbent for the magnetic solid-phase extraction of phenylurea herbicides and would have a great application potential for the extraction and preconcentration of more organic pollutants from real samples. PMID:25819788

  15. Estimating absorbing black carbon and organic carbon optical properties from AERONET and MISR data over East Asia

    NASA Astrophysics Data System (ADS)

    Chen, B.; Ramanathan, V.; Huang, J.; Zhang, G. J.; Xu, Y.

    2011-12-01

    The radiative forcing due to carbonaceous aerosols is one of the largest source of uncertainties in global and regional climate change. Black carbon and organic carbon from biomass and fossil fuel are two major types of carbonaceous aerosols. In this study we use available ground based and satellite observations to infer the optical properties of black and organic carbon. NASA's AERONET and MISR data over East Asia provide the observational basis. We use the spectral variations in the observed aerosol extinction optical depth and absorption optical depth to categorize the optical properties including their mixing state with other aerosols such as dust and other inorganic aerosols. We create 8 different categories of aerosol mixtures: Dust, Biomass Burning, Fossil Fuel, Aged Fossil Fuel, Mixed Dust with Biomass Burning, Mixed Dust with Aged Fossil Fuel, Mixed Biomass Burning with Fossil Fuel, and Mixed Dust, Biomass Burning, with Fossil Fuel, over the following 6 regions of East Asia: Nepal, Gobi, North Industrial China, South Industrial China, Southeast Asia, and Korea/Japan. Our results are compared with independent surface observations over China using Aethalometers and Single Particle Soot Photometers.

  16. Extracting Information about the Electronic Quality of Organic Solar-Cell Absorbers from Fill Factor and Thickness

    NASA Astrophysics Data System (ADS)

    Kaienburg, Pascal; Rau, Uwe; Kirchartz, Thomas

    2016-08-01

    Understanding the fill factor in organic solar cells remains challenging due to its complex dependence on a multitude of parameters. By means of drift-diffusion simulations, we thoroughly analyze the fill factor of such low-mobility systems and demonstrate its dependence on a collection coefficient defined in this work. We systematically discuss the effect of different recombination mechanisms, space-charge regions, and contact properties. Based on these findings, we are able to interpret the thickness dependence of the fill factor for different experimental studies from the literature. The presented model provides a facile method to extract the photoactive layer's electronic quality which is of particular importance for the fill factor. We illustrate that over the past 15 years, the electronic quality has not been continuously improved, although organic solar-cell efficiencies increased steadily over the same period of time. Only recent reports show the synthesis of polymers for semiconducting films of high electronic quality that are able to produce new efficiency records.

  17. METHOD 415.3 - MEASUREMENT OF TOTAL ORGANIC CARBON, DISSOLVED ORGANIC CARBON AND SPECIFIC UV ABSORBANCE AT 254 NM IN SOURCE WATER AND DRINKING WATER

    EPA Science Inventory

    2.0 SUMMARY OF METHOD

    2.1 In both TOC and DOC determinations, organic carbon in the water sample is oxidized to form carbon dioxide (CO2), which is then measured by a detection system. There are two different approaches for the oxidation of organic carbon in water sample...

  18. Thermal conversion of an Fe3O4@metal-organic framework: a new method for an efficient Fe-Co/nanoporous carbon microwave absorbing material

    NASA Astrophysics Data System (ADS)

    Zhang, Xingmiao; Ji, Guangbin; Liu, Wei; Quan, Bin; Liang, Xiaohui; Shang, Chaomei; Cheng, Yan; Du, Youwei

    2015-07-01

    A novel FeCo nanoparticle embedded nanoporous carbon composite (Fe-Co/NPC) was synthesized via in situ carbonization of dehydro-ascorbic acid (DHAA) coated Fe3O4 nanoparticles encapsulated in a metal-organic framework (zeolitic imidazolate framework-67, ZIF-67). The molar ratio of Fe/Co significantly depends on the encapsulated content of Fe3O4 in ZIF-67. The composites filled with 50 wt% of the Fe-Co/NPC-2.0 samples in paraffin show a maximum reflection loss (RL) of -21.7 dB at a thickness of 1.2 mm; in addition, a broad absorption bandwidth for RL < -10 dB which covers from 12.2 to 18 GHz can be obtained, and its minimum reflection loss and bandwidth (RL values exceeding -10 dB) are far greater than those of commercial carbonyl iron powder under a very low thickness (1-1.5 mm). This study not only provides a good reference for future preparation of carbon-based lightweight microwave absorbing materials but also broadens the application of such kinds of metal-organic frameworks.A novel FeCo nanoparticle embedded nanoporous carbon composite (Fe-Co/NPC) was synthesized via in situ carbonization of dehydro-ascorbic acid (DHAA) coated Fe3O4 nanoparticles encapsulated in a metal-organic framework (zeolitic imidazolate framework-67, ZIF-67). The molar ratio of Fe/Co significantly depends on the encapsulated content of Fe3O4 in ZIF-67. The composites filled with 50 wt% of the Fe-Co/NPC-2.0 samples in paraffin show a maximum reflection loss (RL) of -21.7 dB at a thickness of 1.2 mm; in addition, a broad absorption bandwidth for RL < -10 dB which covers from 12.2 to 18 GHz can be obtained, and its minimum reflection loss and bandwidth (RL values exceeding -10 dB) are far greater than those of commercial carbonyl iron powder under a very low thickness (1-1.5 mm). This study not only provides a good reference for future preparation of carbon-based lightweight microwave absorbing materials but also broadens the application of such kinds of metal-organic frameworks. Electronic

  19. Self-assembly of Terbium(III)-based metal-organic complexes with two-photon absorbing active

    NASA Astrophysics Data System (ADS)

    Li, Dandan; Shao, Nanqi; Sun, Xianshun; Zhang, Guocui; Li, Shengli; Zhou, Hongping; Wu, Jieying; Tian, Yupeng

    2014-12-01

    Hybrid complexes based on D-π-A type dyes p-aminostyryl-pyridinum and Terbium(III) complex anion (1, 2) have been synthesized by ionic exchange reaction. Meanwhile two different alkyl-substituted amino groups were used as electron donors in organic dyes cations. The synthesized complexes were characterized by element analysis. In addition, the structural features of them were systematic studied by single crystal X-ray diffraction analysis. Their linear properties have been systematically investigated by absorption spectra and fluorescence, the results show that the energy transfer takes place from the trans-4-[4‧-(N,N-diethylamino)styryl]-N-methyl pyridinium (2‧) cation to Tb(III). In addition, complex 2 exhibit a large two-photon absorption coefficient β: 0.044 cm/GW at 710 nm.

  20. Toxicity of organometal halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Babayigit, Aslihan; Ethirajan, Anitha; Muller, Marc; Conings, Bert

    2016-03-01

    In the last few years, the advent of metal halide perovskite solar cells has revolutionized the prospects of next-generation photovoltaics. As this technology is maturing at an exceptional rate, research on its environmental impact is becoming increasingly relevant.

  1. Effects of halide ions on photodegradation of sulfonamide antibiotics: Formation of halogenated intermediates.

    PubMed

    Li, Yingjie; Qiao, Xianliang; Zhang, Ya-Nan; Zhou, Chengzhi; Xie, Huaijun; Chen, Jingwen

    2016-10-01

    The occurrence of sulfonamide antibiotics (SAs) in estuarine waters urges insights into their environmental fate for ecological risk assessment. Although many studies focused on the photochemical behavior of SAs, yet the effects of halide ions relevant to estuarine and marine environments on their photodegradation have been poorly understood. Here, we investigated the effects of halide ions on the photodegradation of SAs with sulfapyridine, sulfamethazine, and sulfamethoxazole as representative compounds. Results showed that halide ions did not significantly impact the photodegradation of sulfapyridine and sulfamethoxazole, while they significantly promoted the photodegradation of sulfamethazine. Further experiments found that ionic strength applied with NaClO4 significantly enhanced the photodegradation of the SAs, which was attributed to the decreased quenching rate constant of the triplet-excited SAs ((3)SA(∗)). Compared with ionic strength, specific Cl(-) effects retarded the photodegradation of the SAs. Our study found that triplet-excited sulfamethazine can oxidize halide ions to produce halogen radicals, subsequently leading to the halogenation of sulfamethazine, which was confirmed by the identification of both chlorinated and brominated intermediates. These results indicate that halide ions play an important role in the photochemical behavior of some SAs in estuarine waters and seawater. The occurrence of halogenation for certain organic pollutants can be predicted by comparing the oxidation potentials of triplet-excited contaminants with those of halogen radicals. Our findings are helpful in understanding the photochemical behavior and assessing the ecological risks of SAs and other organic pollutants in estuarine and marine environment. PMID:27393965

  2. Spatial Electron-hole Separation in a One Dimensional Hybrid Organic-Inorganic Lead Iodide

    NASA Astrophysics Data System (ADS)

    Savory, Christopher N.; Palgrave, Robert G.; Bronstein, Hugo; Scanlon, David O.

    2016-02-01

    The increasing efficiency of the inorganic-organic hybrid halides has revolutionised photovoltaic research. Despite this rapid progress, the significant issues of poor stability and toxicity have yet to be suitably overcome. In this article, we use Density Functional Theory to examine (Pb2I6) · (H2DPNDI) · (H2O) · (NMP), an alternative lead-based hybrid inorganic-organic solar absorber based on a photoactive organic cation. Our results demonstrate that optical properties suitable for photovoltaic applications, in addition to spatial electron-hole separation, are possible but efficient charge transport may be a limiting factor.

  3. Spatial Electron-hole Separation in a One Dimensional Hybrid Organic-Inorganic Lead Iodide.

    PubMed

    Savory, Christopher N; Palgrave, Robert G; Bronstein, Hugo; Scanlon, David O

    2016-01-01

    The increasing efficiency of the inorganic-organic hybrid halides has revolutionised photovoltaic research. Despite this rapid progress, the significant issues of poor stability and toxicity have yet to be suitably overcome. In this article, we use Density Functional Theory to examine (Pb2I6) · (H2DPNDI) · (H2O) · (NMP), an alternative lead-based hybrid inorganic-organic solar absorber based on a photoactive organic cation. Our results demonstrate that optical properties suitable for photovoltaic applications, in addition to spatial electron-hole separation, are possible but efficient charge transport may be a limiting factor. PMID:26858147

  4. Oxidation of hydrogen halides to elemental halogens

    DOEpatents

    Rohrmann, Charles A.; Fullam, Harold T.

    1985-01-01

    A process for oxidizing hydrogen halides having substantially no sulfur impurities by means of a catalytically active molten salt is disclosed. A mixture of the subject hydrogen halide and an oxygen bearing gas is contacted with a molten salt containing an oxidizing catalyst and alkali metal normal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen and substantially free of sulfur oxide gases.

  5. Deep absorbing porphyrin small molecule for high-performance organic solar cells with very low energy losses.

    PubMed

    Gao, Ke; Li, Lisheng; Lai, Tianqi; Xiao, Liangang; Huang, Yuan; Huang, Fei; Peng, Junbiao; Cao, Yong; Liu, Feng; Russell, Thomas P; Janssen, René A J; Peng, Xiaobin

    2015-06-17

    We designed and synthesized the DPPEZnP-TEH molecule, with a porphyrin ring linked to two diketopyrrolopyrrole units by ethynylene bridges. The resulting material exhibits a very low energy band gap of 1.37 eV and a broad light absorption to 907 nm. An open-circuit voltage of 0.78 V was obtained in bulk heterojunction (BHJ) organic solar cells, showing a low energy loss of only 0.59 eV, which is the first report that small molecule solar cells show energy losses <0.6 eV. The optimized solar cells show remarkable external quantum efficiency, short circuit current, and power conversion efficiency up to 65%, 16.76 mA/cm(2), and 8.08%, respectively, which are the best values for BHJ solar cells with very low energy losses. Additionally, the morphology of DPPEZnP-TEH neat and blend films with PC61BM was studied thoroughly by grazing incidence X-ray diffraction, resonant soft X-ray scattering, and transmission electron microscopy under different fabrication conditions. PMID:26035342

  6. Hydrogen Halides on Jupiter and Saturn

    NASA Astrophysics Data System (ADS)

    Showman, Adam P.

    2001-07-01

    The quest to detect gaseous HCl, HBr, and HF in the atmospheres of Jupiter and Saturn has led to a tentative detection of 1 ppb HCl near Saturn's cloud deck. The detection is puzzling because, while these hydrogen halides may be present several scale heights below the clouds, they are expected to react with ammonia to form solid ammonium halide salts in the upper troposphere. I show that the loss timescale for condensation of gaseous hydrogen halides onto particles is ˜10 3-10 5 s for realistic cloud densities and particle sizes, which is much less than the ˜10 8 s residence time of upper tropospheric air. The hydrogen halides can only survive transport up to the cloud layer if less than 1 in 10 6 of their collisions with particle surfaces leads to condensation, which is unlikely. Even in the absence of foreign particles, homogeneous nucleation would probably prevent supersaturations in excess of a few hundred, which is ˜10 20-10 40 times too low to explain the observation. These calculations therefore suggest that hydrogen halides cannot exist at part-per-billion levels in the upper troposphere. The interplanetary source of halogens is also too low to produce detectable quantities of hydrogen halides except perhaps at pressures less than 1 mbar. A possible detection of chlorine by the Galileo probe at pressures exceeding 9 bars on Jupiter may be consistent with the equilibrium abundance of gaseous HCl or NH 4Cl.

  7. Sources, composition and absorption Ångström exponent of light-absorbing organic components in aerosol extracts from the Los Angeles Basin.

    PubMed

    Zhang, Xiaolu; Lin, Ying-Hsuan; Surratt, Jason D; Weber, Rodney J

    2013-04-16

    We investigate the sources, chemical composition, and spectral properties of light-absorbing organic aerosol extracts (i.e., brown carbon, or BrC) in the Los Angeles (LA) Basin during the CalNex-2010 field campaign. Light absorption of PM2.5 water-soluble components at 365 nm (Abs365), used as a proxy for water-soluble BrC, was well correlated with water-soluble organic carbon (WSOC) (r(2) = 0.55-0.65), indicating secondary organic aerosol (SOA) formation from anthropogenic emissions was the major source of water-soluble BrC in this region. Normalizing Abs365 to WSOC mass yielded an average solution mass absorption efficiency (MAE365) of 0.71 m(2) g(-1) C. Detailed chemical speciation of filter extracts identified eight nitro-aromatic compounds that were correlated with Abs365. These compounds accounted for ∼4% of the overall water-soluble BrC absorption. Methanol-extracted BrC in LA was approximately 3 and 21 times higher than water-soluble BrC at 365 and 532 nm, respectively, and had a MAE365 of 1.58 m(2) g(-1) C (Abs365 normalized to organic carbon mass). The water-insoluble BrC was strongly correlated with ambient elemental carbon concentration, suggesting similar sources. Absorption Ångström exponent (Å(a)) (fitted between 300 and 600 nm wavelengths) was 3.2 (±1.2) for the PILS water-soluble BrC measurement, compared to 4.8 (±0.5) and 7.6 (±0.5) for methanol- and water-soluble BrC from filter extracts, respectively. These results show that fine particle BrC was prevalent in the LA basin during CalNex, yet many of its properties and potential impacts remain unknown. PMID:23506531

  8. Thermal conversion of an Fe₃O₄@metal-organic framework: a new method for an efficient Fe-Co/nanoporous carbon microwave absorbing material.

    PubMed

    Zhang, Xingmiao; Ji, Guangbin; Liu, Wei; Quan, Bin; Liang, Xiaohui; Shang, Chaomei; Cheng, Yan; Du, Youwei

    2015-08-14

    A novel FeCo nanoparticle embedded nanoporous carbon composite (Fe-Co/NPC) was synthesized via in situ carbonization of dehydro-ascorbic acid (DHAA) coated Fe3O4 nanoparticles encapsulated in a metal-organic framework (zeolitic imidazolate framework-67, ZIF-67). The molar ratio of Fe/Co significantly depends on the encapsulated content of Fe3O4 in ZIF-67. The composites filled with 50 wt% of the Fe-Co/NPC-2.0 samples in paraffin show a maximum reflection loss (RL) of -21.7 dB at a thickness of 1.2 mm; in addition, a broad absorption bandwidth for RL < -10 dB which covers from 12.2 to 18 GHz can be obtained, and its minimum reflection loss and bandwidth (RL values exceeding -10 dB) are far greater than those of commercial carbonyl iron powder under a very low thickness (1-1.5 mm). This study not only provides a good reference for future preparation of carbon-based lightweight microwave absorbing materials but also broadens the application of such kinds of metal-organic frameworks. PMID:26167763

  9. Monte Carlo estimation of radiation dose in organs of female and male adult phantoms due to FDG-F18 absorbed in the lungs

    NASA Astrophysics Data System (ADS)

    Belinato, Walmir; Santos, William S.; Silva, Rogério M. V.; Souza, Divanizia N.

    2014-03-01

    The determination of dose conversion factors (S values) for the radionuclide fluorodeoxyglucose (18F-FDG) absorbed in the lungs during a positron emission tomography (PET) procedure was calculated using the Monte Carlo method (MCNPX version 2.7.0). For the obtained dose conversion factors of interest, it was considered a uniform absorption of radiopharmaceutical by the lung of a healthy adult human. The spectrum of fluorine was introduced in the input data file for the simulation. The simulation took place in two adult phantoms of both sexes, based on polygon mesh surfaces called FASH and MASH with anatomy and posture according to ICRP 89. The S values for the 22 internal organs/tissues, chosen from ICRP No. 110, for the FASH and MASH phantoms were compared with the results obtained from a MIRD V phantoms called ADAM and EVA used by the Committee on Medical Internal Radiation Dose (MIRD). We observed variation of more than 100% in S values due to structural anatomical differences in the internal organs of the MASH and FASH phantoms compared to the mathematical phantom.

  10. High voltage and efficient bilayer heterojunction solar cells based on an organic-inorganic hybrid perovskite absorber with a low-cost flexible substrate.

    PubMed

    Chiang, Yi-Fang; Jeng, Jun-Yuan; Lee, Mu-Huan; Peng, Shin-Rung; Chen, Peter; Guo, Tzung-Fang; Wen, Ten-Chin; Hsu, Yao-Jane; Hsu, Ching-Ming

    2014-04-01

    A low temperature (<100 °C), flexible solar cell based on an organic-inorganic hybrid CH3NH3PbI3 perovskite-fullerene planar heterojunction (PHJ) is successfully demonstrated. In this manuscript, we study the effects of energy level offset between a solar absorber (organic-inorganic hybrid CH3NH3PbI3 perovskite) and the selective contact materials on the photovoltaic behaviors of the planar organometallic perovskite-fullerene heterojunction solar cells. We find that the difference between the highest occupied molecular orbital (HOMO) level of CH3NH3PbI3 perovskite and the Fermi level of indium-tin-oxide (ITO) dominates the voltage output of the device. ITO films on glass or on the polyethylene terephthalate (PET) flexible substrate with different work functions are investigated to illustrate this phenomenon. The higher work function of the PET/ITO substrate decreases the energy loss of hole transfer from the HOMO of perovskite to ITO and minimizes the energy redundancy of the photovoltage output. The devices using the high work function ITO substrate as contact material show significant open-circuit voltage enhancement (920 mV), with the power conversion efficiency of 4.54%, and these types of extra-thin planar bilayer heterojunction solar cells have the potential advantages of low-cost and lightweight. PMID:24553998

  11. Charge carrier mobility in hybrid halide perovskites

    PubMed Central

    Motta, Carlo; El-Mellouhi, Fedwa; Sanvito, Stefano

    2015-01-01

    The charge transport properties of hybrid halide perovskites are investigated with a combination of density functional theory including van der Waals interaction and the Boltzmann theory for diffusive transport in the relaxation time approximation. We find the mobility of electrons to be in the range 5–10 cm2V−1s−1 and that for holes within 1–5 cm2V−1s−1, where the variations depend on the crystal structure investigated and the level of doping. Such results, in good agreement with recent experiments, set the relaxation time to about 1 ps, which is the time-scale for the molecular rotation at room temperature. For the room temperature tetragonal phase we explore two possible orientations of the organic cations and find that the mobility has a significant asymmetry depending on the direction of the current with respect to the molecular axis. This is due mostly to the way the PbI3 octahedral symmetry is broken. Interestingly we find that substituting I with Cl has minor effects on the mobilities. Our analysis suggests that the carrier mobility is probably not a key factor in determining the high solar-harvesting efficiency of this class of materials. PMID:26235910

  12. Moisture resistant and anti-reflection optical coatings produced by plasma polymerization of organic compounds

    NASA Technical Reports Server (NTRS)

    Hollahan, J. R.; Wydeven, T.

    1975-01-01

    The need for protective coatings on critical optical surfaces, such as halide crystal windows or lenses used in spectroscopy, has long been recognized. It has been demonstrated that thin, one micron, organic coatings produced by polymerization of flourinated monomers in low temperature gas discharge (plasma) exhibit very high degrees of moisture resistence, e.g., hundreds of hours protection for cesium iodide vs. minutes before degradation sets in for untreated surfaces. The index of refraction of these coatings is intermediate between that of the halide substrate and air, a condition for anti-reflection, another desirable property of optical coatings. Thus, the organic coatings not only offer protection, but improved transmittance as well. The polymer coating is non-absorbing over the range 0.4 to 40 microns with an exception at 8.0 microns, the expected absorption for C-F bonds.

  13. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells

    NASA Astrophysics Data System (ADS)

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-07-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials.

  14. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells.

    PubMed

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-01-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials. PMID:27411487

  15. A composite light-harvesting layer from photoactive polymer and halide perovskite for planar heterojunction solar cells

    PubMed Central

    Wang, Heming; Rahaq, Yaqub; Kumar, Vikas

    2016-01-01

    A new route for fabrication of photoactive materials in organic-inorganic hybrid solar cells is presented in this report. Photoactive materials by blending a semiconductive conjugated polymer with an organolead halide perovskite were fabricated for the first time. The composite active layer was then used to make planar heterojunction solar cells with the PCBM film as the electron-acceptor. Photovoltaic performance of solar cells was investigated by J-V curves and external quantum efficiency spectra. We demonstrated that the incorporation of the conjugated photoactive polymer into organolead halide perovskites did not only contribute to the generation of charges, but also enhance stability of solar cells by providing a barrier protection to halide perovskites. It is expected that versatile of conjugated semi-conductive polymers and halide perovskites in photoactive properties enables to create various combinations, forming composites with advantages offered by both types of photoactive materials. PMID:27411487

  16. Dimming of metal halide lamps

    NASA Technical Reports Server (NTRS)

    Schurer, Kees

    1994-01-01

    We ran some tests on the effect of dimming of metal halide (MH) lamps upon the stability and the spectral quality of the light output. Lamps used were a new Philips lamp HPI-T 250W, a similar Philips lamp with a few thousand burning hours and a new Osram lamp HQI-T 250W/D. The ballast was a BBC type DJ 250/2KS, the starter a BAS TORGI type MZN 250 SE and the dimmer an Elstrom Control System type ERHQ-T 250. Power was derived from a Philips stabilizer, type PE 1602. Lamp output was monitored with a PAR meter. Spectra were taken at 100% and at 50% output as measured with the PAR meter. Lamps were allowed to stabilize at any setting for 30 minutes before measurements were made. Lamp manufacturers advise against dimming for fear of poor stability and intolerable changes of the spectrum. However, none of the lamps showed a decrease in stability, no flicker or wandering of the discharge, and the changes of the spectrum were not negligible, but certainly not dramatic. Lamps of either manufacture retain their white color, relative peak heights of spectral lines did shift, but no gaps in the spectrum occurred. Spectra taken at 50% with 30 minutes intervals coincided. Differences between the new and the older Philips lamp were noticeable, but not really significant.

  17. Efficiency of buffered aqueous carboxylic acid solutions and organic solvents to absorb SO/sub 2/ from industrial flue gas; solubility data from gas-liquid chromatography

    SciTech Connect

    Sanza, G.J.

    1982-01-01

    Nine adsorbents were examined. These potential candidates for flue gas desulfurization included 1-methyl-2-pyrrolidinone, tri-n-butyl phosphate (TBP), both 0.5 M and 1.0 M solutions of citric acid and glycolic acid, buffered to pH's of 4.5 and 3.8, and pure water. Infinite dilution activity coefficients of SO/sub 2/ were obtained by gas-liquid chromatography in a trial solvent of Nitrobenzene, and then in systems of 1-methyl-2-pyrrolidinone and TBP, independently. The solubility data of SO/sub 2/ was derived and found to be comparable to data obtained from a classical bubble-sparger apparatus. Solubility data was then programmed into an absorber-stripper computer simulator in order to calculate the various concentration and temperature profiles that would exist, the degree of desulfurization, and the steam consumption for all nine systems. Concentrated solutions of citric acid buffered to a low pH exhibited the most favorable conditions for application in direct steam regeneration processes. 1-methyl-2-pyrrolidinone yielded better performance than TBP did with high-pressure indirect steam used for stripping. Comparison between the aqueous solution systems which employed direct steam, and the organic systems which used indirect steam was inconclusive.

  18. The Remarkable Reactivity of Aryl Halides with Nucleophiles

    ERIC Educational Resources Information Center

    Bunnett, Joseph F.

    1974-01-01

    Discusses the reactivity of aryl halides with nucleophilic or basic reagents, including nucleophilic attacks on carbon, hydrogen, halogen, and arynes. Suggestions are made concerning revisions of the sections on aryl halide chemistry courses and the corresponding chapters in textbooks. (CC)

  19. Shallow halogen vacancies in halide optoelectronic materials

    SciTech Connect

    Shi, Hongliang; Du, Mao -Hua

    2014-11-05

    Halogen vacancies (VH) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep VH contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH3NH3PbI3 and TlBr. Both CH3NH3PbI3 and TlBr have been found to have shallow VH, in contrast to commonly seen deep VH in halides. In this paper, several halide optoelectronic materials, i.e., CH3NH3PbI3, CH3NH3SnI3 (photovoltaic materials), TlBr, and CsPbBr3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether VH is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns2 ions both play important roles in creating shallow VH in halides such as CH3NH3PbI3, CH3NH3SnI3, and TlBr. The key to identifying halides with shallow VH is to find the right crystal structures and compounds that suppress cation orbital hybridization at VH, such as those with long cation-cation distances and low anion coordination numbers, and those with crystal symmetry that prevents strong hybridization of cation dangling bond orbitals at VH. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow VH as good electronic and optoelectronic materials.

  20. High-performance size exclusion chromatography with a multi-wavelength absorbance detector study on dissolved organic matter characterisation along a water distribution system.

    PubMed

    Huang, Huiping; Sawade, Emma; Cook, David; Chow, Christopher W K; Drikas, Mary; Jin, Bo

    2016-06-01

    This study examined the associations between dissolved organic matter (DOM) characteristics and potential nitrification occurrence in the presence of chloramine along a drinking water distribution system. High-performance size exclusion chromatography (HPSEC) coupled with a multiple wavelength detector (200-280nm) was employed to characterise DOM by molecular weight distribution, bacterial activity was analysed using flow cytometry, and a package of simple analytical tools, such as dissolved organic carbon, absorbance at 254nm, nitrate, nitrite, ammonia and total disinfectant residual were also applied and their applicability to indicate water quality changes in distribution systems were also evaluated. Results showed that multi-wavelength HPSEC analysis was useful to provide information about DOM character while changes in molecule weight profiles at wavelengths less than 230nm were also able to be related to other water quality parameters. Correct selection of the UV wavelengths can be an important factor for providing appropriate indicators associated with different DOM compositions. DOM molecular weight in the range of 0.2-0.5kDa measured at 210nm correlated positively with oxidised nitrogen concentration (r=0.99), and the concentrations of active bacterial cells in the distribution system (r=0.85). Our study also showed that the changes of DOM character and bacterial cells were significant in those sampling points that had decreases in total disinfectant residual. HPSEC-UV measured at 210nm and flow cytometry can detect the changes of low molecular weight of DOM and bacterial levels, respectively, when nitrification occurred within the chloraminated distribution system. PMID:27266320

  1. 40 CFR 721.575 - Substituted alkyl halide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl halide. 721.575... Substances § 721.575 Substituted alkyl halide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted alkyl halide (PMN P-83-1222)...

  2. Method for recovering hydrocarbons from molten metal halides

    DOEpatents

    Pell, Melvyn B.

    1979-01-01

    In a process for hydrocracking heavy carbonaceous materials by contacting such carbonaceous materials with hydrogen in the presence of a molten metal halide catalyst to produce hydrocarbons having lower molecular weights and thereafter recovering the hydrocarbons so produced from the molten metal halide, an improvement comprising injecting into the spent molten metal halide, a liquid low-boiling hydrocarbon stream is disclosed.

  3. Recent advances in technetium halide chemistry.

    PubMed

    Poineau, Frederic; Johnstone, Erik V; Czerwinski, Kenneth R; Sattelberger, Alfred P

    2014-02-18

    Transition metal binary halides are fundamental compounds, and the study of their structure, bonding, and other properties gives chemists a better understanding of physicochemical trends across the periodic table. One transition metal whose halide chemistry is underdeveloped is technetium, the lightest radioelement. For half a century, the halide chemistry of technetium has been defined by three compounds: TcF6, TcF5, and TcCl4. The absence of Tc binary bromides and iodides in the literature was surprising considering the existence of such compounds for all of the elements surrounding technetium. The common synthetic routes that scientists use to obtain binary halides of the neighboring elements, such as sealed tube reactions between elements and flowing gas reactions between a molecular complex and HX gas (X = Cl, Br, or I), had not been reported for technetium. In this Account, we discuss how we used these routes to revisit the halide chemistry of technetium. We report seven new phases: TcBr4, TcBr3, α/β-TcCl3, α/β-TcCl2, and TcI3. Technetium tetrachloride and tetrabromide are isostructural to PtX4 (X = Cl or Br) and consist of infinite chains of edge-sharing TcX6 octahedra. Trivalent technetium halides are isostructural to ruthenium and molybdenum (β-TcCl3, TcBr3, and TcI3) and to rhenium (α-TcCl3). Technetium tribromide and triiodide exhibit the TiI3 structure-type and consist of infinite chains of face-sharing TcX6 (X = Br or I) octahedra. Concerning the trichlorides, β-TcCl3 crystallizes with the AlCl3 structure-type and consists of infinite layers of edge-sharing TcCl6 octahedra, while α-TcCl3 consists of infinite layers of Tc3Cl9 units. Both phases of technetium dichloride exhibit new structure-types that consist of infinite chains of [Tc2Cl8] units. For the technetium binary halides, we studied the metal-metal interaction by theoretical methods and magnetic measurements. The change of the electronic configuration of the metal atom from d(3) (Tc

  4. Vibration-Resistant Support for Halide Lamps

    NASA Technical Reports Server (NTRS)

    Kiss, J.

    1987-01-01

    Lamp envelope protected against breakage. Old and new mounts for halide arc lamp sealed in housing with parabolic refector and quartz window. New version supports lamp with compliant garters instead of rigid brazed joint at top and dimensionally unstable finger stock at bottom.

  5. Molecular compressibility of some halides in alcohols

    NASA Technical Reports Server (NTRS)

    Serban, C.; Auslaender, D.

    1974-01-01

    After measuring ultrasonic velocity and density, the molecular compressibility values from Wada's formula were calculated, for alkali metal halide solutions in methyl, ethyl, butyl, and glycol alcohol. The temperature and concentration dependence were studied, finding deviations due to the hydrogen bonds of the solvent.

  6. The Additive Coloration of Alkali Halides

    ERIC Educational Resources Information Center

    Jirgal, G. H.; and others

    1969-01-01

    Describes the construction and use of an inexpensive, vacuum furnace designed to produce F-centers in alkali halide crystals by additive coloration. The method described avoids corrosion or contamination during the coloration process. Examination of the resultant crystals is discussed and several experiments using additively colored crystals are…

  7. Incorporation of Cl into sequentially deposited lead halide perovskite films for highly efficient mesoporous solar cells

    NASA Astrophysics Data System (ADS)

    Dharani, Sabba; Dewi, Herlina Arianita; Prabhakar, Rajiv Ramanujam; Baikie, Tom; Shi, Chen; Yonghua, Du; Mathews, Nripan; Boix, Pablo P.; Mhaisalkar, Subodh G.

    2014-10-01

    Organic-inorganic lead halide perovskites have been widely used as absorbers on mesoporous TiO2 films as well as thin films in planar heterojunction solar cells, yielding very high photovoltaic conversion efficiencies. Both the addition of chloride and sequential deposition methods were successfully employed to enhance the photovoltaic performance. Here, both approaches are combined in a sequential method by spincoating PbCl2 + PbI2 on a mesoporous TiO2 film followed by the perovskite transformation. The role of Cl in determining the optical, electrical, structural and morphological properties is correlated with the photovoltaic performance. The highest photovoltaic efficiency of 14.15% with the Voc, FF and Jsc being 1.09 V, 0.65 and 19.91 mA cm-2 respectively was achieved with 10 mol% of PbCl2 addition due to an increase of the film conductivity induced by a better perovskite morphology. This is linked to an improvement of the hysteresis and reproducibility of the solar cells.Organic-inorganic lead halide perovskites have been widely used as absorbers on mesoporous TiO2 films as well as thin films in planar heterojunction solar cells, yielding very high photovoltaic conversion efficiencies. Both the addition of chloride and sequential deposition methods were successfully employed to enhance the photovoltaic performance. Here, both approaches are combined in a sequential method by spincoating PbCl2 + PbI2 on a mesoporous TiO2 film followed by the perovskite transformation. The role of Cl in determining the optical, electrical, structural and morphological properties is correlated with the photovoltaic performance. The highest photovoltaic efficiency of 14.15% with the Voc, FF and Jsc being 1.09 V, 0.65 and 19.91 mA cm-2 respectively was achieved with 10 mol% of PbCl2 addition due to an increase of the film conductivity induced by a better perovskite morphology. This is linked to an improvement of the hysteresis and reproducibility of the solar cells. Electronic

  8. Ionic alkali halide XUV laser feasibility study

    SciTech Connect

    Yang, T.T.; Gylys, V.T.; Bower, R.D.; Harris, D.G.; Blauer, J.A.; Turner, C.E.; Hindy, R.N.

    1989-11-10

    The objective of this work is to assess the feasibility of a select set of ionic alkali halide XUV laser concepts by obtaining the relevant kinetic and spectroscopic parameters required for a proof-of-principle and conceptual design. The proposed lasers operate in the 80--200 nm spectral region and do not require input from outside radiation sources for their operation. Frequency up-conversion and frequency mixing techniques and therefore not considered in the work to be described. An experimental and theoretical study of a new type of laser operating in the extreme ultraviolet wavelength region has been conducted. The lasing species are singly ionized alkali halide molecules such as Rb{sup 2+}F{sub {minus}}, Rb{sup 2+}Br{sup {minus}} and Cs{sup 2+}F{sup {minus}}. These species are similar in electronic structure to the rare gas halide excimers, such as XeF and Krf, except that the ionic molecules emit at wavelengths of 80--200 nm, much shorter than the conventional rare-gas halide excimer laser. The radiative lifetime of these molecules are typically near 1 ns, which is about an order of magnitude shorter than that for rare-gas halide systems. The values of the cross section for stimulated emission are on the order of 1 {times} 10{sup {minus}16}cm{sup 2}. Because of the fundamental similarity to existing UV lasers, these systems show promise as a high power, efficient XUV lasers. 55 refs., 50 figs., 5 tabs.

  9. First-principles study on the electronic and optical properties of cubic ABX3 halide perovskites

    NASA Astrophysics Data System (ADS)

    Lang, Li; Yang, Ji-Hui; Liu, Heng-Rui; Xiang, H. J.; Gong, X. G.

    2014-01-01

    The electronic properties of ABX3 type compounds in the cubic phase are systematically studied using the first-principles calculations. The chemical trend of their properties as A or B or X varies is fully investigated. The optical properties of the ABX3 compounds are also investigated. Our calculations show that taking into account the spin-orbit coupling effect is crucial for predicting the accurate band gap of these halide perovskites. We predict that CH3NH3SnBr3 is a promising material for solar cells absorber with a perfect band gap and good optical absorption.

  10. Damage tolerant light absorbing material

    DOEpatents

    Lauf, R.J.; Hamby, C. Jr.; Akerman, M.A.; Seals, R.D.

    1993-09-07

    A light absorbing article comprised of a composite of carbon-bonded carbon fibers, is prepared by: blending carbon fibers with a carbonizable organic powder to form a mixture; dispersing the mixture into an aqueous slurry; vacuum molding the aqueous slurry to form a green article; drying and curing the green article to form a cured article; and, carbonizing the cured article at a temperature of at least about 1000 C to form a carbon-bonded carbon fiber light absorbing composite article having a bulk density less than 1 g/cm[sup 3]. 9 figures.

  11. Damage tolerant light absorbing material

    DOEpatents

    Lauf, Robert J.; Hamby, Jr., Clyde; Akerman, M. Alfred; Seals, Roland D.

    1993-01-01

    A light absorbing article comprised of a composite of carbon-bonded carbon fibers, prepared by: blending carbon fibers with a carbonizable organic powder to form a mixture; dispersing the mixture into an aqueous slurry; vacuum molding the aqueous slurry to form a green article; drying and curing the green article to form a cured article; and, carbonizing the cured article at a temperature of at least about 1000.degree. C. to form a carbon-bonded carbon fiber light absorbing composite article having a bulk density less than 1 g/cm.sup.3.

  12. Enhancement of Exciton Emission in Lead Halide-Based Layered Perovskites by Cation Mixing.

    PubMed

    Era, Masanao; Komatsu, Yumeko; Sakamoto, Naotaka

    2016-04-01

    Spin-coated films of a lead halide, PbX: X = I and Br, layered perovskites having cyclohexenylethyl ammonium molecule as an organic layer, which were mixed with other metal halide-based layered perovskites consisting of various divalent metal halides (for example, Ca2, Cdl2, FeI2, SnBr2 and so on), were prepared. The results of X-ray diffraction measurements exhibited that solid solution formation between PbX-based layered perovskite and other divalent metal halide-based layered perovskites was observed up to very high molar concentration of 50 molar% in the mixed film samples when divalent cations having ionic radius close to that of Pb2+ were employed. In the solid solution films, the exciton emission was much enhanced at room temperature. Exciton emission intensity of Pbl-based layered perovskite mixed with Cal-based layered perovskite (20 molar%) is about 5 times large that of the pristine Pbl-based layered perovskite, and that of PbBr-based layered perovskite mixed with SnBr-based layered perovskite (20 molar%) was also about 5 times large that of the pristine PbBr-based layered perovskite at room temperature. PMID:27451628

  13. Stabilization of Organic-Inorganic Perovskite Layers by Partial Substitution of Iodide by Bromide in Methylammonium Lead Iodide.

    PubMed

    Ruess, Raffael; Benfer, Felix; Böcher, Felix; Stumpp, Martina; Schlettwein, Derck

    2016-05-18

    Thin films of the methylammonium lead halides CH3 NH3 Pb(I1-x Brx )3 are prepared on fluorine-doped tin oxide substrates and exposed to humid air in the dark and under illumination. To characterize the stability of the materials, UV/Vis spectra are acquired at fixed intervals, accompanied by XRD, energy-dispersive X-ray spectroscopy, SEM, and confocal laser scanning microscopy. Different degradation mechanisms are observed depending on the environmental conditions. It is found that bromide can successfully suppress the transformation of the perovskite into the monohydrate, presumably owing to stronger hydrogen-bonding interactions with the organic cation. However, under illumination in humid air, rather rapid decomposition of the perovskites was still observed, which is due to phase segregation. The use of increased bromide content in methylammonium lead halide absorbers is discussed in terms of their application in perovskite solar cells. PMID:26853438

  14. Transport of Soil Halides through Rice Paddies: A Viable Mechanism for Rapid Dispersion of the Soil Halide Reservoir

    NASA Astrophysics Data System (ADS)

    Redeker, K. R.; Manley, S.; Wang, N.; Cicerone, R.

    2002-05-01

    On short time scales (1-10 years) soil halide concentrations have been assumed to be primarily driven by leaching and deposition processes. Recent results however, have shown that terrestrial plants volatilize soil halides in the form of methyl halides. Emissions of methyl chloride, methyl bromide and methyl iodide represent major pathways for delivery of inorganic halogen radicals to the atmosphere. Inorganic halogen radicals destroy ozone in the stratosphere and modify the oxidative capacity of the lower atmosphere. We have previously shown that rice paddies emit methyl halides and that emissions depend on growth stage of the rice plant as well as field water management. We show here that rice grown in a greenhouse at UCI is capable of volatilizing and/or storing up to 30%, 5%, and 10% of the available chloride, bromide and iodide within the top meter of soil. The percent of plant tissue halide volatilized as methyl halide over the course of the season is calculated to be 0.05%, 0.25% and 85.0% for chloride, bromide and iodide. We compare our greenhouse soil halide concentrations to other commercial rice fields around the world and estimate the e-folding time for soil halides within each region. We suggest that rice agriculture is the driving removal mechanism for halides within rice paddies and that terrestrial plants play a larger role in global cycling of halides than previously estimated.

  15. Flame inhibition by hydrogen halides - Some spectroscopic measurements

    NASA Technical Reports Server (NTRS)

    Lerner, N. R.; Cagliostro, D. E.

    1973-01-01

    The far-ultraviolet absorption spectrum of an air-propane diffusion flame inhibited with hydrogen halides has been studied. Plots of the absorption of light by hydrogen halides as a function of position in the flame and also as a function of the amount of hydrogen halide added to the flame have been obtained. The hydrogen halides are shown to be more stable on the fuel side of the reaction zone than they are on the air side. Thermal diffusion is seen to be important in determining the concentration distribution of the heavier hydrogen halides in diffusion flames. The relationship between the concentration distribution of the hydrogen halides in the flame and the flame inhibition mechanism is discussed.

  16. Lanthanide-halide based humidity indicators

    DOEpatents

    Beitz, James V.; Williams, Clayton W.

    2008-01-01

    The present invention discloses a lanthanide-halide based humidity indicator and method of producing such indicator. The color of the present invention indicates the humidity of an atmosphere to which it is exposed. For example, impregnating an adsorbent support such as silica gel with an aqueous solution of the europium-containing reagent solution described herein, and dehydrating the support to dryness forms a substance with a yellow color. When this substance is exposed to a humid atmosphere the water vapor from the air is adsorbed into the coating on the pore surface of the silica gel. As the water content of the coating increases, the visual color of the coated silica gel changes from yellow to white. The color change is due to the water combining with the lanthanide-halide complex on the pores of the gel.

  17. Composition for absorbing hydrogen

    DOEpatents

    Heung, L.K.; Wicks, G.G.; Enz, G.L.

    1995-05-02

    A hydrogen absorbing composition is described. The composition comprises a porous glass matrix, made by a sol-gel process, having a hydrogen-absorbing material dispersed throughout the matrix. A sol, made from tetraethyl orthosilicate, is mixed with a hydrogen-absorbing material and solidified to form a porous glass matrix with the hydrogen-absorbing material dispersed uniformly throughout the matrix. The glass matrix has pores large enough to allow gases having hydrogen to pass through the matrix, yet small enough to hold the particles dispersed within the matrix so that the hydrogen-absorbing particles are not released during repeated hydrogen absorption/desorption cycles.

  18. Composition for absorbing hydrogen

    DOEpatents

    Heung, Leung K.; Wicks, George G.; Enz, Glenn L.

    1995-01-01

    A hydrogen absorbing composition. The composition comprises a porous glass matrix, made by a sol-gel process, having a hydrogen-absorbing material dispersed throughout the matrix. A sol, made from tetraethyl orthosilicate, is mixed with a hydrogen-absorbing material and solidified to form a porous glass matrix with the hydrogen-absorbing material dispersed uniformly throughout the matrix. The glass matrix has pores large enough to allow gases having hydrogen to pass through the matrix, yet small enough to hold the particles dispersed within the matrix so that the hydrogen-absorbing particles are not released during repeated hydrogen absorption/desorption cycles.

  19. Interpulse kinetics in copper and copper halide lasers

    NASA Technical Reports Server (NTRS)

    Harstad, K. G.

    1983-01-01

    The various rate processes that govern the interpulse relaxation in metal vapor and metal halide vapor lasers are considered. Computer calculations indicate that the rapid metastable levels relaxation observed in copper and copper halide laser experiments requires the existence of a relatively small resonance in the cross section for metastable excitation or deexcitation near threshold. The accurate calculation of interpulse relaxation requires knowledge of rate constants presently not well known; this is especially so for metal halide lasers.

  20. Process and composition for drying of gaseous hydrogen halides

    DOEpatents

    Tom, Glenn M.; Brown, Duncan W.

    1989-08-01

    A process for drying a gaseous hydrogen halide of the formula HX, wherein X is selected from the group consisting of bromine, chlorine, fluorine, and iodine, to remove water impurity therefrom, comprising: contacting the water impurity-containing gaseous hydrogen halide with a scavenger including a support having associated therewith one or more members of the group consisting of: (a) an active scavenging moiety selected from one or more members of the group consisting of: (i) metal halide compounds dispersed in the support, of the formula MX.sub.y ; and (ii) metal halide pendant functional groups of the formula -MX.sub.y-1 covalently bonded to the support, wherein M is a y-valent metal, and y is an integer whose value is from 1 to 3; (b) corresponding partially or fully alkylated compounds and/or pendant functional groups, of the metal halide compounds and/or pendant functional groups of (a); wherein the alkylated compounds and/or pendant functional groups, when present, are reactive with the gaseous hydrogen halide to form the corresponding halide compounds and/or pendant functional groups of (a); and M being selected such that the heat of formation, .DELTA.H.sub.f of its hydrated halide, MX.sub.y.(H.sub.2 O).sub.n, is governed by the relationship: .DELTA.H.sub.f .gtoreq.n.times.10.1 kilocalories/mole of such hydrated halide compound wherein n is the number of water molecules bound to the metal halide in the metal halide hydrate. Also disclosed is an appertaining scavenger composition and a contacting apparatus wherein the scavenger is deployed in a bed for contacting with the water impurity-containing gaseous hydrogen halide.

  1. Evaluation of low melting halide systems for battery applications

    NASA Astrophysics Data System (ADS)

    Mamantov, G.; Perrovic, C.

    1981-03-01

    This three year program involves evaluation of selected low temperature molten salt solvent systems containing inorganic and/or organic chlorides and bromides for battery applications. The research involves determination of the liquidus temperatures, the specific electrical conductivity, and the electrochemical span of selected halide systems. Characterization of the solvent species by Raman spectroscopy, vapor pressure measurements, and the electrochemical study of a few cathode and anode systems will be undertaken for the most promising solvent systems. The research during the second year of this project involved the determination of liquidus temperatures and/or specific electrical conductivities for a number of binary and ternary molten salt systems containing AlCl3, AlBr3, SbCl3, FeCl3, and GaCl3.

  2. Giant photostriction in organic–inorganic lead halide perovskites

    PubMed Central

    Zhou, Yang; You, Lu; Wang, Shiwei; Ku, Zhiliang; Fan, Hongjin; Schmidt, Daniel; Rusydi, Andrivo; Chang, Lei; Wang, Le; Ren, Peng; Chen, Liufang; Yuan, Guoliang; Chen, Lang; Wang, Junling

    2016-01-01

    Among the many materials investigated for next-generation photovoltaic cells, organic–inorganic lead halide perovskites have demonstrated great potential thanks to their high power conversion efficiency and solution processability. Within a short period of about 5 years, the efficiency of solar cells based on these materials has increased dramatically from 3.8 to over 20%. Despite the tremendous progress in device performance, much less is known about the underlying photophysics involving charge–orbital–lattice interactions and the role of the organic molecules in this hybrid material remains poorly understood. Here, we report a giant photostrictive response, that is, light-induced lattice change, of >1,200 p.p.m. in methylammonium lead iodide, which could be the key to understand its superior optical properties. The strong photon-lattice coupling also opens up the possibility of employing these materials in wireless opto-mechanical devices. PMID:27044485

  3. Lanthanide doped strontium-barium cesium halide scintillators

    SciTech Connect

    Bizarri, Gregory; Bourret-Courchesne, Edith; Derenzo, Stephen E.; Borade, Ramesh B.; Gundiah, Gautam; Yan, Zewu; Hanrahan, Stephen M.; Chaudhry, Anurag; Canning, Andrew

    2015-06-09

    The present invention provides for a composition comprising an inorganic scintillator comprising an optionally lanthanide-doped strontium-barium, optionally cesium, halide, useful for detecting nuclear material.

  4. Microtitration of various anions with quaternary ammonium halides using solid-state electrodes

    SciTech Connect

    Selig, W.

    1980-01-01

    Many solid-state electrodes were found to respond as endpoint detectors in the potentiometric titration of large inorganic and organic anions with quaternary ammonium halides. The best response was obtained with the iodide and cyanide electrodes although practically any electrode can function as endpoint sensor. The titrants were hexadecylpyridinium chloride and hexadecyltrimethylammonium chloride; hexadecyltrimethylammonium bromide and Hyamine 1622 may also be used. Some inorganic anions thus titratable are perrhenate, persulfate, ferricyanide, hexafluorophosphate, and hexachloroplatinate. Examples of organic anions titratable are nitroform, tetraphenylborate, cyanotriphenylborate, picrate, long-chain sulfates and sulfonates, and some soaps. The reverse titration of quaternary ammonium halides vs dodecylsulfate is also feasible. Some titrations are feasible in a partially nonaqueous medium.

  5. High-performance liquid chromatography - Ultraviolet method for the determination of total specific migration of nine ultraviolet absorbers in food simulants based on 1,1,3,3-Tetramethylguanidine and organic phase anion exchange solid phase extraction to remove glyceride.

    PubMed

    Wang, Jianling; Xiao, Xiaofeng; Chen, Tong; Liu, Tingfei; Tao, Huaming; He, Jun

    2016-06-17

    The glyceride in oil food simulant usually causes serious interferences to target analytes and leads to failure of the normal function of the RP-HPLC column. In this work, a convenient HPLC-UV method for the determination of the total specific migration of nine ultraviolet (UV) absorbers in food simulants was developed based on 1,1,3,3-tetramethylguanidine (TMG) and organic phase anion exchange (OPAE) SPE to efficiently remove glyceride in olive oil simulant. In contrast to the normal ion exchange carried out in an aqueous solution or aqueous phase environment, the OPAE SPE was performed in the organic phase environments, and the time-consuming and challenging extraction of the nine UV absorbers from vegetable oil with aqueous solution could be readily omitted. The method was proved to have good linearity (r≥0.99992), precision (intra-day RSD≤3.3%), and accuracy(91.0%≤recoveries≤107%); furthermore, the lower limit of quantifications (0.05-0.2mg/kg) in five types of food simulants(10% ethanol, 3% acetic acid, 20% ethanol, 50% ethanol and olive oil) was observed. The method was found to be well suited for quantitative determination of the total specific migration of the nine UV absorbers both in aqueous and vegetable oil simulant according to Commission Regulation (EU) No. 10/2011. Migration levels of the nine UV absorbers were determined in 31 plastic samples, and UV-24, UV-531, HHBP and UV-326 were frequently detected, especially in olive oil simulant for UV-326 in PE samples. In addition, the OPAE SPE procedure was also been applied to efficiently enrich or purify seven antioxidants in olive oil simulant. Results indicate that this procedure will have more extensive applications in the enriching or purification of the extremely weak acidic compounds with phenol hydroxyl group that are relatively stable in TMG n-hexane solution and that can be barely extracted from vegetable oil. PMID:27189432

  6. Real Time Monitoring of Dissolved Organic Carbon Concentration and Disinfection By-Product Formation Potential in a Surface Water Treatment Plant with Simulaneous UV-VIS Absorbance and Fluorescence Excitation-Emission Mapping

    NASA Astrophysics Data System (ADS)

    Gilmore, A. M.

    2015-12-01

    This study describes a method based on simultaneous absorbance and fluorescence excitation-emission mapping for rapidly and accurately monitoring dissolved organic carbon concentration and disinfection by-product formation potential for surface water sourced drinking water treatment. The method enables real-time monitoring of the Dissolved Organic Carbon (DOC), absorbance at 254 nm (UVA), the Specific UV Absorbance (SUVA) as well as the Simulated Distribution System Trihalomethane (THM) Formation Potential (SDS-THMFP) for the source and treated water among other component parameters. The method primarily involves Parallel Factor Analysis (PARAFAC) decomposition of the high and lower molecular weight humic and fulvic organic component concentrations. The DOC calibration method involves calculating a single slope factor (with the intercept fixed at 0 mg/l) by linear regression for the UVA divided by the ratio of the high and low molecular weight component concentrations. This method thus corrects for the changes in the molecular weight component composition as a function of the source water composition and coagulation treatment effects. The SDS-THMFP calibration involves a multiple linear regression of the DOC, organic component ratio, chlorine residual, pH and alkalinity. Both the DOC and SDS-THMFP correlations over a period of 18 months exhibited adjusted correlation coefficients with r2 > 0.969. The parameters can be reported as a function of compliance rules associated with required % removals of DOC (as a function of alkalinity) and predicted maximum contaminant levels (MCL) of THMs. The single instrument method, which is compatible with continuous flow monitoring or grab sampling, provides a rapid (2-3 minute) and precise indicator of drinking water disinfectant treatability without the need for separate UV photometric and DOC meter measurements or independent THM determinations.

  7. Mechanism and Selectivity in Nickel-Catalyzed Cross-Electrophile Coupling of Aryl Halides with Alkyl Halides

    PubMed Central

    Biswas, Soumik; Weix, Daniel J.

    2013-01-01

    The direct cross-coupling of two different electrophiles, such as an aryl halide with an alkyl halide, offers many advantages over conventional cross-coupling methods that require a carbon nucleophile. Despite its promise as a versatile synthetic strategy, a limited understanding of the mechanism and origin of cross selectivity has hindered progress in reaction development and design. Herein, we shed light on the mechanism for the nickel-catalyzed cross-electrophile coupling of aryl halides with alkyl halides and demonstrate that the selectivity arises from an unusual catalytic cycle that combines both polar and radical steps to form the new C-C bond. PMID:23952217

  8. Involvement of S-adenosylmethionine-dependent halide/thiol methyltransferase (HTMT) in methyl halide emissions from agricultural plants: isolation and characterization of an HTMT-coding gene from Raphanus sativus (daikon radish)

    PubMed Central

    Itoh, Nobuya; Toda, Hiroshi; Matsuda, Michiko; Negishi, Takashi; Taniguchi, Tomokazu; Ohsawa, Noboru

    2009-01-01

    Background Biogenic emissions of methyl halides (CH3Cl, CH3Br and CH3I) are the major source of these compounds in the atmosphere; however, there are few reports about the halide profiles and strengths of these emissions. Halide ion methyltransferase (HMT) and halide/thiol methyltransferase (HTMT) enzymes concerning these emissions have been purified and characterized from several organisms including marine algae, fungi, and higher plants; however, the correlation between emission profiles of methyl halides and the enzymatic properties of HMT/HTMT, and their role in vivo remains unclear. Results Thirty-five higher plant species were screened, and high CH3I emissions and HMT/HTMT activities were found in higher plants belonging to the Poaceae family, including wheat (Triticum aestivum L.) and paddy rice (Oryza sativa L.), as well as the Brassicaceae family, including daikon radish (Raphanus sativus). The in vivo emission of CH3I clearly correlated with HMT/HTMT activity. The emission of CH3I from the sprouting leaves of R. sativus, T. aestivum and O. sativa grown hydroponically increased with increasing concentrations of supplied iodide. A gene encoding an S-adenosylmethionine halide/thiol methyltransferase (HTMT) was cloned from R. sativus and expressed in Escherichia coli as a soluble protein. The recombinant R. sativus HTMT (RsHTMT) was revealed to possess high specificity for iodide (I-), bisulfide ([SH]-), and thiocyanate ([SCN]-) ions. Conclusion The present findings suggest that HMT/HTMT activity is present in several families of higher plants including Poaceae and Brassicaceae, and is involved in the formation of methyl halides. Moreover, it was found that the emission of methyl iodide from plants was affected by the iodide concentration in the cultures. The recombinant RsHTMT demonstrated enzymatic properties similar to those of Brassica oleracea HTMT, especially in terms of its high specificity for iodide, bisulfide, and thiocyanate ions. A survey of

  9. Modelling Absorbent Phenomena of Absorbent Structure

    NASA Astrophysics Data System (ADS)

    Sayeb, S.; Ladhari, N.; Ben Hassen, M.; Sakli, F.

    Absorption, retention and strike through time, as evaluating criteria of absorbent structures quality were studied. Determination of influent parameters on these criteria were realized by using the design method of experimental sets. In this study, the studied parameters are: Super absorbent polymer (SAP)/fluff ratio, compression and the porosity of the non woven used as a cover stock. Absorption capacity and retention are mostly influenced by SAP/fluff ratio. However, strike through time is affected by compression. Thus, a modelling of these characteristics in function of the important parameter was established.

  10. Methods for absorbing neutrons

    DOEpatents

    Guillen, Donna P.; Longhurst, Glen R.; Porter, Douglas L.; Parry, James R.

    2012-07-24

    A conduction cooled neutron absorber may include a metal matrix composite that comprises a metal having a thermal neutron cross-section of at least about 50 barns and a metal having a thermal conductivity of at least about 1 W/cmK. Apparatus for providing a neutron flux having a high fast-to-thermal neutron ratio may include a source of neutrons that produces fast neutrons and thermal neutrons. A neutron absorber positioned adjacent the neutron source absorbs at least some of the thermal neutrons so that a region adjacent the neutron absorber has a fast-to-thermal neutron ratio of at least about 15. A coolant in thermal contact with the neutron absorber removes heat from the neutron absorber.

  11. Externally tuned vibration absorber

    DOEpatents

    Vincent, Ronald J.

    1987-09-22

    A vibration absorber unit or units are mounted on the exterior housing of a hydraulic drive system of the type that is powered from a pressure wave generated, e.g., by a Stirling engine. The hydraulic drive system employs a piston which is hydraulically driven to oscillate in a direction perpendicular to the axis of the hydraulic drive system. The vibration absorbers each include a spring or other resilient member having one side affixed to the housing and another side to which an absorber mass is affixed. In a preferred embodiment, a pair of vibration absorbers is employed, each absorber being formed of a pair of leaf spring assemblies, between which the absorber mass is suspended.

  12. Methyl halides in and over the eastern Pacific (40 /sup 0/N-32 /sup 0/S)

    SciTech Connect

    Singh, H.B.; Salas, L.J.; Stiles, R.E.

    1983-04-20

    Methyl chloride, methyl bromide, and methyl iodide measurements in and over the eastern Pacific (40 /sup 0/N and 32 /sup 0/S latitude) show mean air concentrations of 633 parts per trillion (ppt), 23 ppt, and 2 ppt, and mean surface seawater concentrations of 11.5 ng/l, 1.2 ng/l, and 1.6 ng/l respectively. Long-term ambient measurements at a marine Pacific site (39 /sup 0/N) show an essentially unchanging background, with some indication of high concentrations of methyl bromide and methyl iodide during summertime. The oceanic data indicate a mean surface supersaturation of 275%, 250%, and 340%, respectively, for these three methyl halides. Depth profiles show that methyl halides are most abundant in the top mixed layer of the ocean. Oceanic concentrations of methyl chloride and methyl bromide are significantly correlated (linear regression coefficient of 0.85), suggesting a common source. No relationship between oceanic methyl iodide concentrations and the other two halides could be found. Coexistence of high concentrations of methyl iodide with relatively low concentrations of methyl chloride and vice versa provided no direct support for the hypothesis that chloride ion reactions with methyl iodide may be the dominant oceanic source of methyl chloride. For the eastern Pacific, mean ocean to air fluxes (in units of 10/sup -7/ g cm/sup -2/ yr/sup -1/) of 13,1, and 1 are determined for methyl chloride, methyl bromine, and methyl iodide, respectively. When extrapolated to global waters, they provide an adequate source to explain the atmospheric reservoir of these organic halides. Total organic bromine and iodine measurements would suggest that methyl bromide and methyl iodide contribute predominately to the tropospheric bromine and iodine organic reservoir.

  13. Controlling Metal-Halide Vapor Density in Lasers

    NASA Technical Reports Server (NTRS)

    Pivirotto, T. J.

    1984-01-01

    Streams of buffer gas convect and dilute metal-halide vapor. Technique uses flow of buffer gas through reservoir, which contains heated metal halide, to convect vapors into discharge tube. Second stream of buffer gas dilutes vapor. Final vapor density in laser tube controlled and changed by adjusting either one or both of buffer gas flow rates.

  14. [Emissions of methyl halides from coastal salt marshes: A review].

    PubMed

    Xie, Wen-xia; Zhao, Quan-sheng; Cui, Yu-qian; Du, Hui-na; Ye, Si-yuan

    2015-11-01

    Methyl halides are the major carrier of halogens in the atmosphere, and they play an important role in tropospheric and stratospheric ozone depletion. Meanwhile, methyl halides can act as greenhouse gases in the atmosphere, and they are also environmentally significant because of their toxicity. Coastal salt marshes, the important intertidal ecosystems at the land-ocean interface, have been considered to be a large potential natural source of methyl halides. In this paper, the research status of the natural source or sink of methyl halides, the mechanisms of their emission from coastal salt marshes and affecting factors were summarized. In view of this, the following research fields need to be strengthened in the future: 1) Long time-scale and large region-range researches about the emission of methyl halides and the evaluation of their source and sink function, 2) Accurate quantification of contribution rates of different plant species and various biological types to fluxes of methyl halides, 3) Further researches on effects of the tidal fluctuation process and flooding duration on methyl halides emission, 4) Effects of the global change and human activities on methyl halides emission. PMID:26915215

  15. How specific halide adsorption varies hydrophobic interactions.

    PubMed

    Stock, Philipp; Müller, Melanie; Utzig, Thomas; Valtiner, Markus

    2016-03-01

    Hydrophobic interactions (HI) are driven by the water structure around hydrophobes in aqueous electrolytes. How water structures at hydrophobic interfaces and how this influences the HI was subject to numerous studies. However, the effect of specific ion adsorption on HI and hydrophobic interfaces remains largely unexplored or controversial. Here, the authors utilized atomic force microscopy force spectroscopy at well-defined nanoscopic hydrophobic interfaces to experimentally address how specific ion adsorption of halide ions as well as NH4 (+), Cs(+), and Na(+) cations alters interaction forces across hydrophobic interfaces. Our data demonstrate that iodide adsorption at hydrophobic interfaces profoundly varies the hydrophobic interaction potential. A long-range and strong hydration repulsion at distances D > 3 nm, is followed by an instability which could be explained by a subsequent rapid ejection of adsorbed iodides from approaching hydrophobic interfaces. In addition, the authors find only a weakly pronounced influence of bromide, and as expected no influence of chloride. Also, all tested cations do not have any significant influence on HI. Complementary, x-ray photoelectron spectroscopy and quartz-crystal-microbalance with dissipation monitoring showed a clear adsorption of large halide ions (Br(-)/I(-)) onto hydrophobic self-assembled monolayers (SAMs). Interestingly, iodide can even lead to a full disintegration of SAMs due to specific and strong interactions of iodide with gold. Our data suggest that hydrophobic surfaces are not intrinsically charged negatively by hydroxide adsorption, as it was generally believed. Hydrophobic surfaces rather interact strongly with negatively charged large halide ions, leading to a surface charging and significant variation of interaction forces. PMID:26753786

  16. Ultraviolet absorption spectra of mercuric halides.

    NASA Technical Reports Server (NTRS)

    Templet, P.; Mcdonald, J. R.; Mcglynn, S. P.; Kendrow, C. H.; Roebber, J. L.; Weiss, K.

    1972-01-01

    The gas phase transitions of the mercuric halides were observed in the UV region by operating at temperatures above 400 K and at vapor pressures on the order of 0.5 mm. Spectral features exhibited by the chloride, bromide, and iodide of mercury correlate energetically with bands previously designated as intermolecular charge transfer transitions. The solution spectra of mercuric iodide and deep color of the crystals (if not due to some solid state interactions) indicate that this molecule may also have longer wavelength transitions.

  17. Raman spectra of hydroxide-halide melts

    NASA Astrophysics Data System (ADS)

    Zakiriyanova, I. D.; Khokhlov, V. A.

    2012-08-01

    The Raman spectra of molten binary mixtures based on sodium hydroxide and containing (mol %) 35 NaCl, 30 NaBr, and 30 NaI have been recorded at various temperatures. An increase in the vibrational frequency and the force constant of the O-H bond is detected under isothermal conditions upon a variation of the anionic composition of a melt in the series I → Br → Cl. Based on the experimental data, the viscosity of the hydroxide-halide melts is estimated.

  18. Advanced neutron absorber materials

    DOEpatents

    Branagan, Daniel J.; Smolik, Galen R.

    2000-01-01

    A neutron absorbing material and method utilizing rare earth elements such as gadolinium, europium and samarium to form metallic glasses and/or noble base nano/microcrystalline materials, the neutron absorbing material having a combination of superior neutron capture cross sections coupled with enhanced resistance to corrosion, oxidation and leaching.

  19. Amine synthesis via iron-catalysed reductive coupling of nitroarenes with alkyl halides.

    PubMed

    Cheung, Chi Wai; Hu, Xile

    2016-01-01

    (Hetero)Aryl amines, an important class of organic molecules in medicinal chemistry, are most commonly synthesized from anilines, which are in turn synthesized by hydrogenation of nitroarenes. Amine synthesis directly from nitroarenes is attractive due to improved step economy and functional group compatibility. Despite these potential advantages, there is yet no general method for the synthesis of (hetero)aryl amines by carbon-nitrogen cross-coupling of nitroarenes. Here we report the reductive coupling of nitroarenes with alkyl halides to yield (hetero)aryl amines. A simple iron catalyst enables the coupling with numerous primary, secondary and tertiary alkyl halides. Broad scope and high functional group tolerance are demonstrated. Mechanistic study suggests that nitrosoarenes and alkyl radicals are involved as intermediates. This new C-N coupling method provides general and step-economical access to aryl amines. PMID:27515391

  20. Amine synthesis via iron-catalysed reductive coupling of nitroarenes with alkyl halides

    PubMed Central

    Cheung, Chi Wai; Hu, Xile

    2016-01-01

    (Hetero)Aryl amines, an important class of organic molecules in medicinal chemistry, are most commonly synthesized from anilines, which are in turn synthesized by hydrogenation of nitroarenes. Amine synthesis directly from nitroarenes is attractive due to improved step economy and functional group compatibility. Despite these potential advantages, there is yet no general method for the synthesis of (hetero)aryl amines by carbon–nitrogen cross-coupling of nitroarenes. Here we report the reductive coupling of nitroarenes with alkyl halides to yield (hetero)aryl amines. A simple iron catalyst enables the coupling with numerous primary, secondary and tertiary alkyl halides. Broad scope and high functional group tolerance are demonstrated. Mechanistic study suggests that nitrosoarenes and alkyl radicals are involved as intermediates. This new C–N coupling method provides general and step-economical access to aryl amines. PMID:27515391

  1. Microscopic Investigation of Grain Boundaries in Organolead Halide Perovskite Solar Cells.

    PubMed

    Li, Jiang-Jun; Ma, Jing-Yuan; Ge, Qian-Qing; Hu, Jin-Song; Wang, Dong; Wan, Li-Jun

    2015-12-30

    Grain boundaries (GBs) play an important role in organic-inorganic halide perovskite solar cells, which have generally been recognized as a new class of materials for photovoltaic applications. To definitely understand the electrical structure and behavior of GBs, here we present Kelvin probe force microscopy and conductive atomic force microscopy (c-AFM) measurements of both typical and inverted planar organolead halide perovskite solar cells. By comparing the contact potential difference (CPD) of these two devices in the dark and under illumination, we found that a downward band bending exists in GBs that predominantly attract photoinduced electrons. The c-AFM measurements observed that higher photocurrents flow through GBs when a low bias overcomes the barrier created by the band bending, indicating that GBs act as effective charge dissociation interfaces and photocurrent transduction pathways rather than recombination sites. PMID:26633192

  2. Tuning the thermal conductivity of methylammonium lead halide by the molecular substructure.

    PubMed

    Caddeo, Claudia; Melis, Claudio; Saba, Maria Ilenia; Filippetti, Alessio; Colombo, Luciano; Mattoni, Alessandro

    2016-09-21

    By using state-of-the-art atomistic methods we provide an accurate estimate of thermal conductivity of methylammonium lead halide as a function of sample size and temperature, in agreement with experimental works. We show that the thermal conductivity of methylammonium lead halide is intrinsically low, due to the low sound velocity of the PbI lattice. Furthermore, by selectively analyzing the effect of different molecular degrees of freedom, we clarify the role of the molecular substructure by showing that the internal modes above 150 cm(-1) (in addition to rotations) are effective in reducing the thermal conductivity of hybrid perovskites. This analysis suggests strategies to tailor the thermal conductivity by modifying the internal structure of organic cations. PMID:27531063

  3. Multispectral metamaterial absorber.

    PubMed

    Grant, J; McCrindle, I J H; Li, C; Cumming, D R S

    2014-03-01

    We present the simulation, implementation, and measurement of a multispectral metamaterial absorber (MSMMA) and show that we can realize a simple absorber structure that operates in the mid-IR and terahertz (THz) bands. By embedding an IR metamaterial absorber layer into a standard THz metamaterial absorber stack, a narrowband resonance is induced at a wavelength of 4.3 μm. This resonance is in addition to the THz metamaterial absorption resonance at 109 μm (2.75 THz). We demonstrate the inherent scalability and versatility of our MSMMA by describing a second device whereby the MM-induced IR absorption peak frequency is tuned by varying the IR absorber geometry. Such a MSMMA could be coupled with a suitable sensor and formed into a focal plane array, enabling multispectral imaging. PMID:24690713

  4. Halide test agent replacement study

    SciTech Connect

    Banks, E.M.; Freeman, W.P.; Kovach, B.J.

    1995-02-01

    The intended phaseout of the chlorofluorocarbons (CFCs) from commercial use required the evaluation of substitute materials for the testing for leak paths through both individual adsorbers and installed adsorbent banks. The American Society of Mechanical Engineers (ASME) Committee on Nuclear Air and Gas Treatment (CONAGT) is in charge of maintaining the standards and codes specifying adsorbent leak test methods for the nuclear safety related air cleaning systems. The currently published standards and codes cite the use of R-11, R-12 and R-112 for leak path test agents. All of these compounds are CFCs. There are other agencies and organizations (USDOE, USDOD and USNRC) also specifying testing for leak paths or in some cases for special life tests using the above compounds. The CONAGT has recently developed criteria for the suitability evaluation of substitute test agents. On the basis of these criteria, several compounds were evaluated for their acceptability as adsorbent bed leak and life test agents. The ASME CONAGT Test Agent Qualification Criteria. The test agent qualification is based on the following parameters: (1) Similar retention times on activated carbons at the same concentration levels as one of the following: R-11, R-12, R-112 or R-112a. (2) Similar lower detection limit sensitivity and precision in the concentration range of use as R-11, R-12, R-112 and R-112a. (3) Gives the same in-place leak test results as R-11, R-12, R-112, or R-112a. (4) Chemical and radiological stability under the use conditions. (5) Causes no degradation of the carbon and its impregnant or of the other NATS components under the use conditions. (6) Is listed in the USEPA Toxic Substances Control Act (TSCA) inventory for commercial use.

  5. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  6. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... 10 Energy 3 2014-01-01 2014-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  7. 10 CFR 429.54 - Metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Metal halide lamp ballasts and fixtures. 429.54 Section... CONSUMER PRODUCTS AND COMMERCIAL AND INDUSTRIAL EQUIPMENT Certification § 429.54 Metal halide lamp ballasts... are applicable to metal halide lamp ballasts; and (2) For each basic model of metal halide...

  8. Methyl halide production associated with kelp

    NASA Technical Reports Server (NTRS)

    Dastoor, Minoo N.; Manley, Steven L.

    1985-01-01

    Methyl halides (MeX) are important trace constituents of the atmosphere because they, mostly MeCl, have a major impact on the atmospheric ozone layer. Also, MeCl may account for 5 pct. of the total Cl budget and MeI may have a central role in the biogeochemical cycling of iodine. High MeI concentrations were found in seawater from kelp beds and it has been suggested that MeI is produced by kelps and that MeI and MeBr along with numerous other halocarbons were released by non-kelp marine macroalgae. The objective was to determine if kelps (and other seaweeds) are sources of MeX and to assess their contribution to the estimated global source strength (EGSS) of MeX. Although the production of MeX appears to be associated with kelp, microbes involved with kelp degradation also produce MeX. Microbial MeX production may be of global significance. The microbial MeX production potential, assuming annual kelp production equals kelp degradation and 100 pct. conversion of kelp halides to MeX, is approx. 2 x the EGSS. This is not achieved but indicates that microbial production of MeX may be of global significance.

  9. Finding new perovskite halides via machine learning

    DOE PAGESBeta

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-26

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach toward rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning, henceforth referred to as ML) via building a support vectormore » machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br, or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 185 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor, and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. As a result, the trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.« less

  10. Finding New Perovskite Halides via Machine learning

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam; Balachandran, Prasanna V.; Kim, Chiho; Lookman, Turab

    2016-04-01

    Advanced materials with improved properties have the potential to fuel future technological advancements. However, identification and discovery of these optimal materials for a specific application is a non-trivial task, because of the vastness of the chemical search space with enormous compositional and configurational degrees of freedom. Materials informatics provides an efficient approach towards rational design of new materials, via learning from known data to make decisions on new and previously unexplored compounds in an accelerated manner. Here, we demonstrate the power and utility of such statistical learning (or machine learning) via building a support vector machine (SVM) based classifier that uses elemental features (or descriptors) to predict the formability of a given ABX3 halide composition (where A and B represent monovalent and divalent cations, respectively, and X is F, Cl, Br or I anion) in the perovskite crystal structure. The classification model is built by learning from a dataset of 181 experimentally known ABX3 compounds. After exploring a wide range of features, we identify ionic radii, tolerance factor and octahedral factor to be the most important factors for the classification, suggesting that steric and geometric packing effects govern the stability of these halides. The trained and validated models then predict, with a high degree of confidence, several novel ABX3 compositions with perovskite crystal structure.

  11. Effects of aqueous-soluble organic compounds on the removal of selected radionuclides from high-level waste part I: Distribution of Sr, Cs, and Tc onto 18 absorbers from an irradiated, organic-containing leachate simulant for Hanford Tank 101-SY

    SciTech Connect

    Marsh, S.F.; Svitra, Z.V.; Bowen, S.M.

    1995-01-01

    Many of the radioactive waste storage tanks at U.S. Department of Energy facilities contain organic compounds that have been degraded by radiolysis and chemical reactions. In this investigation, we measured the effect of some aqueous-soluble organic compounds on the sorption of strontium, cesium, and technetium onto 18 absorbers that offer high sorption of strontium from organic-free solutions. For our test solution we used a leachate from a simulated slurry for Hanford Tank 101-SY that initially contained ethylenediaminetetraacetic acid (EDTA) and then was gamma-irradiated to 34 Mrads. We measured distribution coefficients (Kds) for each element/absorber combination for dynamic contact periods of 30 min, 2 h, and 6 h to obtain information about sorption kinetics. To facilitate comparisons, we include Kd values for these same element/absorber combinations from three organic-free simulant solutions. The Kd values for strontium sorption from the simulant that contained the degraded organics usually decreased by large factors, whereas the Kd values for cesium and technetium sorption were relatively unaffected.

  12. Internal absorber solar collector

    DOEpatents

    Sletten, Carlyle J.; Herskovitz, Sheldon B.; Holt, F. S.; Sletten, E. J.

    1981-01-01

    Thin solar collecting panels are described made from arrays of small rod collectors consisting of a refracting dielectric rod lens with an absorber imbedded within it and a reflecting mirror coated on the back side of the dielectric rod. Non-tracking collector panels on vertical walls or roof tops receive approximately 90% of solar radiation within an acceptance zone 60.degree. in elevation angle by 120.degree. or more in the azimuth sectors with a collector concentration ratio of approximately 3.0. Miniaturized construction of the circular dielectric rods with internal absorbers reduces the weight per area of glass, plastic and metal used in the collector panels. No external parts or insulation are needed as heat losses are low due to partial vacuum or low conductivity gas surrounding heated portions of the collector. The miniature internal absorbers are generally made of solid copper with black selective surface and the collected solar heat is extracted at the collector ends by thermal conductivity along the absorber rods. Heat is removed from end fittings by use of liquid circulants. Several alternate constructions are provided for simplifying collector panel fabrication and for preventing the thermal expansion and contraction of the heated absorber or circulant tubes from damaging vacuum seals. In a modified version of the internal absorber collector, oil with temperature dependent viscosity is pumped through a segmented absorber which is now composed of closely spaced insulated metal tubes. In this way the circulant is automatically diverted through heated portions of the absorber giving higher collector concentration ratios than theoretically possible for an unsegmented absorber.

  13. Method for absorbing an ion from a fluid

    DOEpatents

    Gao, Huizhen; Wang, Yifeng; Bryan, Charles R.

    2007-07-03

    A method for absorbing an ion from a fluid by using dispersing an organic acid into an anion surfactant solution, mixing in a divalent-metal containing compound and a trivalent-metal containing compound and calcining the resulting solid layered double hydroxide product to form an absorbent material and then contacting the absorbent material with an aqueous solution of cations or anions to be absorbed.

  14. Photophysics of Hybrid Lead Halide Perovskites: The Role of Microstructure.

    PubMed

    Srimath Kandada, Ajay Ram; Petrozza, Annamaria

    2016-03-15

    Since the first reports on high efficiency, solution processed solar cells based on hybrid lead halide perovskites, there has been an explosion of activities on these materials. Researchers with interests spanning the full range from conventional inorganic to emerging organic and hybrid optoelectronic technologies have been contributing to the prolific research output. This has led to solar cell power conversion efficiencies now exceeding 20% and the demonstration of proofs of concept for electroluminescent and lasing devices. Hybrid perovskites can be self-assembled by a simple chemical deposition of the constituent units, with the possibility of integrating the useful properties of organic and inorganic compounds at the molecular scale within a single crystalline material, thus enabling a fine-tuning of the electronic properties. Tellingly, the fundamental properties of these materials may make us think of a new, solution processable, GaAs-like semiconductor. While this can be true to a first approximation, hybrid perovskites are intrinsically complex materials, where the presence of various types of interactions and structural disorder may strongly affect their properties. In particular, a clear understanding and control of the relative interactions between the organic and inorganic moieties is of paramount importance to properly disentangle their innate physics. In this Account we review our recent studies which aim to clarify the relationship between structural and electronic properties from a molecular to mesoscopic level. First we identify the markers for local disorder at the molecular level by using Raman spectroscopy as a probe. Then, we exploit such a tool to explore the role of microstructure on the absorption and luminescence properties of the semiconductor. Finally we address the controversy surrounding electron-hole interactions and excitonic effects. We show that in hybrid lead-halide perovskites dielectric screening also depends on the local

  15. Metal shearing energy absorber

    NASA Technical Reports Server (NTRS)

    Fay, R. J.; Wittrock, E. P. (Inventor)

    1973-01-01

    A metal shearing energy absorber is described. The absorber is composed of a flat thin strip of metal which is pulled through a slot in a cutter member of a metal, harder than the metal of the strip. The slot's length, in the direction perpendicular to the pull direction, is less than the strip's width so that as the strip is pulled through the slot, its edges are sheared off, thereby absorbing some of the pulling energy. In one embodiment the cutter member is a flat plate of steel, while in another embodiment the cutter member is U-shaped with the slot at its base.

  16. Lipid-absorbing Polymers

    NASA Technical Reports Server (NTRS)

    Marsh, H. E., Jr.; Wallace, C. J.

    1973-01-01

    The removal of bile acids and cholesterol by polymeric absorption is discussed in terms of micelle-polymer interaction. The results obtained with a polymer composed of 75 parts PEO and 25 parts PB plus curing ingredients show an absorption of 305 to 309%, based on original polymer weight. Particle size effects on absorption rate are analyzed. It is concluded that crosslinked polyethylene oxide polymers will absorb water, crosslinked polybutadiene polymers will absorb lipids; neither polymer will absorb appreciable amounts of lipids from micellar solutions of lipids in water.

  17. A Discovery-Based Experiment Involving Rearrangement in the Conversion of Alcohols to Alkyl Halides: Permanent Magnet [to the thirteenth power]C NMR in the First-Semester Organic Chemistry Lab

    ERIC Educational Resources Information Center

    Kjonaas, Richard A.; Tucker, Ryand J. F.

    2008-01-01

    The use of permanent magnet [to the thirteenth power]C NMR in large-section first-semester organic chemistry lab courses is limited by the availability of experiments that not only hinge on first-semester lecture topics, but which also produce at least 0.5 mL of neat liquid sample. This article reports a discovery-based experiment that meets both…

  18. "Smart" Electromechanical Shock Absorber

    NASA Technical Reports Server (NTRS)

    Stokes, Lebarian; Glenn, Dean C.; Carroll, Monty B.

    1989-01-01

    Shock-absorbing apparatus includes electromechanical actuator and digital feedback control circuitry rather than springs and hydraulic damping as in conventional shock absorbers. Device not subject to leakage and requires little or no maintenance. Attenuator parameters adjusted in response to sensory feedback and predictive algorithms to obtain desired damping characteristic. Device programmed to decelerate slowly approaching vehicle or other large object according to prescribed damping characteristic.

  19. Iron Chalcogenide Photovoltaic Absorbers

    SciTech Connect

    Yu, Liping; Lany, Stephan; Kykyneshi, Robert; Jieratum, Vorranutch; Ravichandran, Ram; Pelatt, Brian; Altschul, Emmeline; Platt, Heather A. S.; Wager, John F.; Keszler, Douglas A.; Zunger, Alex

    2011-08-10

    An integrated computational and experimental study of FeS₂ pyrite reveals that phase coexistence is an important factor limiting performance as a thin-film solar absorber. This phase coexistence is suppressed with the ternary materials Fe₂SiS₄ and Fe₂GeS₄, which also exhibit higher band gaps than FeS₂. Thus, the ternaries provide a new entry point for development of thin-film absorbers and high-efficiency photovoltaics.

  20. Mixed Ge/Pb perovskite light absorbers with an ascendant efficiency explored from theoretical view.

    PubMed

    Sun, Ping-Ping; Li, Quan-Song; Feng, Shuai; Li, Ze-Sheng

    2016-06-01

    Organic-inorganic methylammonium lead halide perovskites have recently attracted great interest emerging as promising photovoltaic materials with a high 20.8% efficiency, but lead pollution is still a problem that may hinder the development and wide spread of MAPbI3 perovskites. To reduce the use of lead, we investigated the structures, electronic and optical properties of mixed MAGexPb(1-x)I3 theoretically by using density functional theory methods at different calculation levels. Results show that the mixed Ge/Pb perovskites exhibit a monotonic decrease evolution in band energy to push the band gap deeper in the near-infrared region and have a red shift optical absorption with an increased proportion of Ge. The results also indicate that lattice distortion and spin-orbit coupling (SOC) strength play important roles in the band gap behavior of MAGexPb(1-x)I3 by affecting the bandwidths of CBM and VBM. The calculations for short circuit current density, open circuit voltage, and theoretical power conversion efficiency suggest that mixed Ge/Pb perovskite solar cells (PSCs) with efficiency over 22% are superior to MAPbI3 and MAGeI3. And notably, MAGe0.75Pb0.25I3 is a promising harmless material for solar cells absorber with the highest theoretical efficiency of 24.24%. These findings are expected to be helpful for further rational design of nontoxic light absorption layer for high-performance PSCs. PMID:27171746

  1. Non-tinted Transparent Luminescent Solar Concentrators Employing Both UV and NIR Selective Absorbers

    NASA Astrophysics Data System (ADS)

    Zhao, Yimu; Lunt, Richard

    2014-03-01

    Luminescent solar concentrators are a potentially low-cost solar harvesting solution that additionally offer opportunities for integration around buildings and windows. However, the visible absorption and emission of previously demonstrated chromophores hamper their widespread applications including solar windows. Here, we demonstrate non-tinted transparent luminescent solar concentrators (TLSC) that employ both ultraviolet (UV) and near-infrared (NIR) selective absorbing luminophores that create an entirely new paradigm for power-producing transparent surfaces and enhances the potential over UV-only TLSCs. We have previously designed UV-harvesting systems composed of metal halide phosphorescent luminophore blends that enable absorption cutoff positioned at the edge of visible spectrum (430nm) and massive-downconverted emission in the near-infrared (800nm) with quantum yields for luminescence of 75%. Here, we have developed a complimentary TLSC employing fluorescent organic salts with both efficient NIR absorption and deeper NIR emission. We will discuss the photophysical properties of these luminophores, the impact of ligand-host control, and optimization of the TLSC architectures.

  2. On the Thermal and Thermodynamic (In)Stability of Methylammonium Lead Halide Perovskites

    PubMed Central

    Brunetti, Bruno; Cavallo, Carmen; Ciccioli, Andrea; Gigli, Guido; Latini, Alessandro

    2016-01-01

    The interest of the scientific community on methylammonium lead halide perovskites (MAPbX3, X = Cl, Br, I) for hybrid organic-inorganic solar cells has grown exponentially since the first report in 2009. This fact is clearly justified by the very high efficiencies attainable (reaching 20% in lab scale devices) at a fraction of the cost of conventional photovoltaics. However, many problems must be solved before a market introduction of these devices can be envisaged. Perhaps the most important to be addressed is the lack of information regarding the thermal and thermodynamic stability of the materials towards decomposition, which are intrinsic properties of them and which can seriously limit or even exclude their use in real devices. In this work we present and discuss the results we obtained using non-ambient X-ray diffraction, Knudsen effusion-mass spectrometry (KEMS) and Knudsen effusion mass loss (KEML) techniques on MAPbCl3, MAPbBr3 and MAPbI3. The measurements demonstrate that all the materials decompose to the corresponding solid lead (II) halide and gaseous methylamine and hydrogen halide, and the decomposition is well detectable even at moderate temperatures (~60 °C). Our results suggest that these materials may be problematic for long term operation of solar devices. PMID:27545661

  3. On the Thermal and Thermodynamic (In)Stability of Methylammonium Lead Halide Perovskites.

    PubMed

    Brunetti, Bruno; Cavallo, Carmen; Ciccioli, Andrea; Gigli, Guido; Latini, Alessandro

    2016-01-01

    The interest of the scientific community on methylammonium lead halide perovskites (MAPbX3, X = Cl, Br, I) for hybrid organic-inorganic solar cells has grown exponentially since the first report in 2009. This fact is clearly justified by the very high efficiencies attainable (reaching 20% in lab scale devices) at a fraction of the cost of conventional photovoltaics. However, many problems must be solved before a market introduction of these devices can be envisaged. Perhaps the most important to be addressed is the lack of information regarding the thermal and thermodynamic stability of the materials towards decomposition, which are intrinsic properties of them and which can seriously limit or even exclude their use in real devices. In this work we present and discuss the results we obtained using non-ambient X-ray diffraction, Knudsen effusion-mass spectrometry (KEMS) and Knudsen effusion mass loss (KEML) techniques on MAPbCl3, MAPbBr3 and MAPbI3. The measurements demonstrate that all the materials decompose to the corresponding solid lead (II) halide and gaseous methylamine and hydrogen halide, and the decomposition is well detectable even at moderate temperatures (~60 °C). Our results suggest that these materials may be problematic for long term operation of solar devices. PMID:27545661

  4. Simultaneous analyses and applications of multiple fluorobenzoate and halide tracers in hydrologic studies

    NASA Astrophysics Data System (ADS)

    Hu, Qinhong; Moran, Jean E.

    2005-09-01

    An analytical method that employs ion chromatography has been developed to exploit the use of fluorobenzoic acids (FBAs) and halides more fully as hydrologic tracers. In a single run, this reliable, sensitive, and robust method can simultaneously separate and quantify halides (fluoride, chloride, bromide, and iodide) and up to seven FBAs from other common groundwater constituents (e.g. nitrate and sulphate). The usefulness of this analytical method is demonstrated in both field and laboratory tracer experiments. The field study examines the hydrologic response of fractures and the matrix to different flow rates and the contribution of matrix diffusion in chemical transport. Laboratory tracer experiments with eight geologic media from across the USA - mostly from Department of Energy facilities where groundwater contamination is prevalent and where subsurface characterization employing tracers has been ongoing or is in need - reveal several insights about tracer transport behaviour: (1) bromide and FBAs are not always transported conservatively; (2) the delayed transport of these anionic tracers is likely related to geologic media characteristics, such as organic matter, pH, iron oxide content, and clay mineralogy; (3) use of iodine as a hydrologic tracer should take into account the different sorption behaviours of iodide and iodate and the possible conversion of iodine's initial chemical form; (4) the transport behaviour of potential FBA and halide tracers under relevant geochemical conditions should be evaluated before beginning ambitious, large-scale field tracer experiments.

  5. Alkali metal and alkali earth metal gadolinium halide scintillators

    DOEpatents

    Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

    2016-08-02

    The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

  6. Simultaneous Analyses and Applications of Multiple Fluorobenzoate and Halide Tracers in Hydrologic Studies

    SciTech Connect

    Hu, Q; Moran, J E

    2004-01-22

    An analytical method that employs ion chromatography has been developed to more fully exploit the use of fluorobenzoic acids (FBAs) and halides as hydrologic tracers. In a single run, this reliable, sensitive, and robust method can simultaneously separate and quantify halides (fluoride, chloride, bromide, and iodide) and up to seven FBAs from other common groundwater constituents (e.g., nitrate and sulfate). The usefulness of this ion chromatographic (IC) analytical method is demonstrated in both field and laboratory tracer experiments. Field experiments in unsaturated tuff featuring fractures or a fault show that this efficient and cost-effective method helps achieve the objectives of tracer studies that use multiple FBAs and/or diffusivity tracers (simultaneous use of one or more FBA and halide). The field study examines the hydrologic response of fractures and the matrix to different flow rates and the contribution of matrix diffusion in chemical transport. Laboratory tracer experiments with eight geologic media from across the United States--mostly from Department of Energy facilities where groundwater contamination is prevalent and where subsurface characterization employing tracers has been ongoing or is in need--reveal several insights about tracer transport behavior: (1) Bromide and FBAs are not always transported conservatively. (2) The delayed transport of these anionic tracers is likely related to geologic media characteristics, such as organic matter, pH, iron oxide content, and clay mineralogy. (3) Any use of iodine as a hydrologic tracer should take into account the different sorption behaviors of iodide and iodate and the possible conversion of iodine's initial chemical form. (4) The transport behavior of potential FBA and halide tracers under relevant geochemical conditions should be evaluated before beginning ambitious, large-scale field tracer experiments.

  7. Halide-Substituted Electronic Properties of Organometal Halide Perovskite Films: Direct and Inverse Photoemission Studies.

    PubMed

    Li, Chi; Wei, Jian; Sato, Mikio; Koike, Harunobu; Xie, Zhong-Zhi; Li, Yan-Qing; Kanai, Kaname; Kera, Satoshi; Ueno, Nobuo; Tang, Jian-Xin

    2016-05-11

    Solution-processed perovskite solar cells are attracting increasing interest due to their potential in next-generation hybrid photovoltaic devices. Despite the morphological control over the perovskite films, quantitative information on electronic structures and interface energetics is of paramount importance to the optimal photovoltaic performance. Here, direct and inverse photoemission spectroscopies are used to determine the electronic structures and chemical compositions of various methylammonium lead halide perovskite films (MAPbX3, X = Cl, Br, and I), revealing the strong influence of halide substitution on the electronic properties of perovskite films. Precise control over halide compositions in MAPbX3 films causes the manipulation of the electronic properties, with a qualitatively blue shift along the I → Br → Cl series and showing the increase in ionization potentials from 5.96 to 7.04 eV and the change of transport band gaps in the range from 1.70 to 3.09 eV. The resulting light absorption of MAPbX3 films can cover the entire visible region from 420 to 800 nm. The results presented here provide a quantitative guide for the analysis of perovskite-based solar cell performance and the selection of optimal carrier-extraction materials for photogenerated electrons and holes. PMID:27101940

  8. Vibrational Spectroscopy of Sodium Halide and Hydrogen Halide Aqueous Solutions: Application to Atmospheric Aerosol Chemistry

    NASA Astrophysics Data System (ADS)

    Levering, L. M.; Liu, D.; Allen, H. C.

    2003-12-01

    Heterogeneous reactions on the surfaces of atmospheric aerosols play an important role in atmospheric chemistry. These reactions are capable of converting alkyl and hydrogen halides (common constituents of marine boundary aerosols) into active halogen compounds. Fundamental questions still remain concerning surface species and reaction mechanisms pertaining to marine boundary aerosols. The first step in beginning to understand these heterogeneous reactions is to determine how ions in solution affect the structure of water at the interface. Vibrational sum frequency generation spectroscopy is used to examine the air-liquid interface of sodium halide and hydrogen halide (i.e. strong acid) solutions. In addition, comparison of the bulk water structure to that of the interface is accomplished using Raman spectroscopy. The hydrogen-bonding environment at the surface of NaCl is found to be similar to that of the air-water interface. In contrast, the interfacial water structure of NaBr, HCl, and HBr solutions is significantly altered from that of neat water. In the bulk, NaCl, NaBr, HCl, and HBr solutions disturb the hydrogen-bonding network of neat water. A comparison between the corresponding salts and acids show that the salts produce greater disorder (i.e. less coupling of the water symmetric stretching modes) in the bulk water structure.

  9. Experimental and theoretical optical properties of methylammonium lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Leguy, Aurélien M. A.; Azarhoosh, Pooya; Alonso, M. Isabel; Campoy-Quiles, Mariano; Weber, Oliver J.; Yao, Jizhong; Bryant, Daniel; Weller, Mark T.; Nelson, Jenny; Walsh, Aron; van Schilfgaarde, Mark; Barnes, Piers R. F.

    2016-03-01

    The optical constants of methylammonium lead halide single crystals CH3NH3PbX3 (X = I, Br, Cl) are interpreted with high level ab initio calculations using the relativistic quasiparticle self-consistent GW approximation (QSGW). Good agreement between the optical constants derived from QSGW and those obtained from spectroscopic ellipsometry enables the assignment of the spectral features to their respective inter-band transitions. We show that the transition from the highest valence band (VB) to the lowest conduction band (CB) is responsible for almost all the optical response of MAPbI3 between 1.2 and 5.5 eV (with minor contributions from the second highest VB and the second lowest CB). The calculations indicate that the orientation of [CH3NH3]+ cations has a significant influence on the position of the bandgap suggesting that collective orientation of the organic moieties could result in significant local variations of the optical properties. The optical constants and energy band diagram of CH3NH3PbI3 are then used to simulate the contributions from different optical transitions to a typical transient absorption spectrum (TAS).The optical constants of methylammonium lead halide single crystals CH3NH3PbX3 (X = I, Br, Cl) are interpreted with high level ab initio calculations using the relativistic quasiparticle self-consistent GW approximation (QSGW). Good agreement between the optical constants derived from QSGW and those obtained from spectroscopic ellipsometry enables the assignment of the spectral features to their respective inter-band transitions. We show that the transition from the highest valence band (VB) to the lowest conduction band (CB) is responsible for almost all the optical response of MAPbI3 between 1.2 and 5.5 eV (with minor contributions from the second highest VB and the second lowest CB). The calculations indicate that the orientation of [CH3NH3]+ cations has a significant influence on the position of the bandgap suggesting that collective

  10. An above-room-temperature ferroelectric organo-metal halide perovskite: (3-pyrrolinium)(CdCl₃).

    PubMed

    Ye, Heng-Yun; Zhang, Yi; Fu, Da-Wei; Xiong, Ren-Gen

    2014-10-13

    Hybrid organo-metal halide perovskite materials, such as CH3NH3PbI3, have been shown to be some of the most competitive candidates for absorber materials in photovoltaic (PV) applications. However, their potential has not been completely developed, because a photovoltaic effect with an anomalously large voltage can be achieved only in a ferroelectric phase, while these materials are probably ferroelectric only at temperatures below 180 K. A new hexagonal stacking perovskite-type complex (3-pyrrolinium)(CdCl3) exhibits above-room-temperature ferroelectricity with a Curie temperature T(c)=316 K and a spontaneous polarization P(s)=5.1 μC cm(-2). The material also exhibits antiparallel 180° domains which are related to the anomalous photovoltaic effect. The open-circuit photovoltage for a 1 mm-thick bulky crystal reaches 32 V. This finding could provide a new approach to develop solar cells based on organo-metal halide perovskites in photovoltaic research. PMID:25196506

  11. Passive particle dosimetry. [silver halide crystal growth

    NASA Technical Reports Server (NTRS)

    Childs, C. B.

    1977-01-01

    Present methods of dosimetry are reviewed with emphasis on the processes using silver chloride crystals for ionizing particle dosimetry. Differences between the ability of various crystals to record ionizing particle paths are directly related to impurities in the range of a few ppm (parts per million). To understand the roles of these impurities in the process, a method for consistent production of high purity silver chloride, and silver bromide was developed which yields silver halides with detectable impurity content less than 1 ppm. This high purity silver chloride was used in growing crystals with controlled doping. Crystals were grown by both the Czochalski method and the Bridgman method, and the Bridgman grown crystals were used for the experiments discussed. The distribution coefficients of ten divalent cations were determined for the Bridgman crystals. The best dosimeters were made with silver chloride crystals containing 5 to 10 ppm of lead; other impurities tested did not produce proper dosimeters.

  12. Metal halide perovskites for energy applications

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.

    2016-06-01

    Exploring prospective materials for energy production and storage is one of the biggest challenges of this century. Solar energy is one of the most important renewable energy resources, due to its wide availability and low environmental impact. Metal halide perovskites have emerged as a class of semiconductor materials with unique properties, including tunable bandgap, high absorption coefficient, broad absorption spectrum, high charge carrier mobility and long charge diffusion lengths, which enable a broad range of photovoltaic and optoelectronic applications. Since the first embodiment of perovskite solar cells showing a power conversion efficiency of 3.8%, the device performance has been boosted up to a certified 22.1% within a few years. In this Perspective, we discuss differing forms of perovskite materials produced via various deposition procedures. We focus on their energy-related applications and discuss current challenges and possible solutions, with the aim of stimulating potential new applications.

  13. Fabrication of a Homogeneous, Integrated, and Compact Film of Organic-Inorganic Hybrid Ni(en)3Ag2I4 with Near-Infrared Absorbance and Semiconducting Features.

    PubMed

    Chen, Tian-Yu; Shi, Lei; Yang, Hao; Ren, Xiao-Ming; Xiao, Chen; Jin, Wanqin

    2016-02-01

    The organic-inorganic hybrid crystal Ni(en)3Ag2I4 (where en represents 1,2-ethylenediamine) crystallizes in hexagonal space group P63, in which the AgI4(3-) tetrahedra connect into a diamondlike inorganic framework via sharing of the vertex and the Ni(en)3(2+) octahedra fill in the pores of the framework. UV-vis-near-IR (NIR) spectroscopy disclosed that this hybrid shows intense NIR absorbance centered at ca. 870 nm, and the variable-temperature conductivity measurement revealed that the hybrid is a semiconductor with Ea = 0.46 eV. The electronic band structure of Ni(en)3Ag2I4 was calculated using the density functional theory method, indicating that the NIR absorbance arises from d-d transition within the Ni(2+) cation of Ni(en)3(2+). The homogeneous, compact, and transparent crystalline film of Ni(en)3Ag2I4 was fabricated via a secondary seed growth strategy, which has promising application in NIR devices. PMID:26771538

  14. Electronic and Ionic Transport Dynamics in Organolead Halide Perovskites.

    PubMed

    Li, Dehui; Wu, Hao; Cheng, Hung-Chieh; Wang, Gongming; Huang, Yu; Duan, Xiangfeng

    2016-07-26

    Ion migration has been postulated as the underlying mechanism responsible for the hysteresis in organolead halide perovskite devices. However, the electronic and ionic transport dynamics and how they impact each other in organolead halide perovskites remain elusive to date. Here we report a systematic investigation of the electronic and ionic transport dynamics in organolead halide perovskite microplate crystals and thin films using temperature-dependent transient response measurements. Our study reveals that thermally activated ionic and electronic conduction coexist in perovskite devices. The extracted activation energies suggest that the electronic transport is easier, but ions migrate harder in microplates than in thin films, demonstrating that the crystalline quality and grain boundaries can fundamentally modify electronic and ionic transport in perovskites. These findings offer valuable insight on the electronic and ionic transport dynamics in organolead halide perovskites, which is critical for optimizing perovskite devices with reduced hysteresis and improved stability and efficiency. PMID:27315525

  15. Unidirectional perfect absorber.

    PubMed

    Jin, L; Wang, P; Song, Z

    2016-01-01

    This study proposes a unidirectional perfect absorber (UPA), which we realized with a two-arm Aharonov-Bohm interferometer, that consists of a dissipative resonator side-coupled to a uniform resonator array. The UPA has reflection-less full absorption on one direction, and reflectionless full transmission on the other, with an appropriate magnetic flux and coupling, detuning, and loss of the side-coupled resonator. The magnetic flux controls the transmission, the left transmission is larger for magnetic flux less than one-half flux quantum; and the right transmission is larger for magnetic flux between one-half and one flux quantum. Besides, a perfect absorber (PA) can be realized based on the UPA, in which light waves from both sides, with arbitrary superposition of the ampli- tude and phase, are perfectly absorbed. The UPA is expected to be useful in the design of novel optical devices. PMID:27615125

  16. Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

    SciTech Connect

    Bory, Benjamin F.; Wang, Jingxin; Janssen, René A. J.; Meskers, Stefan C. J.; Gomes, Henrique L.; De Leeuw, Dago M.

    2014-12-08

    Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10{sup 25}/m{sup 3}. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

  17. Nanocrystals of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut

    PubMed Central

    2015-01-01

    Metal halides perovskites, such as hybrid organic–inorganic CH3NH3PbI3, are newcomer optoelectronic materials that have attracted enormous attention as solution-deposited absorbing layers in solar cells with power conversion efficiencies reaching 20%. Herein we demonstrate a new avenue for halide perovskites by designing highly luminescent perovskite-based colloidal quantum dot materials. We have synthesized monodisperse colloidal nanocubes (4–15 nm edge lengths) of fully inorganic cesium lead halide perovskites (CsPbX3, X = Cl, Br, and I or mixed halide systems Cl/Br and Br/I) using inexpensive commercial precursors. Through compositional modulations and quantum size-effects, the bandgap energies and emission spectra are readily tunable over the entire visible spectral region of 410–700 nm. The photoluminescence of CsPbX3 nanocrystals is characterized by narrow emission line-widths of 12–42 nm, wide color gamut covering up to 140% of the NTSC color standard, high quantum yields of up to 90%, and radiative lifetimes in the range of 1–29 ns. The compelling combination of enhanced optical properties and chemical robustness makes CsPbX3 nanocrystals appealing for optoelectronic applications, particularly for blue and green spectral regions (410–530 nm), where typical metal chalcogenide-based quantum dots suffer from photodegradation. PMID:25633588

  18. Experimental and theoretical optical properties of methylammonium lead halide perovskites.

    PubMed

    Leguy, Aurélien M A; Azarhoosh, Pooya; Alonso, M Isabel; Campoy-Quiles, Mariano; Weber, Oliver J; Yao, Jizhong; Bryant, Daniel; Weller, Mark T; Nelson, Jenny; Walsh, Aron; van Schilfgaarde, Mark; Barnes, Piers R F

    2016-03-17

    The optical constants of methylammonium lead halide single crystals CH3NH3PbX3 (X = I, Br, Cl) are interpreted with high level ab initio calculations using the relativistic quasiparticle self-consistent GW approximation (QSGW). Good agreement between the optical constants derived from QSGW and those obtained from spectroscopic ellipsometry enables the assignment of the spectral features to their respective inter-band transitions. We show that the transition from the highest valence band (VB) to the lowest conduction band (CB) is responsible for almost all the optical response of MAPbI3 between 1.2 and 5.5 eV (with minor contributions from the second highest VB and the second lowest CB). The calculations indicate that the orientation of [CH3NH3](+) cations has a significant influence on the position of the bandgap suggesting that collective orientation of the organic moieties could result in significant local variations of the optical properties. The optical constants and energy band diagram of CH3NH3PbI3 are then used to simulate the contributions from different optical transitions to a typical transient absorption spectrum (TAS). PMID:26477295

  19. Tallgrass Prairie as a Source and Sink of Methyl Halides

    NASA Astrophysics Data System (ADS)

    Abel, T.; Rhew, R. C.; Mazeas, O.; Atwood, A.; King, A. J.; Ma, L.; Whelan, M.

    2007-12-01

    Temperate grasslands are believed to be a globally significant sink for methyl bromide (CH3Br) and perhaps methyl chloride (CH3Cl), compounds which lead to stratospheric ozone destruction. Fluxes of these compounds were measured at Konza Prairie, a tallgrass prairie in the Flint Hills of Kansas, during June 2006 and August 2007. A stable isotope tracer technique was used to distinguish between simultaneous production and oxidation processes, allowing the first gross flux measurements of CH3Cl and CH3Br from a tallgrass prairie. Observed gross uptake rates of CH3Cl and CH3Br were similar to what we previously observed from the shortgrass steppe in Colorado and annual grasslands in California, but much lower than reported fluxes from a grassland in northeastern North America. A water manipulation experiment was performed both under controlled laboratory conditions, as well as in the field, demonstrating that uptake rates of both CH3Cl and CH3Br were strongly affected by soil moisture. On the production side, new sources of methyl halides were identified in association with certain plant species. Fluxes of these halogenated trace gases were compared to environmental variables, such as air temperature and volumetric water content. Net fluxes of methyl iodide (CH3I), carbon tetrachloride (CCl4), and other halogenated volatile organic compounds (HVOCs), were also measured.

  20. Emission Enhancement and Intermittency in Polycrystalline Organolead Halide Perovskite Films.

    PubMed

    Li, Cheng; Zhong, Yu; Luna, Carlos Andres Melo; Unger, Thomas; Deichsel, Konstantin; Gräser, Anna; Köhler, Jürgen; Köhler, Anna; Hildner, Richard; Huettner, Sven

    2016-01-01

    Inorganic-organic halide organometal perovskites have demonstrated very promising performance for opto-electronic applications, such as solar cells, light-emitting diodes, lasers, single-photon sources, etc. However, the little knowledge on the underlying photophysics, especially on a microscopic scale, hampers the further improvement of devices based on this material. In this communication, correlated conventional photoluminescence (PL) characterization and wide-field PL imaging as a function of time are employed to investigate the spatially- and temporally-resolved PL in CH₃NH₃PbI3-xClx perovskite films. Along with a continuous increase of the PL intensity during light soaking, we also observe PL blinking or PL intermittency behavior in individual grains of these films. Combined with significant suppression of PL blinking in perovskite films coated with a phenyl-C61-butyric acid methyl ester (PCBM) layer, it suggests that this PL intermittency is attributed to Auger recombination induced by photoionized defects/traps or mobile ions within grains. These defects/traps are detrimental for light conversion and can be effectively passivated by the PCBM layer. This finding paves the way to provide a guideline on the further improvement of perovskite opto-electronic devices. PMID:27548128

  1. Effects of soluble organic complexants and their degradation products on the removal of selected radionuclides from high-level waste. Part 3, Distributions of Sr, Cs, Tc, Pu, and Am onto 33 absorbers from four variations of a 3:1 dilution of Hanford complexant concentrate (CC) simulant: Part 4, The effects of varying dilution ratios on the distributions of Sr, Cs, Tc, Pu, and Am onto 12 absorbers

    SciTech Connect

    Marsh, S.F.; Svitra, Z.V.; Bowen, S.M.

    1995-09-01

    Many of the radioactive waste storage tanks at USDOE facilities contain organic compounds that have been degraded by radiolysis and chemical reactions during decades of storage. Objective of this study was to measure effects of soluble organic complexants and their degradation products on sorption of Sr, Cs, Tc, Pu and Am onto 33 absorbers that in the absence of these organic compounds offer high sorption of these elements. The elements were in a generic simulant for Hanford complexant concentrate supernate that initially contained six organic complexants: EDTA, HEDTA, NTA, citrate, gluconate, and iminodiacetate. This simulant was tested as prepared and after gamma-irradiation to approximately 34 Mrads. Two other variations consisted of the unirradiated and irradiated simulants after treatment at 450C and 15,000 psi in a hydrothermal organic-destruction process. These experiments were conducted with a 3:1 water-to-simulant dilution of each of the four simulant variations. To determine effects of varying dilution ratios on the sorption of these five elements from the unirradiated and gamma-irradiated simulants that were not treated with the hydrothermal process, we measured their distribution from a 1:1 dilution, using 1 M NaOH as the diluent, onto the 12 best-performing absorbers. We then measured the sorption of these five elements from solutions having diluent-simulant ratios of 0, 0.5, 2.0, and 3.0 onto the three absorbers that performed best for sorbing Sr, Pu and Am from the 1:1 dilution. For each of 900 element/absorber/solution combinations, we measured distribution coefficients (Kd values) twice for each period for dynamic contact periods of 30 min, 2 h, and 6 h to obtain information about absorber stability and sorption kinetics. The 5400 measured Kd values indicate that the sorption of Sr, Pu, and Am is significantly decreased by the organic complexants in these simulant solutions, whereas the sorption of Cs and Tc is much less affected.

  2. Multiple-layer Radiation Absorber

    NASA Astrophysics Data System (ADS)

    Baker, Robert M. L.; Baker, Bonnie Sue

    A structure is discussed for absorbing incident radiation, either electromagnetic (EM) or sound. Such a surface structure is needed, for example, in a highly sensitive high-frequency gravitational wave or HFGW detector such as the Li-Baker. The multi-layer absorber, which is discussed, is constructed with metamaterial [MM] layer or layers on top. This MM is configured for a specific EM or sound radiation frequency band, which absorbs incident EM or sound radiation without reflection. Below these top MM layers is a substrate of conventional EM-radiation absorbing or acoustical absorbing reflective material, such as an array of pyramidal foam absorbers. Incident radiation is partially absorbed by the MM layer or layers, and then it is more absorbed by the lower absorbing and reflecting substrate. The remaining reflected radiation is even further absorbed by the MM layers on its "way out_ so that essentially all of the incident radiation is absorbed _ a nearly perfect black-body absorber. In a HFGW detector a substrate, such as foam absorbers, may outgas into a high vacuum and reduce the capability of the vacuum-producing equipment, however, the layers above this lowest substrate will seal the absorbing and reflecting substrate from any external vacuum. The layers also serve to seal the absorbing material against air or water flow past the surfaces of aircraft, watercraft or submarines. Other applications for such a multiple-level radiation absorber include stealth aircraft, missiles and submarines.

  3. Density functional studies on hydrogen-bonded clusters of hydrogen halides and the interaction on halide anions

    NASA Astrophysics Data System (ADS)

    Nirmala, V.; Kolandaivel, P.

    Density functional theory (DFT) calculations have been performed to study the structures and stability of X-·(HX)n=2-5 clusters where X = F, Cl, Br at B3LYP/6-311++G** level of theory. The presence of halide ions in these clusters disintegrates the hydrogen halide clusters. All the hydrogen halides are then hydrogen bonded to the centrally placed halide ions, thereby forming multiple hydrogen bonds. The interaction energies have been corrected for the basis set superposition error (BSSE) using Boy's counterpoise correction method. Evidence for the destruction of hydrogen bonds in hydrogen halide clusters due to the presence of halide ions is further obtained from topological analysis and natural bond orbital analysis. The chemical hardness and chemical potential have been calculated for all the anion clusters. The above analysis reveals that hydrogen bonding in these systems is not an essentially electrostatic interaction. The nature of the stabilization interactions operative in these multiple hydrogen-bonded clusters has been explained in terms of many-body contribution to interaction energies. From these studies, an attempt has been made to understand the nature of the molecular properties resulting from different electronegativities of the halogens.

  4. Metallaphotoredox-catalysed sp(3)-sp(3) cross-coupling of carboxylic acids with alkyl halides.

    PubMed

    Johnston, Craig P; Smith, Russell T; Allmendinger, Simon; MacMillan, David W C

    2016-08-18

    In the past 50 years, cross-coupling reactions mediated by transition metals have changed the way in which complex organic molecules are synthesized. The predictable and chemoselective nature of these transformations has led to their widespread adoption across many areas of chemical research. However, the construction of a bond between two sp(3)-hybridized carbon atoms, a fundamental unit of organic chemistry, remains an important yet elusive objective for engineering cross-coupling reactions. In comparison to related procedures with sp(2)-hybridized species, the development of methods for sp(3)-sp(3) bond formation via transition metal catalysis has been hampered historically by deleterious side-reactions, such as β-hydride elimination with palladium catalysis or the reluctance of alkyl halides to undergo oxidative addition. To address this issue, nickel-catalysed cross-coupling processes can be used to form sp(3)-sp(3) bonds that utilize organometallic nucleophiles and alkyl electrophiles. In particular, the coupling of alkyl halides with pre-generated organozinc, Grignard and organoborane species has been used to furnish diverse molecular structures. However, the manipulations required to produce these activated structures is inefficient, leading to poor step- and atom-economies. Moreover, the operational difficulties associated with making and using these reactive coupling partners, and preserving them through a synthetic sequence, has hindered their widespread adoption. A generically useful sp(3)-sp(3) coupling technology that uses bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be valuable. Here we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp(3)-sp(3) bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox

  5. Neutron Absorbing Alloys

    DOEpatents

    Mizia, Ronald E.; Shaber, Eric L.; DuPont, John N.; Robino, Charles V.; Williams, David B.

    2004-05-04

    The present invention is drawn to new classes of advanced neutron absorbing structural materials for use in spent nuclear fuel applications requiring structural strength, weldability, and long term corrosion resistance. Particularly, an austenitic stainless steel alloy containing gadolinium and less than 5% of a ferrite content is disclosed. Additionally, a nickel-based alloy containing gadolinium and greater than 50% nickel is also disclosed.

  6. Palladium-catalyzed cross-coupling reactions of aryl boronic acids with aryl halides in water.

    PubMed

    Wang, Shaoyan; Zhang, Zhiqiang; Hu, Zhizhi; Wang, Yue; Lei, Peng; Chi, Haijun

    2009-01-01

    An efficient Suzuki cross-coupling reaction using a variety of aryl halides in neat water was developed. The Pd-catalyzed reaction between aryl bromides or chlorides and phenyl boronic acids was compatible with various functional groups and affords biphenyls in good to excellent yields without requirement of organic cosolvents. The air stability and solubility in water of the palladium-phosphinous acid complexes were considered to facilitate operation of the coupling reaction and product isolation. The reaction conditions including Pd catalyst selection, temperature, base and catalyst recoverability were also investigated. PMID:25084408

  7. Organic chemistry: No double bond left behind

    NASA Astrophysics Data System (ADS)

    Sarlah, David

    2016-03-01

    Alkenyl halides are some of the most useful building blocks for synthesizing small organic molecules. A catalyst has now allowed their direct preparation from widely available alkenes using the cross-metathesis reaction. See Article p.459

  8. Transformation of molecular weight distributions of dissolved organic carbon and UV-absorbing compounds at full-scale wastewater-treatment plants.

    PubMed

    Esparza-Soto, Mario; Fox, Peter; Westerhoff, Paul

    2006-03-01

    The molecular-weight distribution (MWD) of wastewater dissolved-organic carbon (DOC) was determined in samples from seven full-scale wastewater-treatment plants (WWTPs) that use different biological treatments (air activated sludge [air-AS], pure-oxygen AS [O2-AS], and trickling filters). The research objective was to determine how different biological treatments influenced the MWD of wastewater DOC. Primary sedimentation effluent DOC from most of the WWTPs exhibited a skewed distribution toward the low-molecular-weight fraction (MWF) (40 to 50%, < 0.5 K Daltons [KDa]). The Air-AS effluent DOC exhibited a centrally clustered distribution, with the majority of DOC in the intermediate MWF (0.5 to 3 KDa). The O2-AS effluent DOC exhibited a skewed distribution toward the high MWF (> 3 KDa). The removal of DOC by air- and O2-AS bacteria followed trends predicted by a macromolecule degradation model. Trickling-filter effluent DOC exhibited a skewed distribution toward the high MWF (50% DOC, > 3 KDa). PMID:16629265

  9. Color silver halide hologram production and mastering

    NASA Astrophysics Data System (ADS)

    Bjelkhagen, Hans I.; Huang, Qiang

    1997-04-01

    Color reflection holograms recorded with the Denisyuk geometry have been demonstrated by the recently formed HOLOS Corporation in New Hampshire. The Slavich red-green-blue (RGB) sensitized ultra-high resolution silver halide emulsion was used for the hologram recording. The employed laser wavelengths were 647 nm, 532 nm, and 476 nm, generated by an argon ion, a frequency doubled Nd:YAG, and a krypton ion laser, respectively. A beam combination mechanism with dichroic filters enabled a simultaneous RGB exposure, which made the color balance and overall exposure energy easy to control as well as simplifying the recording procedure. HOLOS has been producing limited edition color holograms in various sizes from 4' X 5' to 12' X 16'. A 30 foot long optical table and high power lasers will enable HOLOS to record color holograms up to the size of one meter square in the near future. Various approaches have been investigated in generating color hologram masters which have sufficiently high diffraction efficiency to contact copy the color images onto photopolymer materials. A specially designed test object including the 1931 CIE chromaticity diagram, a rainbow ribbon cable, pure yellow dots, and a cloisonne elephant was used for color recording experiments. In addition, the Macbeth Color Checker chart was used. Both colorimetric evaluation and scattering noise measurements were performed using the PR-650 Photo Research SpectraScan SpectraCalorimeter.

  10. Light Absorbing Organic Carbon from Wood Pyrolysis: Closure Study between Measured and Modeled Optical Properties at Controlled Relative Humidity between 40 and 95%

    NASA Astrophysics Data System (ADS)

    Mena, F. C.; Brem, B. T.; Chen, Y.; Bond, T. C.; Rood, M. J.

    2012-12-01

    Hygroscopic aerosols uptake water at increased ambient relative humidity (RH), and this changes their size, shape, and composition. This affects their optical properties, and thus their radiative forcing. Organic carbon (OC) is an important component of the aerosol system due to its ubiquity and because its hygroscopic and light absorption properties are not well understood. In this work we have modeled the hygroscopic growth and optical properties (extinction, scattering, absorption, and single scattering albedo) at three wavelengths of OC from wood pyrolysis at increasing RH from 40 to 95%. Our goal was to reproduce laboratory measurements of the optical properties, particularly absorption of OC. Measurements included hygroscopicity with an H-TDMA, extinction with an extinction cell, and scattering with a nephelometer. Absorption was calculated by difference of extinction and scattering. The κ-Köhler model was used to model the hygroscopic growth, and different refractive index mixing rules were used to model the mixing state of OC+water mixtures. The hygroscopic growth factor (κ) for OC was 0.08 ± 0.02 (corresponding to a growth factor (GF) = 1.19 ± 0.03 at 90% RH). The linear volume average mixing rule, Lorentz-Lorenz, Maxwell-Garnett, Bruggeman, and Core-Shell configuration were not able to reproduce the laboratory results. The mixing rule that was able to reproduce the structure of the absorption dependence on RH was the Dynamic Effective Medium Approximation (DEMA). Using refractive indices of m = 1.57 + 0.017i at 467 nm, 1.57 + 0.01i at 530 nm, and 1.57 + 0.002i nm at 660 nm, which were adjusted to obtain absorption measurements at dry conditions, we obtained closure at 467 nm and 530 nm wavelengths at RH from 40 to 95%, within the uncertainties of the model and the measurements. Absorption at 660 nm was very low, and it was not possible to confirm closure due to detection limitations of the measurements. Our results indicate that absorption by OC is

  11. Ab initio modeling of the optical properties in organometallic halide perovskites for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Neukirch, Amanda; Nei, Wanyi; Pedesseau, Laurent; Even, Jacky; Katan, Claudine; Mohite, Aditya; Tretiak, Segrei

    2015-03-01

    The need for an inexpensive, clean, and plentiful source of energy has generated large amounts of research in an assortment of solution processed organic and hybrid organic-inorganic solar cells. A relative newcomer to the field of solution processed photovoltaics is the lead halide perovskite solar cell. In the past 5 years, the efficiencies of devices made from this material have increased from 3.5% to nearly 20%. Despite the rapid development of organic-inorganic perovskite solar cells, a thorough understanding of the fundamental photophysical processes driving the high performance of these devices is not well understood. I am using state-of-the-art ab initio computational techniques in order to characterize the properties at the interface of perovskite devices in order to aide in materials design and device engineering. I will present an in-depth analysis of the electronic and optical properties of bulk and surface states of pure and mixed halide systems. The high-level static quantum mechanical calculations, including spin-orbit-coupling and the many body GW approach, identify the key electronic states involved in photoinduced dynamics. This knowledge provides important information on how the optical properties change with variations to the system. Supported by the DOE, the LANL LDRD program XW11, and CNLS.

  12. Highly Tunable Colloidal Perovskite Nanoplatelets through Variable Cation, Metal, and Halide Composition.

    PubMed

    Weidman, Mark C; Seitz, Michael; Stranks, Samuel D; Tisdale, William A

    2016-08-23

    Colloidal perovskite nanoplatelets are a promising class of semiconductor nanomaterials-exhibiting bright luminescence, tunable and spectrally narrow absorption and emission features, strongly confined excitonic states, and facile colloidal synthesis. Here, we demonstrate the high degree of spectral tunability achievable through variation of the cation, metal, and halide composition as well as nanoplatelet thickness. We synthesize nanoplatelets of the form L2[ABX3]n-1BX4, where L is an organic ligand (octylammonium, butylammonium), A is a monovalent metal or organic molecular cation (cesium, methylammonium, formamidinium), B is a divalent metal cation (lead, tin), X is a halide anion (chloride, bromide, iodide), and n-1 is the number of unit cells in thickness. We show that variation of n, B, and X leads to large changes in the absorption and emission energy, while variation of the A cation leads to only subtle changes but can significantly impact the nanoplatelet stability and photoluminescence quantum yield (with values over 20%). Furthermore, mixed halide nanoplatelets exhibit continuous spectral tunability over a 1.5 eV spectral range, from 2.2 to 3.7 eV. The nanoplatelets have relatively large lateral dimensions (100 nm to 1 μm), which promote self-assembly into stacked superlattice structures-the periodicity of which can be adjusted based on the nanoplatelet surface ligand length. These results demonstrate the versatility of colloidal perovskite nanoplatelets as a material platform, with tunability extending from the deep-UV, across the visible, into the near-IR. In particular, the tin-containing nanoplatelets represent a significant addition to the small but increasingly important family of lead- and cadmium-free colloidal semiconductors. PMID:27471862

  13. Metasurface Broadband Solar Absorber

    DOE PAGESBeta

    Azad, Abul K.; Kort-Kamp, Wilton J. M.; Sykora, Milan; Weisse-Bernstein, Nina R.; Luk, Ting S.; Taylor, Antoinette J.; Dalvit, Diego A. R.; Chen, Hou-Tong

    2016-02-01

    Here, we demonstrate a broadband, polarization independent, wide-angle absorber based on a metallic metasurface architecture, which accomplishes greater than 90% absorptance in the visible and near-infrared range of the solar spectrum, and exhibits low absorptivity (emissivity) at mid- and far-infrared wavelengths. The complex unit cell of the metasurface solar absorber consists of eight pairs of gold nano-resonators that are separated from a gold ground plane by a thin silicon dioxide spacer. Moreover, our experimental measurements reveal high-performance absorption over a wide range of incidence angles for both s- and p-polarizations. We also investigate numerically the frequency-dependent field and current distributionsmore » to elucidate how the absorption occurs within the metasurface structure.« less

  14. Metasurface Broadband Solar Absorber

    PubMed Central

    Azad, Abul K.; Kort-Kamp, Wilton J. M.; Sykora, Milan; Weisse-Bernstein, Nina R.; Luk, Ting S.; Taylor, Antoinette J.; Dalvit, Diego A. R.; Chen, Hou-Tong

    2016-01-01

    We demonstrate a broadband, polarization independent, wide-angle absorber based on a metallic metasurface architecture, which accomplishes greater than 90% absorptance in the visible and near-infrared range of the solar spectrum, and exhibits low absorptivity (emissivity) at mid- and far-infrared wavelengths. The complex unit cell of the metasurface solar absorber consists of eight pairs of gold nano-resonators that are separated from a gold ground plane by a thin silicon dioxide spacer. Our experimental measurements reveal high-performance absorption over a wide range of incidence angles for both s- and p-polarizations. We also investigate numerically the frequency-dependent field and current distributions to elucidate how the absorption occurs within the metasurface structure. PMID:26828999

  15. Metasurface Broadband Solar Absorber

    NASA Astrophysics Data System (ADS)

    Azad, Abul K.; Kort-Kamp, Wilton J. M.; Sykora, Milan; Weisse-Bernstein, Nina R.; Luk, Ting S.; Taylor, Antoinette J.; Dalvit, Diego A. R.; Chen, Hou-Tong

    2016-02-01

    We demonstrate a broadband, polarization independent, wide-angle absorber based on a metallic metasurface architecture, which accomplishes greater than 90% absorptance in the visible and near-infrared range of the solar spectrum, and exhibits low absorptivity (emissivity) at mid- and far-infrared wavelengths. The complex unit cell of the metasurface solar absorber consists of eight pairs of gold nano-resonators that are separated from a gold ground plane by a thin silicon dioxide spacer. Our experimental measurements reveal high-performance absorption over a wide range of incidence angles for both s- and p-polarizations. We also investigate numerically the frequency-dependent field and current distributions to elucidate how the absorption occurs within the metasurface structure.

  16. Metasurface Broadband Solar Absorber.

    PubMed

    Azad, Abul K; Kort-Kamp, Wilton J M; Sykora, Milan; Weisse-Bernstein, Nina R; Luk, Ting S; Taylor, Antoinette J; Dalvit, Diego A R; Chen, Hou-Tong

    2016-01-01

    We demonstrate a broadband, polarization independent, wide-angle absorber based on a metallic metasurface architecture, which accomplishes greater than 90% absorptance in the visible and near-infrared range of the solar spectrum, and exhibits low absorptivity (emissivity) at mid- and far-infrared wavelengths. The complex unit cell of the metasurface solar absorber consists of eight pairs of gold nano-resonators that are separated from a gold ground plane by a thin silicon dioxide spacer. Our experimental measurements reveal high-performance absorption over a wide range of incidence angles for both s- and p-polarizations. We also investigate numerically the frequency-dependent field and current distributions to elucidate how the absorption occurs within the metasurface structure. PMID:26828999

  17. Laser cooling of organic-inorganic lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Ha, Son-Tung; Shen, Chao; Zhang, Jun; Xiong, Qihua

    2016-02-01

    Optical irradiation with suitable energy can cool solids, a phenomenon known as optical refrigeration, first proposed in 1929 and experimentally achieved in ytterbium-doped glasses in 1995. Since then, considerable progress has been made in various rare earth element-doped materials, with a recent record of cooling to 91 K directly from ambient temperatures. For practical use and to suit future applications of optical refrigeration, the discovery of materials with facile and scalable synthesis and high cooling power density will be required. Herein we present the realization of a net cooling of 23.0 K in micrometre-thick 3D CH3NH3PbI3 (MAPbI3) and 58.7 K in exfoliated 2D (C6H5C2H4NH3)2PbI4 (PhEPbI4) perovskite crystals directly from room temperature. We found that the perovskite crystals exhibit strong photoluminescence upconversion and near unity external quantum efficiency, properties that are responsible for the realization of net laser cooling. Our findings indicate that solution-processed perovskite thin films may be a highly suitable candidate for constructing integrated optical cooler devices.

  18. Ionized Absorbers in AGN

    NASA Astrophysics Data System (ADS)

    Mathur, S.

    1999-08-01

    As a part of this program, we observed three AGN:PKS2251 + 113, PG0043 = 039 and PLH909. Two objects show signatures of absorbtion in their UV spectra. Based on our earlier modeling of X-ray warm absorbents, we expected to observe X-ray observation in these objects. The third, PLH909, is known to have soft excess in EINSTEIN data. Attachment: "Exploratory ASCA observation of broad absorption line quasi-stellar objects".

  19. Ionized Absorbers in AGN

    NASA Technical Reports Server (NTRS)

    Mathur, S.

    1999-01-01

    As a part of this program, we observed three AGN:PKS2251 + 113, PG0043 = 039 and PLH909. Two objects show signatures of absorbtion in their UV spectra. Based on our earlier modeling of X-ray warm absorbents, we expected to observe X-ray observation in these objects. The third, PLH909, is known to have soft excess in EINSTEIN data. Attachment: "Exploratory ASCA observation of broad absorption line quasi-stellar objects".

  20. Vitrification of IFR and MSBR halide salt reprocessing wastes

    SciTech Connect

    Siemer, D.D.

    2013-07-01

    Both of the genuinely sustainable (breeder) nuclear fuel cycles (IFR - Integral Fast Reactor - and MSBR - Molten Salt Breeder Reactor -) studied by the USA's national laboratories would generate high level reprocessing waste (HLRW) streams consisting of a relatively small amount ( about 4 mole %) of fission product halide (chloride or fluoride) salts in a matrix comprised primarily (about 95 mole %) of non radioactive alkali metal halide salts. Because leach resistant glasses cannot accommodate much of any of the halides, most of the treatment scenarios previously envisioned for such HLRW have assumed a monolithic waste form comprised of a synthetic analog of an insoluble crystalline halide mineral. In practice, this translates to making a 'substituted' sodalite ('Ceramic Waste Form') of the IFR's chloride salt-based wastes and fluoroapatite of the MSBR's fluoride salt-based wastes. This paper discusses my experimental studies of an alternative waste management scenario for both fuel cycles that would separate/recycle the waste's halide and immobilize everything else in iron phosphate (Fe-P) glass. It will describe both how the work was done and what its results indicate about how a treatment process for both of those wastes should be implemented (fluoride and chloride behave differently). In either case, this scenario's primary advantages include much higher waste loadings, much lower overall cost, and the generation of a product (glass) that is more consistent with current waste management practices. (author)

  1. Genetic Control of Methyl Halide Production in Arabidopsis

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Ostergaard, L.; Saltzman, E. S.; Yanofsky, M. F.

    2003-12-01

    Methyl chloride and methyl bromide are the primary carriers of natural chlorine and bromine to the stratosphere where they catalyze the destruction of ozone, whereas methyl iodide influences aerosol formation and ozone loss in the troposphere. Methyl bromide is also an agricultural fumigant whose use is scheduled to be phased out by international agreement. Despite the economic and environmental importance of these methyl halides, their natural sources and biological production mechanisms are poorly understood. Currently identified sources include oceans, biomass burning, industrial and agricultural use, fuel combustion, salt marshes, wetlands, rice paddies, certain terrestrial plants and fungi, and abiotic processes. We demonstrate that the model plant Arabidopsis thaliana produces and emits methyl halides and that the enzyme primarily responsible for the production is encoded by the HARMLESS TO OZONE LAYER (HOL) gene located on chromosome II. In mutant plants that have a disruption of the HOL gene, methyl halide production is largely eliminated. A phylogenetic analysis using the HOL gene suggests that the ability to produce methyl halides is widespread among vascular plants. This approach provides a genetic basis for understanding and predicting patterns of methyl halide production by plants.

  2. Halide Perovskites: Poor Man's High-Performance Semiconductors.

    PubMed

    Stoumpos, Constantinos C; Kanatzidis, Mercouri G

    2016-07-01

    Halide perovskites are a rapidly developing class of medium-bandgap semiconductors which, to date, have been popularized on account of their remarkable success in solid-state heterojunction solar cells raising the photovoltaic efficiency to 20% within the last 5 years. As the physical properties of the materials are being explored, it is becoming apparent that the photovoltaic performance of the halide perovskites is just but one aspect of the wealth of opportunities that these compounds offer as high-performance semiconductors. From unique optical and electrical properties stemming from their characteristic electronic structure to highly efficient real-life technological applications, halide perovskites constitute a brand new class of materials with exotic properties awaiting discovery. The nature of halide perovskites from the materials' viewpoint is discussed here, enlisting the most important classes of the compounds and describing their most exciting properties. The topics covered focus on the optical and electrical properties highlighting some of the milestone achievements reported to date but also addressing controversies in the vastly expanding halide perovskite literature. PMID:27174223

  3. Regeneration of zinc halide catalyst used in the hydrocracking of polynuclear hydrocarbons

    DOEpatents

    Gorin, Everett

    1978-01-01

    Improved recovery of spent molten zinc halide hydro-cracking catalyst is achieved in the oxidative vapor phase regeneration thereof by selective treatment of the zinc oxide carried over by the effluent vapors from the regeneration zone with hydrogen halide gas under conditions favoring the reaction of the zinc oxide with the hydrogen halide, whereby regenerated zinc halide is recovered in a solids-free state with little loss of zinc values.

  4. Rare-earth tri-halides methanol-adduct single-crystal scintillators for gamma ray and neutron detection

    NASA Astrophysics Data System (ADS)

    Boatner, L. A.; Wisniewski, D. J.; Neal, J. S.; Bell, Z. W.; Ramey, J. O.; Kolopus, J. A.; Chakoumakos, B. C.; Custelcean, R.; Wisniewska, M.; Pena, K. E.

    2009-08-01

    Cerium activated rare-earth tri- halides represent a well-known family of high performance inorganic rare-earth scintillators - including the high-light-yield, high-energy-resolution scintillator, cerium-doped lanthanum tribromide. These hygroscopic inorganic rare-earth halides are currently grown as single crystals from the melt - either by the Bridgman or Czochralski techniques - slow and expensive processes that are frequently characterized by severe cracking of the material due to anisotropic thermal stresses and cleavage effects. We have recently discovered a new family of cerium-activated rare-earth metal organic scintillators consisting of tri-halide methanol adducts of cerium and lanthanum - namely CeCl3(CH3OH)4 and LaBr3(CH3OH)4:Ce. These methanol-adduct scintillator materials can be grown near room temperature from a methanol solution, and their high solubility is consistent with the application of the rapid solution growth methods that are currently used to grow very large single crystals of potassium dihydrogen phosphate. The structures of these new rare-earth metal-organic scintillating compounds were determined by single crystal x-ray refinements, and their scintillation response to both gamma rays and neutrons, as presented here, was characterized using different excitation sources. Tri-halide methanol-adduct crystals activated with trivalent cerium apparently represent the initial example of a solution-grown rare-earth metal-organic molecular scintillator that is applicable to gamma ray, x-ray, and fast neutron detection.

  5. High Biomass Specific Methyl Halide Production Rates of Selected Coastal Marsh Plants and its Relationship to Halide Content

    NASA Astrophysics Data System (ADS)

    Manley, S. L.; Wang, N.; Cicerone, R. J.

    2002-12-01

    Salt tolerant coastal marsh plants (halophytes) have previously been shown to be globally significant producers of methyl chloride (MeCl) and methyl bromide (MeBr). While halophytes are known for their high salt content, there are few reports of their halide content. Our studies have attempted to quantify biomass specific methyl halide (MeX) production from these plants and relate it to tissue halide levels. MeCl, MeBr and MeI production rates and tissue chloride, bromide and iodide concentrations from selected coastal marsh plants were measured for nearly a year. Certain halophyte species (i.e. Batis and Frankenia) have very high summer biomass specific production rates for MeX (e.g. Frankenia: 1 ug MeCl /gfwt/hr; 80 ng MeBr/gfwt/hr; 8 ng MeI/gfwt/hr). These rates of MeCl and MeBr production are much higher than those from other coastal marsh plants or seaweeds. Plant halide levels remain high throughout the year, while MeX production peaks at a high level in mid summer falling to low winter rates. This implies a linkage to plant growth. Higher levels of chloride and bromide were seen in the fleshy marsh plants such as Batis (saltwort, approximately 20 percent dry wt chloride, 0.4 percent dry wt bromide) and Salicornia (pickleweed) than in the others such as Frankenia (alkali heath) approx 7 percent dry wt chloride, 0.1 percent dry wt bromide) or Spartina (cordgrass). No such trend was seen for iodide, which ranged from 4 - 10 ppm. Calculations show the daily halide losses from MeX production are far less than the variability in tissue halide content. MeX production removes a small fraction of the total tissue halide from these plants suggesting that MeX production is not a mechanism used by these species to control internal halide levels. Saltwort cell-free extracts incubated with bromide or iodide in the presence of S-adenosyl-L-methionine (SAM) produced the corresponding MeX. MeBr production was inhibited by caffeic acid the substrate of lignin-specific O

  6. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 10 Energy 3 2010-01-01 2010-01-01 false Definitions concerning metal halide lamp ballasts and... FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide lamp ballasts and fixtures. Ballast efficiency means, in the case of...

  7. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 10 Energy 3 2012-01-01 2012-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  8. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... 10 Energy 3 2013-01-01 2013-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  9. 10 CFR 431.322 - Definitions concerning metal halide lamp ballasts and fixtures.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... 10 Energy 3 2011-01-01 2011-01-01 false Definitions concerning metal halide lamp ballasts and fixtures. 431.322 Section 431.322 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.322 Definitions concerning metal halide...

  10. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  11. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  12. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  13. 40 CFR 721.10181 - Halide salt of an alkylamine (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Halide salt of an alkylamine (generic... Specific Chemical Substances § 721.10181 Halide salt of an alkylamine (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as halide salt...

  14. Metal-halide mixtures for latent heat energy storage

    NASA Technical Reports Server (NTRS)

    Chen, K.; Manvi, R.

    1981-01-01

    Alkali metal and alkali halide mixtures are identified which may be suitable for thermal energy storage at temperatures above 600 C. The use of metal-halides is appropriate because of their tendency to form two immiscible melts with a density difference, which reduces scale formation and solidification on heat transfer surfaces. Also, the accumulation of phase change material along the melt interface is avoided by the self-dispersing characteristic of some metal-halides, in particular Sr-SrCl2, Ba-BaCl2, and Ba-BaBr2 mixtures. Further advantages lie in their high thermal conductivities, ability to cope with thermal shock, corrosion inhibition, and possibly higher energy densities.

  15. Absorber for terahertz radiation management

    DOEpatents

    Biallas, George Herman; Apeldoorn, Cornelis; Williams, Gwyn P.; Benson, Stephen V.; Shinn, Michelle D.; Heckman, John D.

    2015-12-08

    A method and apparatus for minimizing the degradation of power in a free electron laser (FEL) generating terahertz (THz) radiation. The method includes inserting an absorber ring in the FEL beam path for absorbing any irregular THz radiation and thus minimizes the degradation of downstream optics and the resulting degradation of the FEL output power. The absorber ring includes an upstream side, a downstream side, and a plurality of wedges spaced radially around the absorber ring. The wedges form a scallop-like feature on the innermost edges of the absorber ring that acts as an apodizer, stopping diffractive focusing of the THz radiation that is not intercepted by the absorber. Spacing between the scallop-like features and the shape of the features approximates the Bartlett apodization function. The absorber ring provides a smooth intensity distribution, rather than one that is peaked on-center, thereby eliminating minor distortion downstream of the absorber.

  16. Corrosion resistant neutron absorbing coatings

    SciTech Connect

    Choi, Jor-Shan; Farmer, Joseph C.; Lee, Chuck K.; Walker, Jeffrey; Russell, Paige; Kirkwood, Jon; Yang, Nancy; Champagne, Victor

    2012-05-29

    A method of forming a corrosion resistant neutron absorbing coating comprising the steps of spray or deposition or sputtering or welding processing to form a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material. Also a corrosion resistant neutron absorbing coating comprising a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material.

  17. Corrosion resistant neutron absorbing coatings

    SciTech Connect

    Choi, Jor-Shan; Farmer, Joseph C; Lee, Chuck K; Walker, Jeffrey; Russell, Paige; Kirkwood, Jon; Yang, Nancy; Champagne, Victor

    2013-11-12

    A method of forming a corrosion resistant neutron absorbing coating comprising the steps of spray or deposition or sputtering or welding processing to form a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material. Also a corrosion resistant neutron absorbing coating comprising a composite material made of a spray or deposition or sputtering or welding material, and a neutron absorbing material.

  18. Metallotropic liquid crystals formed by surfactant templating of molten metal halides.

    PubMed

    Martin, James D; Keary, Cristin L; Thornton, Todd A; Novotnak, Mark P; Knutson, Jeremey W; Folmer, Jacob C W

    2006-04-01

    Liquid crystals consist of anisotropic molecular units, and most are organic molecules. Materials incorporating metals into anisotropic molecules, described as metallomesogens, have been prepared. Anisotropic structures such as one-dimensional chains and two-dimensional layers are frequently observed in solid-state inorganic materials, however, little is understood about structural organization in melts of such materials. Achieving liquid-crystalline behaviour in inorganic fluids should be possible if the anisotropic structure can be retained or designed into the molten phase. We demonstrated the ability to engineer zeolite-type structures into metal halide glasses and liquids. In this work we have engineered lamellar, cubic and hexagonal liquid-crystalline structure in metal-halide melts by controlling the volume fraction and nature of the inorganic block (up to 80 mol%) with respect to alkylammonium surfactants. The high metal content of these liquid-crystalline systems significantly advances the field of metallomesogens, which seeks to combine magnetic, electronic, optical, redox and catalytic properties common to inorganic materials with the fluid properties of liquid crystals. PMID:16547520

  19. Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis

    NASA Astrophysics Data System (ADS)

    Koh, Ming Joo; Nguyen, Thach T.; Zhang, Hanmo; Schrock, Richard R.; Hoveyda, Amir H.

    2016-03-01

    Olefin metathesis has had a large impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is limited. Here we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of a catalyst that is generated in situ and used with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents, and proceed to high conversion at ambient temperature within four hours. We obtain many alkenyl chlorides, bromides and fluorides in up to 91 per cent yield and complete Z selectivity. This method can be used to synthesize biologically active compounds readily and to perform site- and stereoselective fluorination of complex organic molecules.

  20. Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis.

    PubMed

    Koh, Ming Joo; Nguyen, Thach T; Zhang, Hanmo; Schrock, Richard R; Hoveyda, Amir H

    2016-03-24

    Olefin metathesis has had a large impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is limited. Here we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of a catalyst that is generated in situ and used with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents, and proceed to high conversion at ambient temperature within four hours. We obtain many alkenyl chlorides, bromides and fluorides in up to 91 per cent yield and complete Z selectivity. This method can be used to synthesize biologically active compounds readily and to perform site- and stereoselective fluorination of complex organic molecules. PMID:27008965

  1. Characterizing the Sources and Sinks of Methyl Halides in the Florida Everglades and Coastal Waters by Isotopic Analysis

    NASA Astrophysics Data System (ADS)

    Scully, N. M.; Jones, R. D.; Raffel, A.; Rice, A. L.

    2012-12-01

    Recent studies have demonstrated that the methyl halides, methyl chloride and methyl bromide, are produced in significant quantities by phytoplankton and by the photochemical oxidation of dissolved organic matter (DOM). However, we know little of the mechanisms responsible for the photochemical production of methyl halides and also the factors which affect the microbial formation and consumption in the surface waters. We are currently conducting laboratory experiments to elucidate the mechanisms responsible for the photochemical and microbial formation and consumption of methyl chloride and methyl bromide in the Florida Everglades and coastal waters. We present data from laboratory experiments using a stable isotope spiking tracer method to quantify photochemical flux rates of methyl chloride and methyl bromide from wetland and estuarine water samples collected at FCE-LTER sites located in Taylor Slough and Florida Bay. These photochemical experiments include waters that span a wide range of halide and DOM concentrations. We use these results to estimate the net photochemical flux of methyl chloride and methyl bromide from the Florida Everglades. We have also conducted stable carbon isotope analysis of the methyl chloride. These experiments are being conducted to determine the carbon isotopic ratios (d13C) of methyl chloride produced from the photolysis of organic matter in natural waters and will provide an inventory of d13C values from one of the sources within the studied Everglades ecotones. This research was supported by the National Science Foundation Chemical Oceanography Program Award No. 1029710.

  2. Thermodynamic reactivity, growth and characterization of mercurous halide crystals

    NASA Technical Reports Server (NTRS)

    Singh, N. B.; Gottlieb, M.; Henningsen, T.; Hopkins, R. H.; Mazelsky, R.; Singh, M.; Glicksman, M. E.; Paradies, C.

    1992-01-01

    Thermodynamic calculations were carried out for the Hg-X-O system (X = Cl, Br, I) to identify the potential sources of contamination and relative stability of oxides and oxy-halide phases. The effect of excess mercury vapor pressure on the optical quality of mercurous halide crystal was studied by growing several mercurous chloride crystals from mercury-rich composition. The optical quality of crystals was examined by birefringence interferometry and laser scattering studies. Crystals grown in slightly mercury-rich composition showed improved optical quality relative to stoichiometric crystals.

  3. Thallous halide materials for use in cryogenic applications

    NASA Technical Reports Server (NTRS)

    Lawless, William N. (Inventor)

    1981-01-01

    Thallous halides, either alone or in combination with other ceramic materials, are used in cryogenic applications such as heat exchange material for the regenerator section of a closed-cycle cryogenic refrigeration section, as stabilizing coatings for superconducting wires, and as dielectric insulating materials. The thallous halides possess unusually large specific heats at low temperatures, have large thermal conductivities, are nonmagnetic, and are nonconductors of electricity. They can be formed into a variety of shapes such as spheres, bars, rods, or the like and can be coated onto substrates.

  4. Boron and aluminum halides under pressure - polymerization and chemical transformations

    NASA Astrophysics Data System (ADS)

    Yao, Yansun

    2013-06-01

    High-pressure phase transitions of boron and aluminum halides have been theoretically studied. At low pressure, crystals of the familiar monomers (BX3) and dimers (Al2X6) are the structures of choice. While the higher oligomers as well as three dimensional infinite polymers are unstable at ambient pressure, they are stabilized by application of external pressure, taking advantage of the extra orbitals made accessible by the increased coordination. Several new crystal structures of boron and aluminum halides have been predicted at high pressures. Calculated x-ray diffraction patterns and Raman spectra of these phases are in good agreement with available experimental data.

  5. Applications of Raman scattering spectroscopy to halide glasses

    NASA Astrophysics Data System (ADS)

    Bendow, B.; Banerjee, P. K.; Drexhage, M. G.

    1983-04-01

    Polarized Raman scattering spectroscopy is a useful tool for investigating fundamental vibrational properties, structure and bonding, origins of IR edge absorption, and dispersion of the IR refractive index. In this paper, the application of Raman spectroscopy to halide glasses and, in particular, heavy metal fluoride glasses, is described. The spectra of the latter differ substantially from those of simple oxide, halide or chalcogenide glasses and, moreover, display a wide range of vibrational characteristics, depending on composition. In combination with infrared spectroscopy, useful guidelines can be developed for tailoring glass compositions for specific applications.

  6. Solar radiation absorbing material

    DOEpatents

    Googin, John M.; Schmitt, Charles R.; Schreyer, James M.; Whitehead, Harlan D.

    1977-01-01

    Solar energy absorbing means in solar collectors are provided by a solar selective carbon surface. A solar selective carbon surface is a microporous carbon surface having pores within the range of 0.2 to 2 micrometers. Such a surface is provided in a microporous carbon article by controlling the pore size. A thermally conductive substrate is provided with a solar selective surface by adhering an array of carbon particles in a suitable binder to the substrate, a majority of said particles having diameters within the range of about 0.2-10 microns.

  7. Absorber for solar power.

    PubMed

    Powell, W R

    1974-10-01

    A simple, economical absorber utilizing a new principle of operation to achieve very low reradiation losses while generating temperatures limited by material properties of quartz is described. Its performance is analyzed and indicates approximately 90% thermal efficiency and 73% conversion efficiency for an earth based unit with moderately concentrated (~tenfold) sunlight incident. It is consequently compatible with the most economic of concentrator mirrors (stamped) or mirrors deployable in space. Space applications are particularly attractive, as temperatures significantly below 300 K are possible and permit even higher conversion efficiency. PMID:20134700

  8. On the definition of absorbed dose

    NASA Astrophysics Data System (ADS)

    Grusell, Erik

    2015-02-01

    Purpose: The quantity absorbed dose is used extensively in all areas concerning the interaction of ionizing radiation with biological organisms, as well as with matter in general. The most recent and authoritative definition of absorbed dose is given by the International Commission on Radiation Units and Measurements (ICRU) in ICRU Report 85. However, that definition is incomplete. The purpose of the present work is to give a rigorous definition of absorbed dose. Methods: Absorbed dose is defined in terms of the random variable specific energy imparted. A random variable is a mathematical function, and it cannot be defined without specifying its domain of definition which is a probability space. This is not done in report 85 by the ICRU, mentioned above. Results: In the present work a definition of a suitable probability space is given, so that a rigorous definition of absorbed dose is possible. This necessarily includes the specification of the experiment which the probability space describes. In this case this is an irradiation, which is specified by the initial particles released and by the material objects which can interact with the radiation. Some consequences are discussed. Specific energy imparted is defined for a volume, and the definition of absorbed dose as a point function involves the specific energy imparted for a small mass contained in a volume surrounding the point. A possible more precise definition of this volume is suggested and discussed. Conclusions: The importance of absorbed dose motivates a proper definition, and one is given in the present work. No rigorous definition has been presented before.

  9. Liquid Cryogen Absorber for MICE

    SciTech Connect

    Baynham, D.E.; Bish, P.; Bradshaw, T.W.; Cummings, M.A.; Green,M.A.; Ishimoto, S.; Ivaniouchenkov, I.; Lau, W.; Yang, S.Q.; Zisman, M.S.

    2005-08-20

    The Muon Ionization Cooling Experiment (MICE) will test ionization cooling of muons. In order to have effective ionization cooling, one must use an absorber that is made from a low-z material. The most effective low z materials for ionization cooling are hydrogen, helium, lithium hydride, lithium and beryllium, in that order. In order to measure the effect of material on cooling, several absorber materials must be used. This report describes a liquid-hydrogen absorber that is within a pair of superconducting focusing solenoids. The absorber must also be suitable for use with liquid helium. The following absorber components are discussed in this report; the absorber body, its heat exchanger, the hydrogen system, and the hydrogen safety. Absorber cooling and the thin windows are not discussed here.

  10. Structural Characterization of Methanol Substituted Lanthanum Halides

    PubMed Central

    Boyle, Timothy J.; Ottley, Leigh Anna M.; Alam, Todd M.; Rodriguez, Mark A.; Yang, Pin; Mcintyre, Sarah K.

    2010-01-01

    The first study into the alcohol solvation of lanthanum halide [LaX3] derivatives as a means to lower the processing temperature for the production of the LaBr3 scintillators was undertaken using methanol (MeOH). Initially the de-hydration of {[La(µ-Br)(H2O)7](Br)2}2 (1) was investigated through the simple room temperature dissolution of 1 in MeOH. The mixed solvate monomeric [La(H2O)7(MeOH)2](Br)3 (2) compound was isolated where the La metal center retains its original 9-coordination through the binding of two additional MeOH solvents but necessitates the transfer of the innersphere Br to the outersphere. In an attempt to in situ dry the reaction mixture of 1 in MeOH over CaH2, crystals of [Ca(MeOH)6](Br)2 (3) were isolated. Compound 1 dissolved in MeOH at reflux temperatures led to the isolation of an unusual arrangement identified as the salt derivative {[LaBr2.75•5.25(MeOH)]+0.25 [LaBr3.25•4.75(MeOH)]−0.25} (4). The fully substituted species was ultimately isolated through the dissolution of dried LaBr3 in MeOH forming the 8-coordinated [LaBr3(MeOH)5] (5) complex. It was determined that the concentration of the crystallization solution directed the structure isolated (4 concentrated; 5 dilute) The other LaX3 derivatives were isolated as [(MeOH)4(Cl)2La(µ-Cl)]2 (6) and [La(MeOH)9](I)3•MeOH (7). Beryllium Dome XRD analysis indicated that the bulk material for 5 appear to have multiple solvated species, 6 is consistent with the single crystal, and 7 was too broad to elucidate structural aspects. Multinuclear NMR (139La) indicated that these compounds do not retain their structure in MeOD. TGA/DTA data revealed that the de-solvation temperatures of the MeOH derivatives 4 – 6 were slightly higher in comparison to their hydrated counterparts. PMID:20514349

  11. 40 CFR 721.10698 - Polyfluorinated alkyl halide (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polyfluorinated alkyl halide (generic). 721.10698 Section 721.10698 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances §...

  12. Method for calcining nuclear waste solutions containing zirconium and halides

    DOEpatents

    Newby, Billie J.

    1979-01-01

    A reduction in the quantity of gelatinous solids which are formed in aqueous zirconium-fluoride nuclear reprocessing waste solutions by calcium nitrate added to suppress halide volatility during calcination of the solution while further suppressing chloride volatility is achieved by increasing the aluminum to fluoride mole ratio in the waste solution prior to adding the calcium nitrate.

  13. Methyl halide emission estimates from domestic biomass burning in Africa

    NASA Astrophysics Data System (ADS)

    Mead, M. I.; Khan, M. A. H.; White, I. R.; Nickless, G.; Shallcross, D. E.

    Inventories of methyl halide emissions from domestic burning of biomass in Africa, from 1950 to the present day and projected to 2030, have been constructed. By combining emission factors from Andreae and Merlet [2001. Emission of trace gases and aerosols from biomass burning. Global Biogeochemical Cycles 15, 955-966], the biomass burning estimates from Yevich and Logan [2003. An assessment of biofuel use and burning of agricultural waste in the developing world. Global Biogeochemical Cycles 17(4), 1095, doi:10.1029/2002GB001952] and the population data from the UN population division, the emission of methyl halides from domestic biomass usage in Africa has been estimated. Data from this study suggest that methyl halide emissions from domestic biomass burning have increased by a factor of 4-5 from 1950 to 2005 and based on the expected population growth could double over the next 25 years. This estimated change has a non-negligible impact on the atmospheric budgets of methyl halides.

  14. CO2 electrochemical reduction via adsorbed halide anions

    NASA Astrophysics Data System (ADS)

    Ogura, Kotaro; Salazar-Villalpando, Maria D.

    2011-01-01

    The electrochemical reduction of CO2 was studied utilizing halide ions as electrolytes, specifically, aqueous solutions of KCl, KBr, KI. Electrochemical experiments were carried out in a laboratory-made, divided H-type cell. The working electrode was a copper mesh, while the counter and reference electrodes were a Pt wire and an Ag/AgCl electrode, respectively. The results of our work suggest a reaction mechanism for the electrochemical reduction of CO2 where the presence of Cu-X as the catalytic layer facilitates the electron transfer from the electrode to CO2. Electron-transfer to CO2 may occur via the X- ad(Br-, Cl-, I-)-C bond, which is formed by the electron flow from the specifically adsorbed halide anion to the vacant orbital of CO2. The stronger the adsorption of the halide anion to the electrode, the more strongly CO2 is restrained, resulting in higher CO2 reduction current. Furthermore, it is suggested that specifically adsorbed halide anions could suppress the adsorption of protons; leading to a higher hydrogen overvoltage. These effects may synergistically mitigate the over potential necessary for CO2 reduction, and thus increase the rate of electrochemical CO2 reduction.

  15. Electro-optic contribution to Raman scattering from alkali halides

    SciTech Connect

    Mahan, G.D.; Subbaswamy, K.R.

    1986-06-15

    The electro-optic contributions to second-order Raman scattering and field-induced first-order scattering from alkali halides are calculated explicitly in terms of the ionic hyperpolarizability coefficients. The relevant local-field corrections are evaluated. Illustrative numerical results are presented.

  16. Metamaterial electromagnetic wave absorbers.

    PubMed

    Watts, Claire M; Liu, Xianliang; Padilla, Willie J

    2012-06-19

    The advent of negative index materials has spawned extensive research into metamaterials over the past decade. Metamaterials are attractive not only for their exotic electromagnetic properties, but also their promise for applications. A particular branch-the metamaterial perfect absorber (MPA)-has garnered interest due to the fact that it can achieve unity absorptivity of electromagnetic waves. Since its first experimental demonstration in 2008, the MPA has progressed significantly with designs shown across the electromagnetic spectrum, from microwave to optical. In this Progress Report we give an overview of the field and discuss a selection of examples and related applications. The ability of the MPA to exhibit extreme performance flexibility will be discussed and the theory underlying their operation and limitations will be established. Insight is given into what we can expect from this rapidly expanding field and future challenges will be addressed. PMID:22627995

  17. Absorber coatings' degradation

    SciTech Connect

    Moore, S.W.

    1984-01-01

    This report is intended to document some of the Los Alamos efforts that have been carried out under the Department of Energy (DOE) Active Heating and Cooling Materials Reliability, Maintainability, and Exposure Testing program. Funding for these activities is obtained directly from DOE although they represent a variety of projects and coordination with other agencies. Major limitations to the use of solar energy are the uncertain reliability and lifetimes of solar systems. This program is aimed at determining material operating limitations, durabilities, and failure modes such that materials improvements can be made and lifetimes can be extended. Although many active and passive materials and systems are being studied at Los Alamos, this paper will concentrate on absorber coatings and degradation of these coatings.

  18. Color-Pure Violet-Light-Emitting Diodes Based on Layered Lead Halide Perovskite Nanoplates.

    PubMed

    Liang, Dong; Peng, Yuelin; Fu, Yongping; Shearer, Melinda J; Zhang, Jingjing; Zhai, Jianyuan; Zhang, Yi; Hamers, Robert J; Andrew, Trisha L; Jin, Song

    2016-07-26

    Violet electroluminescence is rare in both inorganic and organic light-emitting diodes (LEDs). Low-cost and room-temperature solution-processed lead halide perovskites with high-efficiency and color-tunable photoluminescence are promising for LEDs. Here, we report room-temperature color-pure violet LEDs based on a two-dimensional lead halide perovskite material, namely, 2-phenylethylammonium (C6H5CH2CH2NH3(+), PEA) lead bromide [(PEA)2PbBr4]. The natural quantum confinement of two-dimensional layered perovskite (PEA)2PbBr4 allows for photoluminescence of shorter wavelength (410 nm) than its three-dimensional counterpart. By converting as-deposited polycrystalline thin films to micrometer-sized (PEA)2PbBr4 nanoplates using solvent vapor annealing, we successfully integrated this layered perovskite material into LEDs and achieved efficient room-temperature violet electroluminescence at 410 nm with a narrow bandwidth. This conversion to nanoplates significantly enhanced the crystallinity and photophysical properties of the (PEA)2PbBr4 samples and the external quantum efficiency of the violet LED. The solvent vapor annealing method reported herein can be generally applied to other perovskite materials to increase their grain size and, ultimately, improve the performance of optoelectronic devices based on perovskite materials. PMID:27336850

  19. Photo-induced halide redistribution in organic–inorganic perovskite films

    DOE PAGESBeta

    deQuilettes, Dane W.; Zhang, Wei; Burlakov, Victor M.; Graham, Daniel J.; Leijtens, Tomas; Osherov, Anna; Bulovic, Vladimir; Snaith, Henry J.; Ginger, David S.; Stranks, Samuel D.

    2016-05-24

    Organic-inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced 'brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging themore » same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. In conclusion, our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance.« less

  20. Multiple neutral alkali halide attachments onto oligosaccharides in electrospray ionization mass spectrometry

    NASA Astrophysics Data System (ADS)

    Striegel, André M.; Timpa, Judy D.; Piotrowiak, Piotr; Cole, Richard B.

    1997-03-01

    Oligosaccharides perform essential functions in a variety of biological and agricultural processes. Recent approaches to characterization of these molecules by mass spectrometry have utilized mainly soft-ionization methods such as electrospray ionization (ESI) and thermospray (TS), as well as fast atom bombardment (FAB). The behavior of a series of maltooligosaccharides with [alpha]-(1 --> 4) linkages, maltose (G2) through maltoheptaose (G7), under ESI conditions, has been investigated here. The oligosaccharides were dissolved in N,N-dimethylacetamide containing lithium chloride (DMAc/LiCl) prior to analysis by ESI-MS. A highly unusual feature, evident in all mass spectra obtained using this solvent system, was the presence of multiple [`]neutral' salt attachments onto lithium adducts of the sugars. Resultant ions took the form of [Gx + Li + nLiCl+, where n may reach a value as high as eight. Compared to LiCl, the propensity for alkali halide attachment using other alkali chlorides or lithium halides was greatly reduced. An investigation of this phenomenon is presented in which the organic and inorganic portions of the employed solvent were systematically varied, and semi-empirical computer modeling was performed to better understand lithium coordination by the sugars.

  1. Calorimetric and theoretical study of the interaction between some saccharides and sodium halide in water.

    PubMed

    Zhuo, Kelei; Fu, Yingyi; Bai, Guangyue; Wang, Jianji; Yan, Haike; Wang, Hanqing

    2012-08-23

    Dilution enthalpies and mixing enthalpies of sodium halide and some saccharides (glucose, galactose, xylose, arabinose, fructose, and sucrose) in aqueous solution were determined by calorimetric measurements at 298.15 K. The values were used to determine enthalpic pair interaction parameters. Combined with Gibbs energy pair parameters, entropic pair interaction parameters were also obtained. Theoretical calculations at the B3LYP/6-311++G(d,p) level were carried out to provide the information of structures and thermodynamic functions. The information reveals the thermodynamic essence of the interactions between sodium halide and saccharides in aqueous solutions. The experimental results and theoretical calculations show that the sign of enthalpic pair interaction parameter 2υh(ES) is determined by the direct interaction between saccharides and ions, whereas the difference in value of 2υh(ES) for different saccharides or electrolytes depends on the partial dehydration of saccharides or anions in aqueous solution. The difference in value of entropic pair interaction parameters depends partly on the different dominant interactions in the process of partial dehydration of saccharides or ions. An enthalpy-entropy compensation relationship was observed for the sodium bromide-aldopyranose-water systems. Remarkably, it can be conjectured that the hydration entropy of glucose is lower than for other monosaccharides. Perhaps it is one of the reasons why glucose plays an important role in living organisms rather than other monosaccharides. PMID:22779908

  2. Spectral and Dynamical Properties of Single Excitons, Biexcitons, and Trions in Cesium-Lead-Halide Perovskite Quantum Dots.

    PubMed

    Makarov, Nikolay S; Guo, Shaojun; Isaienko, Oleksandr; Liu, Wenyong; Robel, István; Klimov, Victor I

    2016-04-13

    Organic-inorganic lead-halide perovskites have been the subject of recent intense interest due to their unusually strong photovoltaic performance. A new addition to the perovskite family is all-inorganic Cs-Pb-halide perovskite nanocrystals, or quantum dots, fabricated via a moderate-temperature colloidal synthesis. While being only recently introduced to the research community, these nanomaterials have already shown promise for a range of applications from color-converting phosphors and light-emitting diodes to lasers, and even room-temperature single-photon sources. Knowledge of the optical properties of perovskite quantum dots still remains vastly incomplete. Here we apply various time-resolved spectroscopic techniques to conduct a comprehensive study of spectral and dynamical characteristics of single- and multiexciton states in CsPbX3 nanocrystals with X being either Br, I, or their mixture. Specifically, we measure exciton radiative lifetimes, absorption cross-sections, and derive the degeneracies of the band-edge electron and hole states. We also characterize the rates of intraband cooling and nonradiative Auger recombination and evaluate the strength of exciton-exciton coupling. The overall conclusion of this work is that spectroscopic properties of Cs-Pb-halide quantum dots are largely similar to those of quantum dots of more traditional semiconductors such as CdSe and PbSe. At the same time, we observe some distinctions including, for example, an appreciable effect of the halide identity on radiative lifetimes, considerably shorter biexciton Auger lifetimes, and apparent deviation of their size dependence from the "universal volume scaling" previously observed for many traditional nanocrystal systems. The high efficiency of Auger decay in perovskite quantum dots is detrimental to their prospective applications in light-emitting devices and lasers. This points toward the need for the development of approaches for effective suppression of Auger

  3. Electrochemically regenerable carbon dioxide absorber

    NASA Technical Reports Server (NTRS)

    Woods, R. R.; Marshall, R. D.; Schubert, F. H.; Heppner, D. B.

    1979-01-01

    Preliminary designs were generated for two electrochemically regenerable carbon dioxide absorber concepts. Initially, an electrochemically regenerable absorption bed concept was designed. This concept incorporated the required electrochemical regeneration components in the absorber design, permitting the absorbent to be regenerated within the absorption bed. This hardware was identified as the electrochemical absorber hardware. The second hardware concept separated the functional components of the regeneration and absorption process. This design approach minimized the extravehicular activity component volume by eliminating regeneration hardware components within the absorber. The electrochemical absorber hardware was extensively characterized for major operating parameters such as inlet carbon dioxide partial pressure, process air flow rate, operational pressure, inlet relative humidity, regeneration current density and absorption/regeneration cycle endurance testing.

  4. Liquid Hydrogen Absorber for MICE

    SciTech Connect

    Ishimoto, S.; Suzuki, S.; Yoshida, M.; Green, Michael A.; Kuno, Y.; Lau, Wing

    2010-05-30

    Liquid hydrogen absorbers for the Muon Ionization Cooling Experiment (MICE) have been developed, and the first absorber has been tested at KEK. In the preliminary test at KEK we have successfully filled the absorber with {approx}2 liters of liquid hydrogen. The measured hydrogen condensation speed was 2.5 liters/day at 1.0 bar. No hydrogen leakage to vacuum was found between 300 K and 20 K. The MICE experiment includes three AFC (absorber focusing coil) modules, each containing a 21 liter liquid hydrogen absorber made of aluminum. The AFC module has safety windows to separate its vacuum from that of neighboring modules. Liquid hydrogen is supplied from a cryocooler with cooling power 1.5 W at 4.2 K. The first absorber will be assembled in the AFC module and installed in MICE at RAL.

  5. Broadband patterned magnetic microwave absorber

    SciTech Connect

    Li, Wei; Wu, Tianlong; Wang, Wei; Guan, Jianguo; Zhai, Pengcheng

    2014-07-28

    It is a tough task to greatly improve the working bandwidth for the traditional flat microwave absorbers because of the restriction of available material parameters. In this work, a simple patterning method is proposed to drastically broaden the absorption bandwidth of a conventional magnetic absorber. As a demonstration, an ultra-broadband microwave absorber with more than 90% absorption in the frequency range of 4–40 GHz is designed and experimentally realized, which has a thin thickness of 3.7 mm and a light weight equivalent to a 2-mm-thick flat absorber. In such a patterned absorber, the broadband strong absorption is mainly originated from the simultaneous incorporation of multiple λ/4 resonances and edge diffraction effects. This work provides a facile route to greatly extend the microwave absorption bandwidth for the currently available absorbing materials.

  6. Plants absorb heavy metals

    SciTech Connect

    Parry, J.

    1995-02-01

    Decontamination of heavy metals-polluted soils remains one of the most intractable problems of cleanup technology. Currently available techniques include extraction of the metals by physical and chemical means, such as acid leaching and electroosmosis, or immobilization by vitrification. There are presently no techniques for cleanup which are low cost and retain soil fertility after metals removal. But a solution to the problem could be on the horizon. A small but growing number of plants native to metalliferous soils are known to be capable of accumulating extremely high concentrations of metals in their aboveground portions. These hyperaccumulators, as they are called, contain up to 1,000 times larger metal concentrations in their aboveground parts than normal species. Their distribution is global, including many different families of flowering plants of varying growth forms, from herbaceous plants to trees. Hyperaccumulators absorb metals they do not need for their own nutrition. The metals are accumulated in the leaf and stem vacuoles, and to a lesser extent in the roots.

  7. Electronic properties of perovskite absorbers for solar cell applications

    NASA Astrophysics Data System (ADS)

    Filip, Marina; Giustino, Feliciano

    2015-03-01

    Metal halide perovskite absorbers have captured the attention of the photovoltaics research community in the past 3 years, reaching efficiencies over 19%. Despite this unprecedented progress, the remarkable physical properties of these materials are not yet fully understood. In this work we show an exhaustive computational study of CH3NH3PbI3 within density functional theory and the GW approximation. We show the effect of semicore states and spin-orbit coupling on the quasiparticle band gap of CH3NH3PbI3 and describe a straightforward ``self-consistent scissor'' method to correct the underestimated dielectric screening in the G0W0 approach. Finally, we model the interplay between the structural and electronic properties of lead-iodide perovskites and propose novel lead-iodide peroskite absorbers with different cations at the center of the cuboctahedral cavity facilitating the tunning of the fundamental band gap. This work was supported by the ERC (EU FP7 / ERC 239578), UK EPSRC (EP/J009857/1) and the Leverhulme Trust (RL-2012-001).

  8. Transformation of Sintered CsPbBr3 Nanocrystals to Cubic CsPbI3 and Gradient CsPbBrxI3-x through Halide Exchange.

    PubMed

    Hoffman, Jacob B; Schleper, A Lennart; Kamat, Prashant V

    2016-07-13

    All-inorganic cesium lead halide (CsPbX3, X = Br(-), I(-)) perovskites could potentially provide comparable photovoltaic performance with enhanced stability compared to organic-inorganic lead halide species. However, small-bandgap cubic CsPbI3 has been difficult to study due to challenges forming CsPbI3 in the cubic phase. Here, a low-temperature procedure to form cubic CsPbI3 has been developed through a halide exchange reaction using films of sintered CsPbBr3 nanocrystals. The reaction was found to be strongly dependent upon temperature, featuring an Arrhenius relationship. Additionally, film thickness played a significant role in determining internal film structure at intermediate reaction times. Thin films (50 nm) showed only a small distribution of CsPbBrxI3-x species, while thicker films (350 nm) exhibited much broader distributions. Furthermore, internal film structure was ordered, featuring a compositional gradient within film. Transient absorption spectroscopy showed the influence of halide exchange on the excited state of the material. In thicker films, charge carriers were rapidly transferred to iodide-rich regions near the film surface within the first several picoseconds after excitation. This ultrafast vectorial charge-transfer process illustrates the potential of utilizing compositional gradients to direct charge flow in perovskite-based photovoltaics. PMID:27322132

  9. Spectroscopic effects of disorder and vibrational localization in mixed-halide metal-halide chain solids

    SciTech Connect

    Love, S.P.; Scott, B.; Worl, L.A.; Huckett, S.C.; Saxena, A.; Huang, X.Z.; Bishop, A.R.; Swanson, B.I.

    1993-02-01

    Resonance Raman techniques, together with lattice-dynamics and Peierls-Hubbard modelling, are used to explore the electronic and vibrational dynamics of the quasi-one-dimensional metal-halogen chain solids [Pt(en){sub 2}][R(en){sub 2}X{sub 2}](ClO{sub 4}){sub 4}, (en = C{sub 2}H{sub 8}N{sub 2} and X=Cl, Br), abbreviated ``PLX.`` The mixed-halide materials PtCl{sub 1-x}Br{sub x} and PtCl{sub 1-x}I{sub x} consist of long mixed chains with heterojunctions between segments of the two constituent materials. Thus, in addition to providing mesoscale modulation of the chain electronic states, they serve as prototypes for elucidating the properties to be expected for macroscopic heterojunctions of these highly nonlinear materials. Once a detailed understanding of the various local vibrational modes occurring in these disordered solids is developed, the electronic structure of the chain segments and junctions can be probed by tuning the Raman excitation through their various electronic resonances.

  10. Matrix isolation infrared spectra of hydrogen halide and halogen complexes with nitrosyl halides

    NASA Technical Reports Server (NTRS)

    Allamandola, Louis J.; Lucas, Donald; Pimentel, George C.

    1982-01-01

    Matrix isolation infrared spectra of nitrosyl halide (XNO) complexes with HX and X2 (X = Cl, Br) are presented. The relative frequency shifts of the HX mode are modest (ClNO H-Cl, delta-nu/nu = -0.045; BrNO H-Br, delta-nu/nu = -0.026), indicating weak hydrogen bonds 1-3 kcal/mol. These shifts are accompanied by significant shifts to higher frequencies in the XN-O stretching mode (CIN-O HCl, delta-nu/nu = +0.016; BrN-O HBr, delta-nu/nu = +0.011). Similar shifts were observed for the XN-O X2 complexes (ClN-O Cl2, delta-nu/nu = +0.009; BrN-O-Br2, delta-nu/nu = +0.013). In all four complexes, the X-NO stretching mode relative shift is opposite in sign and about 1.6 times that of the NO stretching mode. These four complexes are considered to be similar in structure and charge distribution. The XN-O frequency shift suggests that complex formation is accompanied by charge withdrawal from the NO bond ranging from about .04 to .07 electron charges. The HX and X2 molecules act as electron acceptors, drawing electrons out of the antibonding orbital of NO and strengthening the XN-O bond. The implications of the pattern of vibrational shifts concerning the structure of the complexes are discussed.

  11. Methods and Mechanisms for Cross-Electrophile Coupling of Csp(2) Halides with Alkyl Electrophiles.

    PubMed

    Weix, Daniel J

    2015-06-16

    Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C-H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of generally cross-selective reactions of aryl halides and acyl halides with alkyl halides, the mechanistic studies that illuminated the underlying principles of these reactions, and the use of these fundamental principles in the rational design of new cross-electrophile coupling reactions. Although the coupling of two different electrophiles under reducing conditions often leads primarily to symmetric dimers, the subtle differences in reactivity of aryl halides and alkyl halides with nickel catalysts allowed for generally cross-selective coupling reactions. These conditions could also be extended to the coupling of acyl halides with alkyl halides. These reactions are exceptionally functional group tolerant and can be assembled on the benchtop. A combination of stoichiometric and catalytic studies on the mechanism of these reactions revealed an unusual radical-chain mechanism and suggests that selectivity arises from (1) the preference of nickel(0) for oxidative addition to aryl halides and acyl halides over alkyl halides and (2) the greater propensity of alkyl halides to form free radicals. Bipyridine-ligated arylnickel intermediates react with alkyl radicals to efficiently form, after reductive elimination, new C-C bonds. Finally, the resulting nickel(I) species is proposed to regenerate an alkyl radical to carry the chain. Examples of new reactions designed using these principles include carbonylative coupling of aryl halides with alkyl halides to form ketones, arylation of epoxides to form β-aryl alcohols, and coupling of benzyl sulfonate esters with aryl halides to form

  12. Methods and Mechanisms for Cross-Electrophile Coupling of Csp2 Halides with Alkyl Electrophiles

    PubMed Central

    2016-01-01

    Conspectus Cross-electrophile coupling, the cross-coupling of two different electrophiles, avoids the need for preformed carbon nucleophiles, but development of general methods has lagged behind cross-coupling and C–H functionalization. A central reason for this slow development is the challenge of selectively coupling two substrates that are alike in reactivity. This Account describes the discovery of generally cross-selective reactions of aryl halides and acyl halides with alkyl halides, the mechanistic studies that illuminated the underlying principles of these reactions, and the use of these fundamental principles in the rational design of new cross-electrophile coupling reactions. Although the coupling of two different electrophiles under reducing conditions often leads primarily to symmetric dimers, the subtle differences in reactivity of aryl halides and alkyl halides with nickel catalysts allowed for generally cross-selective coupling reactions. These conditions could also be extended to the coupling of acyl halides with alkyl halides. These reactions are exceptionally functional group tolerant and can be assembled on the benchtop. A combination of stoichiometric and catalytic studies on the mechanism of these reactions revealed an unusual radical-chain mechanism and suggests that selectivity arises from (1) the preference of nickel(0) for oxidative addition to aryl halides and acyl halides over alkyl halides and (2) the greater propensity of alkyl halides to form free radicals. Bipyridine-ligated arylnickel intermediates react with alkyl radicals to efficiently form, after reductive elimination, new C–C bonds. Finally, the resulting nickel(I) species is proposed to regenerate an alkyl radical to carry the chain. Examples of new reactions designed using these principles include carbonylative coupling of aryl halides with alkyl halides to form ketones, arylation of epoxides to form β-aryl alcohols, and coupling of benzyl sulfonate esters with aryl

  13. Energy absorber for the CETA

    NASA Astrophysics Data System (ADS)

    Wesselski, Clarence J.

    1994-05-01

    The energy absorber that was developed for the CETA (Crew Equipment and Translation Aid) on Space Station Freedom is a metal on metal frictional type and has a load regulating feature that prevents excessive stroking loads from occurring while in operation. This paper highlights some of the design and operating aspects and the testing of this energy absorber.

  14. Energy absorber for the CETA

    NASA Technical Reports Server (NTRS)

    Wesselski, Clarence J.

    1994-01-01

    The energy absorber that was developed for the CETA (Crew Equipment and Translation Aid) on Space Station Freedom is a metal on metal frictional type and has a load regulating feature that prevents excessive stroking loads from occurring while in operation. This paper highlights some of the design and operating aspects and the testing of this energy absorber.

  15. Metal-shearing energy absorber

    NASA Technical Reports Server (NTRS)

    Fay, R. J.; Wittrock, E. P.

    1971-01-01

    Device, consisting of tongue of thin aluminum alloy strip, pull tab, slotted steel plate which serves as cutter, and steel buckle, absorbs mechanical energy when its ends are subjected to tensile loading. Device is applicable as auxiliary shock absorbing anchor for automobile and airplane safety belts.

  16. Leaf absorbance and photosynthesis

    NASA Technical Reports Server (NTRS)

    Schurer, Kees

    1994-01-01

    The absorption spectrum of a leaf is often thought to contain some clues to the photosynthetic action spectrum of chlorophyll. Of course, absorption of photons is needed for photosynthesis, but the reverse, photosynthesis when there is absorption, is not necessarily true. As a check on the existence of absorption limits we measured spectra for a few different leaves. Two techniques for measuring absorption have been used, viz. the separate determination of the diffuse reflectance and the diffuse transmittance with the leaf at a port of an integrating sphere and the direct determination of the non-absorbed fraction with the leaf in the sphere. In a cross-check both methods yielded the same results for the absorption spectrum. The spectrum of a Fuchsia leaf, covering the short-wave region from 350 to 2500 nm, shows a high absorption in UV, blue and red, the well known dip in the green and a steep fall-off at 700 nm. Absorption drops to virtually zero in the near infrared, with subsequent absorptions, corresponding to the water absorption bands. In more detailed spectra, taken at 5 nm intervals with a 5 nm bandwidth, differences in chlorophyll content show in the different depths of the dip around 550 nm and in a small shift of the absorption edge at 700 nm. Spectra for Geranium (Pelargonium zonale) and Hibiscus (with a higher chlorophyll content) show that the upper limit for photosynthesis can not be much above 700 nm. No evidence, however, is to be seen of a lower limit for photosynthesis and, in fact, some experiments down to 300 nm still did not show a decrease of the absorption although it is well recognized that no photosynthesis results with 300 nm wavelengths.

  17. Visible light broadband perfect absorbers

    NASA Astrophysics Data System (ADS)

    Jia, X. L.; Meng, Q. X.; Yuan, C. X.; Zhou, Z. X.; Wang, X. O.

    2016-03-01

    The visible light broadband perfect absorbers based on the silver (Ag) nano elliptical disks and holes array are studied using finite difference time domain simulations. The semiconducting indium silicon dioxide thin film is introduced as the space layer in this sandwiched structure. Utilizing the asymmetrical geometry of the structures, polarization sensitivity for transverse electric wave (TE)/transverse magnetic wave (TM) and left circular polarization wave (LCP)/right circular polarization wave (RCP) of the broadband absorption are gained. The absorbers with Ag nano disks and holes array show several peaks absorbance of 100% by numerical simulation. These simple and flexible perfect absorbers are particularly desirable for various potential applications including the solar energy absorber.

  18. Electrolytic systems and methods for making metal halides and refining metals

    SciTech Connect

    Holland, Justin M.; Cecala, David M.

    2015-05-26

    Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

  19. Alkali Halide Microstructured Optical Fiber for X-Ray Detection

    NASA Technical Reports Server (NTRS)

    DeHaven, S. L.; Wincheski, R. A.; Albin, S.

    2014-01-01

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

  20. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides.

    PubMed

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-01-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F(-), Cl(-), Br(-)). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs. PMID:27184228

  1. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides

    PubMed Central

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-01-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F−, Cl−, Br−). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs. PMID:27184228

  2. Alkali halide microstructured optical fiber for X-ray detection

    SciTech Connect

    DeHaven, S. L. E-mail: russel.a.wincheski@nasa.gov; Wincheski, R. A. E-mail: russel.a.wincheski@nasa.gov; Albin, S.

    2015-03-31

    Microstructured optical fibers containing alkali halide scintillation materials of CsI(Na), CsI(Tl), and NaI(Tl) are presented. The scintillation materials are grown inside the microstructured fibers using a modified Bridgman-Stockbarger technique. The x-ray photon counts of these fibers, with and without an aluminum film coating are compared to the output of a collimated CdTe solid state detector over an energy range from 10 to 40 keV. The photon count results show significant variations in the fiber output based on the materials. The alkali halide fiber output can exceed that of the CdTe detector, dependent upon photon counter efficiency and fiber configuration. The results and associated materials difference are discussed.

  3. Gaseous NH3 Confers Porous Pt Nanodendrites Assisted by Halides

    NASA Astrophysics Data System (ADS)

    Lu, Shuanglong; Eid, Kamel; Li, Weifeng; Cao, Xueqin; Pan, Yue; Guo, Jun; Wang, Liang; Wang, Hongjing; Gu, Hongwei

    2016-05-01

    Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F‑, Cl‑, Br‑). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs.

  4. Large methyl halide emissions from south Texas salt marshes

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Whelan, M. E.; Min, D.-H.

    2014-06-01

    Coastal salt marshes are natural sources of methyl chloride (CH3Cl) and methyl bromide (CH3Br) to the atmosphere, but measured emission rates vary widely by geography. Here we report large methyl halide fluxes from subtropical salt marshes of south Texas. Sites with the halophytic plant, Batis maritima, emitted methyl halides at rates that are orders of magnitude greater than sites containing other vascular plants or macroalgae. B. maritima emissions were generally highest at midday; however, diurnal variability was more pronounced for CH3Br than CH3Cl, and surprisingly high nighttime CH3Cl fluxes were observed in July. Seasonal and intra-site variability were large, even taking into account biomass differences. Overall, these subtropical salt marsh sites show much higher emission rates than temperate salt marshes at similar times of the year, supporting the contention that low-latitude salt marshes are significant sources of CH3Cl and CH3Br.

  5. Large methyl halide emissions from south Texas salt marshes

    NASA Astrophysics Data System (ADS)

    Rhew, R. C.; Whelan, M. E.; Min, D.-H.

    2014-11-01

    Coastal salt marshes are natural sources of methyl chloride (CH3Cl) and methyl bromide (CH3Br) to the atmosphere, but measured emission rates vary widely by geography. Here we report large methyl halide fluxes from subtropical salt marshes of south Texas. Sites with the halophytic plant, Batis maritima, emitted methyl halides at rates that are orders of magnitude greater than sites containing other vascular plants or macroalgae. B. maritima emissions were generally highest at midday; however, diurnal variability was more pronounced for CH3Br than CH3Cl, and surprisingly high nighttime CH3Cl fluxes were observed in July. Seasonal and intra-site variability were large, even taking into account biomass differences. Overall, these subtropical salt marsh sites show much higher emission rates than temperate salt marshes at similar times of the year, supporting the contention that low-latitude salt marshes are significant sources of CH3Cl and CH3Br.

  6. Electronic excitation in bulk and nanocrystalline alkali halides.

    PubMed

    Bichoutskaia, Elena; Pyper, Nicholas C

    2012-11-14

    The lowest energy excitations in bulk alkali halides are investigated by considering five different excited state descriptions. It is concluded that excitation transfers one outermost halide electron in the fully ionic ground state to the lowest energy vacant s orbital of one closest cation neighbour to produce the excited state termed dipolar. The excitation energies of seven salts were computed using shell model description of the lattice polarization produced by the effective dipole moment of the excited state neutral halogen-neutral metal pair. Ab initio uncorrelated short-range inter-ionic interactions computed from anion wavefunctions adapted to the in-crystal environment were augmented by short-range electron correlation contributions derived from uniform electron-gas density functional theory. Dispersive attractions including wavefunction overlap damping were introduced using reliable semi-empirical dispersion coefficients. The good agreement between the predicted excitation energies and experiment provides strong evidence that the excited state is dipolar. In alkali halide nanocrystals in which each ionic plane contains only four ions, the Madelung energies are significantly reduced compared with the bulk. This predicts that the corresponding intra-crystal excitation energies in the nanocrystals, where there are two excited states depending on whether the halide electron is transferred to a cation in the same or in the neighbouring plane, will be reduced by almost 2 eV. For such an encapsulated KI crystal, it has been shown that the greater polarization in the excited state of the bulk crystal causes these reductions to be lowered to a 1.1 eV-1.5 eV range for the case of charge transfer to a neighbouring plane. For intra-plane charge transfer the magnitude of the polarization energy is further reduced thus causing the excitation in these encapsulated materials to be only 0.2 eV less than in the bulk crystal. PMID:23163361

  7. Oxidative alkoxylation of phosphine in alcohol solutions of copper halides

    NASA Astrophysics Data System (ADS)

    Polimbetova, G. S.; Borangazieva, A. K.; Ibraimova, Zh. U.; Bugubaeva, G. O.; Keynbay, S.

    2016-08-01

    The phosphine oxidation reaction with oxygen in alcohol solutions of copper (I, II) halides is studied. Kinetic parameters, intermediates, and by-products are studied by means of NMR 31Р-, IR-, UV-, and ESR- spectroscopy; and by magnetic susceptibility, redox potentiometry, gas chromatography, and elemental analysis. A reaction mechanism is proposed, and the optimum conditions are found for the reaction of oxidative alkoxylation phosphine.

  8. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents

    PubMed Central

    Shrestha, Bijay

    2015-01-01

    Summary We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N’,N’-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  9. Copper-catalyzed arylation of alkyl halides with arylaluminum reagents.

    PubMed

    Shrestha, Bijay; Giri, Ramesh

    2015-01-01

    We report a Cu-catalyzed coupling between triarylaluminum reagents and alkyl halides to form arylalkanes. The reaction proceeds in the presence of N,N,N',N'-tetramethyl-o-phenylenediamine (NN-1) as a ligand in combination with CuI as a catalyst. This catalyst system enables the coupling of primary alkyl iodides and bromides with electron-neutral and electron-rich triarylaluminum reagents and affords the cross-coupled products in good to excellent yields. PMID:26734088

  10. Organolead Halide Perovskites for Low Operating Voltage Multilevel Resistive Switching.

    PubMed

    Choi, Jaeho; Park, Sunghak; Lee, Joohee; Hong, Kootak; Kim, Do-Hong; Moon, Cheon Woo; Park, Gyeong Do; Suh, Junmin; Hwang, Jinyeon; Kim, Soo Young; Jung, Hyun Suk; Park, Nam-Gyu; Han, Seungwu; Nam, Ki Tae; Jang, Ho Won

    2016-08-01

    Organolead halide perovskites are used for low-operating-voltage multilevel resistive switching. Ag/CH3 NH3 PbI3 /Pt cells exhibit electroforming-free resistive switching at an electric field of 3.25 × 10(3) V cm(-1) for four distinguishable ON-state resistance levels. The migration of iodine interstitials and vacancies with low activation energies is responsible for the low-electric-field resistive switching via filament formation and annihilation. PMID:27192161

  11. thin films as absorber

    NASA Astrophysics Data System (ADS)

    González, J. O.; Shaji, S.; Avellaneda, D.; Castillo, G. A.; Das Roy, T. K.; Krishnan, B.

    2014-09-01

    Photovoltaic structures were prepared using AgSb(S x Se1- x )2 as absorber and CdS as window layer at various conditions via a hybrid technique of chemical bath deposition and thermal evaporation followed by heat treatments. Silver antimony sulfo selenide thin films [AgSb(S x Se1- x )2] were prepared by heating multilayers of sequentially deposited Sb2S3/Ag dipped in Na2SeSO3 solution, glass/Sb2S3/Ag/Se. For this, Sb2S3 thin films were deposited from a chemical bath containing SbCl3 and Na2S2O3. Then, Ag thin films were thermally evaporated on glass/Sb2S3, followed by selenization by dipping in an acidic solution of Na2SeSO3. The duration of dipping was varied as 3, 4 and 5 h. Two different heat treatments, one at 350 °C for 20 min in vacuum followed by a post-heat treatment at 325 °C for 2 h in Ar, and the other at 350 °C for 1 h in Ar, were applied to the multilayers of different configurations. X-ray diffraction results showed the formation of AgSb(S x Se1- x )2 thin films as the primary phase and AgSb(S,Se)2 and Sb2S3 as secondary phases. Morphology and elemental detection were done by scanning electron microscopy and energy dispersive X-ray analysis. X-ray photoelectron spectroscopic studies showed the depthwise composition of the films. Optical properties were determined by UV-vis-IR transmittance and reflection spectral analysis. AgSb(S x Se1- x )2 formed at different conditions was incorporated in PV structures glass/FTO/CdS/AgSb(S x Se1- x )2/C/Ag. Chemically deposited post-annealed CdS thin films of various thicknesses were used as window layer. J- V characteristics of the cells were measured under dark and AM1.5 illumination. Analysis of the J- V characteristics resulted in the best solar cell parameters of V oc = 520 mV, J sc = 9.70 mA cm-2, FF = 0.50 and η = 2.7 %.

  12. Role of Microstructure in the Electron-Hole Interaction of Hybrid Lead-Halide Perovskites

    PubMed Central

    Frost, Jarvist M.; Barker, Alex J.; De Bastiani, Michele; Gandini, Marina; Marras, Sergio; Lanzani, Guglielmo; Walsh, Aron; Petrozza, Annamaria

    2015-01-01

    Solar cells based on hybrid inorganic-organic halide perovskites have demonstrated high power conversion efficiencies in a range of architectures. The existence and stability of bound electron-hole pairs in these materials, and their role in the exceptional performance of optoelectronic devices, remains a controversial issue. Here we demonstrate, through a combination of optical spectroscopy and multiscale modeling as a function of the degree of polycrystallinity and temperature, that the electron-hole interaction is sensitive to the microstructure of the material. The long-range order is disrupted by polycrystalline disorder and the variations in electrostatic potential found for smaller crystals suppress exciton formation, while larger crystals of the same composition demonstrate an unambiguous excitonic state. We conclude that fabrication procedures and morphology strongly influence perovskite behaviour, with both free carrier and excitonic regimes possible, with strong implications for optoelectronic devices. PMID:26442125

  13. Artifacts in Absorption Measurements of Organometal Halide Perovskite Materials: What Are the Real Spectra?

    PubMed

    Tian, Yuxi; Scheblykin, Ivan G

    2015-09-01

    Organometal halide (OMH) perovskites have attracted lots of attention over the last several years due to their very promising performance as the materials for solar cells and light-emitting devices. Photophysical processes in these hybrid organic-inorganic semiconductors are still heavily debated. To know precise absorption spectra is absolutely necessary for quantitative understanding of the fundamental properties of OMH perovskites. We show that to measure the absorption of perovskite materials correctly is a difficult task which could be easily overlooked by the community. Many of the published absorption spectra exhibit a characteristic step-like featureless shape due to light scattering, high optical density of individual perovskite crystals and poor coverage of the substrate. We show how to recognize these artifacts, to avoid them, and to use absorption spectra of films for estimation of the surface coverage ratio. PMID:27120683

  14. Polar-solvent-free colloidal synthesis of highly luminescent alkylammonium lead halide perovskite nanocrystals.

    PubMed

    Vybornyi, Oleh; Yakunin, Sergii; Kovalenko, Maksym V

    2016-03-17

    A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm(-2). PMID:26645348

  15. Lasing in robust cesium lead halide perovskite nanowires

    PubMed Central

    Eaton, Samuel W.; Lai, Minliang; Gibson, Natalie A.; Wong, Andrew B.; Dou, Letian; Ma, Jie; Wang, Lin-Wang; Leone, Stephen R.; Yang, Peidong

    2016-01-01

    The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic–inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored and handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry–Pérot lasing occurs in CsPbBr3 nanowires with an onset of 5 μJ cm−2 with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 109 excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication. PMID:26862172

  16. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    DOE PAGESBeta

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher; Geohegan, David B.; Xiao, Kai

    2016-03-01

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films a major unresolved question is the competition between multiple halide species (e.g. I-, Cl-, Br-) in the formation of the mixed halide perovskite crystals. Whether Cl- ions are successfully incorporated into the perovskite crystal structure or alternatively, where they are located, is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br- or Cl- ions can promote crystal growth, yet reactive I- ionsmore » prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl- ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites, and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performance and cost-effective optoelectronic devices.« less

  17. Environmental controls over methyl halide emissions from rice paddies

    NASA Astrophysics Data System (ADS)

    Redeker, K. R.; Cicerone, R. J.

    2004-03-01

    This paper examines primary controlling factors that affect methyl halide emissions from rice paddy ecosystems. Observations of four cultivars under multiple growth conditions during studies in commercial fields and the University of California, Irvine, greenhouse lead to the conclusion that daily emissions of methyl halides are primarily determined by the growth stage of the rice plant, with the exception that methyl chloride emissions show no clear seasonal pattern. Methyl chloride emissions appear to be more from the paddy water and/or soil as opposed to the plants; however, in soils with high chloride content, these emissions appear to peak during the reproductive phase. Strong secondary influences include air temperature, soil halide concentration, and soil pore water saturation. The cultivars studied had statistically separate seasonally integrated emissions. Irradiant light and aboveground biomass appear to have little effect on emissions. Emissions of methyl chloride, methyl bromide, and methyl iodide are estimated to be 3.5, 2.3, and 48 mg/m2/yr, or 5.3, 3.5, and 72 Gg/yr, from rice paddies globally.

  18. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth.

    PubMed

    Yang, Bin; Keum, Jong; Ovchinnikova, Olga S; Belianinov, Alex; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

    2016-04-20

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films, a major unresolved question is the competition between multiple halide species (e.g., I(-), Cl(-), Br(-)) in the formation of the mixed-halide perovskite crystals. Whether Cl(-) ions are successfully incorporated into the perovskite crystal structure or, alternatively, where they are located is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br(-) or Cl(-) ions can promote crystal growth, yet reactive I(-) ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl(-) ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performing and cost-effective optoelectronic devices. PMID:26931634

  19. Insights from the Adsorption of Halide Ions on Graphene Materials.

    PubMed

    Zhu, Chang; Yang, Gang

    2016-08-18

    Graphene has recently found applications in a wide range of fields. Density functional calculations show that halide ions can be adsorbed on pristine graphene, but only F(-) has an appreciable binding energy (-97.0 kJ mol(-1) ). Graphene materials, which are mainly electron donors, can be made strong electron acceptors by edge functionalization with F atoms. The binding strengths of halide ions are greatly enhanced by edge functionalization and show direct proportionality with the degree of functionalization Θ and increased charge transfer. In contrast, the adsorption strengths of metal ions on pristine graphene are clearly superior to those of halide ions but decline substantially with increasing degree of edge functionalization, and for Θ=100 %, the binding energies of -95.7, -44.8, and -25.9 kJ mol(-1) that are calculated for Li(+) , Na(+) , and K(+) , respectively, are obviously inferior to that of F(-) (-186.3 kJ mol(-1) ). Thus, the electronic properties of graphene are fundamentally regulated by edge functionalization, and the preferential adsorption of certain metal ions or anions can be facilely realized by choice of an appropriate degree of functionalization. Adsorbed metal ions and anions behave differently on gradual addition of water molecules, and their binding strengths remain substantial when graphene materials are in the pristine and highly edge functionalized states, respectively. PMID:27127939

  20. Depth profile of halide anions under highly charged biological membrane

    NASA Astrophysics Data System (ADS)

    Sung, Woongmo; Wang, Wenjie; Lee, Jonggwan; Vaknin, David; Kim, Doseok

    2015-03-01

    Halide ion (Cl- and I-) distribution under a cationic Langmuir monolayer consisting of 1,2-dipalmitoyl-3 trimethylammonium-propane (DPTAP) molecules was investigated by vibrational sum-frequency generation (VSFG) and X-ray spectroscopy. From VSFG spectra, it was observed that large halide anions (I-) screen surface charge more efficiently so that interfacial water alignment becomes more randomized. On the other hand, number density of ions directly measured by X-ray fluorescence spectroscopy at grazing incidence angle reveals that the ion densities within 6 ~ 8 nm are the same for both I- and Cl-. Since the observed ion densities in both cases are almost equal to the charge density of the DPTAP monolayer, we propose that larger halide anions are attracted closer to the surface making direct binding with the charged headgroups of the molecules in the monolayer, accomplishing charge neutrality in short distance. This direct adsorption of anions also disturbs the monolayer structure both in terms of the conformation of alkyl chains and the vertical configuration of the monolayer, with iodine having the stronger effect. Our study shows that the length scale that ions neutralize a charged interface varies significantly and specifically even between monovalent ions.

  1. Iodomethane-Mediated Organometal Halide Perovskite with Record Photoluminescence Lifetime.

    PubMed

    Xu, Weidong; McLeod, John A; Yang, Yingguo; Wang, Yimeng; Wu, Zhongwei; Bai, Sai; Yuan, Zhongcheng; Song, Tao; Wang, Yusheng; Si, Junjie; Wang, Rongbin; Gao, Xingyu; Zhang, Xinping; Liu, Lijia; Sun, Baoquan

    2016-09-01

    Organometallic lead halide perovskites are excellent light harvesters for high-efficiency photovoltaic devices. However, as the key component in these devices, a perovskite thin film with good morphology and minimal trap states is still difficult to obtain. Herein we show that by incorporating a low boiling point alkyl halide such as iodomethane (CH3I) into the precursor solution, a perovskite (CH3NH3PbI3-xClx) film with improved grain size and orientation can be easily achieved. More importantly, these films exhibit a significantly reduced amount of trap states. Record photoluminescence lifetimes of more than 4 μs are achieved; these lifetimes are significantly longer than that of pristine CH3NH3PbI3-xClx films. Planar heterojunction solar cells incorporating these CH3I-mediated perovskites have demonstrated a dramatically increased power conversion efficiency compared to the ones using pristine CH3NH3PbI3-xClx. Photoluminescence, transient absorption, and microwave detected photoconductivity measurements all provide consistent evidence that CH3I addition increases the number of excitons generated and their diffusion length, both of which assist efficient carrier transport in the photovoltaic device. The simple incorporation of alkyl halide to enhance perovskite surface passivation introduces an important direction for future progress on high efficiency perovskite optoelectronic devices. PMID:27529636

  2. Extensive and Highly Accurate Line Lists for Hydrogen Halides

    NASA Astrophysics Data System (ADS)

    Li, G.; Bernath, P. F.; Gordon, I. E.; Rothman, L. S.; Richard, C.; Le Roy, R. J.; Coxon, J. A.; Hajigeorgiou, P.

    2011-06-01

    New dipole moment functions (DMF) for the ground X 1Σ+ electronic states of the hydrogen halides (HF, HCl, HBr, HI) have been obtained using a direct fit approach that fits the best available and appropriately weighted experimental line intensity data for individual ro-vibrational transitions. Combining the newly developed (taking into account the most recent experiments) empirical potential energy functions and the DMFs, line positions and line intensities of the hydrogen halides and their isotopologues have been calculated numerically using program LEVEL. In addition, new semi-empirical algorithms for assigning line-shape parameters for these species have been developed. Using these improvements, new line lists for hydrogen halides were created to update the HITRAN spectroscopic database. These new lists are more accurate and significantly more extensive than those included in the current version of the database (HITRAN2008). R.J. Le Roy, ``LEVEL 8.0, 2007'', University of Waterloo Chemical Physics Research Report CP-663 (2007); see http://leroy.uwaterloo.ca/programs/. L.S. Rothman, I.E. Gordon, A. Barbe, D.C. Benner, P.F. Bernath, et al., ``The HITRAN 2008 Molecular Spectroscopic Database,'' JQSRT 110, 532-572 (2009).

  3. Indirect detection of halide ions via fluorescence quenching of quinine sulfate in microcolumn ion chromatography.

    PubMed

    Takeuchi, Toyohide; Sumida, Junichi

    2004-06-01

    Halide ions could be visualized via fluorescence quenching in microcolumn ion chromatography. The fluorescence of quinine sulfate, which was contained in an acidic eluent, was quenched by halide ions. The observed fluorescence quenching values increased in this order: iodide, bromide, and chloride. The present detection system was relatively sensitive to halide ions except for fluoride: other anions gave smaller signals than halide ions. The present detection system provided quantitative information, so it could be applied to the determination of chloride in water samples. PMID:15228124

  4. Method for producing hydrocarbon fuels from heavy polynuclear hydrocarbons by use of molten metal halide catalyst

    DOEpatents

    Gorin, Everett

    1979-01-01

    In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst, thereafter separating at least a substantial portion of the carbonaceous material associated with the reaction mixture from the spent molten metal halide and thereafter regenerating the metal halide catalyst, an improvement comprising contacting the spent molten metal halide catalyst after removal of a major portion of the carbonaceous material therefrom with an additional quantity of hydrogen is disclosed.

  5. Direct X-ray detection with hybrid solar cells based on organolead halide perovskites

    NASA Astrophysics Data System (ADS)

    Gill, Hardeep Singh; Elshahat, Bassem; Sajo, Erno; Kumar, Jayant; Kokil, Akshay; Zygmanski, Piotr; Li, Lian; Mosurkal, Ravi

    2014-03-01

    Organolead halide perovskite materials are attracting considerable interest due to their exceptional opto-electronic properties, such as, high charge carrier mobilities, high exciton diffusion length, high extinction coefficients and broad-band absorption. These interesting properties have enabled their application in high performance hybrid photovoltaic devices. The high Z value of their constituents also makes these materials efficient for absorbing X-rays. Here we will present on the efficient use of hybrid solar cells based on organolead perovskite materials as X-ray detectors. Hybrid solar cells based on CH3NH3PbI3 were fabricated using facile processing techniques on patterned indium tin oxide coated glass substrates. The solar cells typically had a planar configuration of ITO/CH3NH3PbI3/P3HT/Ag. High sensitivity for X-rays due to high Z value, larger carrier mobility and better charge collection was observed. Detecting X-rays with energies relevant to medical oncology applications opens up the potential for diagnostic imaging applications.

  6. Effects of soluble organic complexants and their degradation products on the removal of selected radionuclides from high-level waste. Part II: Distributions of Sr, Cs, Tc, and Am onto 32 absorbers from four variations of Hanford tank 101-SY simulant solution

    SciTech Connect

    Marsh, S.F.; Svitra, Z.V.; Bowen, S.M.

    1995-04-01

    Many of the radioactive waste storage tanks at U.S. Department of Energy facilities contain organic compounds that have been degraded by radiolysis and chemical reactions during decades of storage. In this second part of our three-part investigation of the effects of soluble organic complexants and their degradation products, we measured the sorption of strontium, cesium, technetium, and americium onto 32 absorbers that offer high sorption of these elements in the absence of organic complexants. The four solutions tested were (1) a simulant for a 3:1 dilution of Hanford Tank 101-SY contents that initially contained ethylenediaminetetraacetic acid (EDTA), (2) this simulant after gamma-irradiation to 34 Mrads, (3) the unirradiated simulant after treatment with a hydrothermal organic-destruction process, and (4) the irradiated simulant after hydrothermal processing. For each of 512 element/absorber/solution combinations, we measured distribution coefficients (Kds) twice for each period for dynamic contact periods of 30 min, 2 h, and 6 h to obtain information about sorption kinetics. On the basis of our 3,072 measured Kd values, the sorption of strontium and americium is significantly decreased by the organic components of the simulant solutions, whereas the sorption of cesium and technetium appears unaffected by the organic components of the simulant solutions.

  7. Absorbent product to absorb fluids. [for collection of human wastes

    NASA Technical Reports Server (NTRS)

    Dawn, F. S.; Correale, J. V. (Inventor)

    1982-01-01

    A multi-layer absorbent product for use in contact with the skin to absorb fluids is discussed. The product utilizes a water pervious facing layer for contacting the skin, overlayed by a first fibrous wicking layer, the wicking layer preferably being of the one-way variety in which fluid or liquid is moved away from the facing layer. The product further includes a first container section defined by inner and outer layer of a water pervious wicking material between which is disposed a first absorbent mass. A second container section defined by inner and outer layers between which is disposed a second absorbent mass and a liquid impermeable/gas permeable layer. Spacesuit applications are discussed.

  8. Polar-solvent-free colloidal synthesis of highly luminescent alkylammonium lead halide perovskite nanocrystals

    NASA Astrophysics Data System (ADS)

    Vybornyi, Oleh; Yakunin, Sergii; Kovalenko, Maksym V.

    2016-03-01

    A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2.A novel synthesis of hybrid organic-inorganic lead halide perovskite nanocrystals (CH3NH3PbX3, X = Br or I) that does not involve the use of dimethylformamide or other polar solvents is presented. The reaction between methylamine and PbX2 salts is conducted in a high-boiling nonpolar solvent (1-octadecene) in the presence of oleylamine and oleic acid as coordinating ligands. The resulting nanocrystals are characterized by high photoluminescence quantum efficiencies of 15-50%, outstanding phase purity and tunable shapes (nanocubes, nanowires, and nanoplatelets). Nanoplatelets spontaneously assemble into micrometer-length wires by face-to-face stacking. In addition, we demonstrate amplified spontaneous emission from thin films of green-emitting CH3NH3PbBr3 nanowires with low pumping thresholds of 3 μJ cm-2. Electronic supplementary information (ESI) available: Materials and methods, additional figures. See DOI: 10.1039/c5nr06890h

  9. Absorbing Software Testing into the Scrum Method

    NASA Astrophysics Data System (ADS)

    Tuomikoski, Janne; Tervonen, Ilkka

    In this paper we study, how to absorb software testing into the Scrum method. We conducted the research as an action research during the years 2007-2008 with three iterations. The result showed that testing can and even should be absorbed to the Scrum method. The testing team was merged into the Scrum teams. The teams can now deliver better working software in a shorter time, because testing keeps track of the progress of the development. Also the team spirit is higher, because the Scrum team members are committed to the same goal. The biggest change from test manager’s point of view was the organized Product Owner Team. Test manager don’t have testing team anymore, and in the future all the testing tasks have to be assigned through the Product Backlog.

  10. All-solid-state hybrid solar cells based on a new organometal halide perovskite sensitizer and one-dimensional TiO2 nanowire arrays

    NASA Astrophysics Data System (ADS)

    Qiu, Jianhang; Qiu, Yongcai; Yan, Keyou; Zhong, Min; Mu, Cheng; Yan, He; Yang, Shihe

    2013-03-01

    A novel organometal halide perovskite (CH3NH3PbI2Br) is synthesized and used as a visible light absorber to sensitize one-dimensional (1D) TiO2 nanowire arrays (NWAs) for all-solid-state hybrid solar cells. It achieved a power conversion efficiency (PCE) of 4.87% and an open circuit voltage (Voc) of 0.82 V, both higher than those of its analogue CH3NH3PbI3.A novel organometal halide perovskite (CH3NH3PbI2Br) is synthesized and used as a visible light absorber to sensitize one-dimensional (1D) TiO2 nanowire arrays (NWAs) for all-solid-state hybrid solar cells. It achieved a power conversion efficiency (PCE) of 4.87% and an open circuit voltage (Voc) of 0.82 V, both higher than those of its analogue CH3NH3PbI3. Electronic supplementary information (ESI) available: Experimental procedures, characterization details, including additional SEM, TEM, EDS, XRD and photovoltaic characteristics of cells based on TiO2 NWAs with different film thickness. See DOI: 10.1039/c3nr00218g

  11. Process for absorbing toxic gas

    SciTech Connect

    Nelson, S.G.

    1988-11-22

    This patent describes a process for removing sulfur oxides, nitrogen oxides, and hydrogen halides from a gas contaminated with same in which the gas is contacted at a temperature below 250/sup 0/C with particulate solid acceptor comprising a mineral support having a coating containing divalent metal oxide, hydroxide, or both, the support being water-moistened particles selected from the group consisting of exfoliated vermiculite, expanded perlite, or a mixture thereof, the improvement which comprises: heating the acceptor before its first use at a temperature of at least about 400/sup 0/C until it is conditioned for the accepting purpose; dampening the conditioned acceptor with water; contacting contaminated gas with the acceptor; and separating resulting cleansed gas from the acceptor.

  12. Countercurrent flow absorber and desorber

    DOEpatents

    Wilkinson, William H.

    1984-01-01

    Countercurrent flow absorber and desorber devices are provided for use in absorption cycle refrigeration systems and thermal boosting systems. The devices have increased residence time and surface area resulting in improved heat and mass transfer characteristics. The apparatuses may be incorporated into open cycle thermal boosting systems in which steam serves both as the refrigerant vapor which is supplied to the absorber section and as the supply of heat to drive the desorber section of the system.

  13. Hyperuniformity of critical absorbing states.

    PubMed

    Hexner, Daniel; Levine, Dov

    2015-03-20

    The properties of the absorbing states of nonequilibrium models belonging to the conserved directed percolation universality class are studied. We find that, at the critical point, the absorbing states are hyperuniform, exhibiting anomalously small density fluctuations. The exponent characterizing the fluctuations is measured numerically, a scaling relation to other known exponents is suggested, and a new correlation length relating to this ordering is proposed. These results may have relevance to photonic band-gap materials. PMID:25839254

  14. Hyperuniformity of Critical Absorbing States

    NASA Astrophysics Data System (ADS)

    Hexner, Daniel; Levine, Dov

    2015-03-01

    The properties of the absorbing states of nonequilibrium models belonging to the conserved directed percolation universality class are studied. We find that, at the critical point, the absorbing states are hyperuniform, exhibiting anomalously small density fluctuations. The exponent characterizing the fluctuations is measured numerically, a scaling relation to other known exponents is suggested, and a new correlation length relating to this ordering is proposed. These results may have relevance to photonic band-gap materials.

  15. Packed Alumina Absorbs Hypergolic Vapors

    NASA Technical Reports Server (NTRS)

    Thomas, J. J.; Mauro, D. M.

    1984-01-01

    Beds of activated alumina effective as filters to remove hypergolic vapors from gas streams. Beds absorb such substances as nitrogen oxides and hydrazines and may also absorb acetylene, ethylene, hydrogen sulfide, benzene, butadiene, butene, styrene, toluene, and xoylene. Bed has no moving parts such as pumps, blowers and mixers. Reliable and energy-conservative. Bed readily adapted to any size from small portable units for use where little vapor release is expected to large stationary units for extensive transfer operations.

  16. Countercurrent flow absorber and desorber

    DOEpatents

    Wilkinson, W.H.

    1984-10-16

    Countercurrent flow absorber and desorber devices are provided for use in absorption cycle refrigeration systems and thermal boosting systems. The devices have increased residence time and surface area resulting in improved heat and mass transfer characteristics. The apparatuses may be incorporated into open cycle thermal boosting systems in which steam serves both as the refrigerant vapor which is supplied to the absorber section and as the supply of heat to drive the desorber section of the system. 9 figs.

  17. A Series of Synthetic Organic Experiments Demonstrating Physical Organic Principles.

    ERIC Educational Resources Information Center

    Sayed, Yousry; And Others

    1989-01-01

    Describes several common synthetic organic transformations involving alkenes, alcohols, alkyl halides, and ketones. Includes concepts on kinetic versus thermodynamic control of reaction, rearrangement of a secondary carbocation to a tertiary cation, and the effect of the size of the base on orientation during elimination. (MVL)

  18. Rare-Earth Tri-Halide Methanol-Adduct Single-Crystal Scintillators for Gamma Ray and Neutron Detection - 8/17/09

    SciTech Connect

    Boatner, Lynn A; Wisniewski, D.; Neal, John S; Bell, Zane W; Ramey, Joanne Oxendine; Kolopus, James A; Chakoumakos, Bryan C; Custelcean, Radu; Wisniewska, Monika; Peña, K. E.

    2009-01-01

    Cerium activated rare-earth tri- halides represent a well-known family of high performance inorganic rare-earth scintillators - including the high-light-yield, high-energy-resolution scintillator, cerium-doped lanthanum tribromide. These hygroscopic inorganic rare-earth halides are currently grown as single crystals from the melt - either by the Bridgman or Czochralski techniques slow and expensive processes that are frequently characterized by severe cracking of the material due to anisotropic thermal stresses and cleavage effects. We have recently discovered a new family of cerium-activated rare-earth metal organic scintillators consisting of tri-halide methanol adducts of cerium and lanthanum namely CeCl3(CH3OH)4 and LaBr3(CH3OH)4:Ce. These methanol-adduct scintillator materials can be grown near room temperature from a methanol solution, and their high solubility is consistent with the application of the rapid solution growth methods that are currently used to grow very large single crystals of potassium dihydrogen phosphate. The structures of these new rare-earth metal-organic scintillating compounds were determined by single crystal x-ray refinements, and their scintillation response to both gamma rays and neutrons, as presented here, was characterized using different excitation sources. Tri-halide methanol-adduct crystals activated with trivalent cerium apparently represent the initial example of a solution-grown rare-earth metal-organic molecular scintillator that is applicable to gamma ray, x-ray, and fast neutron detection.

  19. Femtosecond time-resolved photodissociation dynamics of methyl halide molecules on ultrathin gold films

    PubMed Central

    Vaida, Mihai E; Tchitnga, Robert

    2011-01-01

    Summary The photodissociation of small organic molecules, namely methyl iodide, methyl bromide, and methyl chloride, adsorbed on a metal surface was investigated in real time by means of femtosecond-laser pump–probe mass spectrometry. A weakly interacting gold surface was employed as substrate because the intact adsorption of the methyl halide molecules was desired prior to photoexcitation. The gold surface was prepared as an ultrathin film on Mo(100). The molecular adsorption behavior was characterized by coverage dependent temperature programmed desorption spectroscopy. Submonolayer preparations were irradiated with UV light of 266 nm wavelength and the subsequently emerging methyl fragments were probed by photoionization and mass spectrometric detection. A strong dependence of the excitation mechanism and the light-induced dynamics on the type of molecule was observed. Possible photoexcitation mechanisms included direct photoexcitation to the dissociative A-band of the methyl halide molecules as well as the attachment of surface-emitted electrons with transient negative ion formation and subsequent molecular fragmentation. Both reaction pathways were energetically possible in the case of methyl iodide, yet, no methyl fragments were observed. As a likely explanation, the rapid quenching of the excited states prior to fragmentation is proposed. This quenching mechanism could be prevented by modification of the gold surface through pre-adsorption of iodine atoms. In contrast, the A-band of methyl bromide was not energetically directly accessible through 266 nm excitation. Nevertheless, the one-photon-induced dissociation was observed in the case of methyl bromide. This was interpreted as being due to a considerable energetic down-shift of the electronic A-band states of methyl bromide by about 1.5 eV through interaction with the gold substrate. Finally, for methyl chloride no photofragmentation could be detected at all. PMID:22003467

  20. Artificial Synapses: Organometal Halide Perovskite Artificial Synapses (Adv. Mater. 28/2016).

    PubMed

    Xu, Wentao; Cho, Himchan; Kim, Young-Hoon; Kim, Young-Tae; Wolf, Christoph; Park, Chan-Gyung; Lee, Tae-Woo

    2016-07-01

    A synapse-emulating electronic device based on organometal halide perovskite thin films is described by T.-W. Lee and co-workers on page 5916. The device successfully emulates important characteristics of a biological synapse. This work extends the application of organometal halide perovskites to bioinspired electronic devices, and contributes to the development of neuromorphic electronics. PMID:27442971

  1. Aryl-triazole foldamers incorporating a pyridinium motif for halide anion binding in aqueous media.

    PubMed

    Shang, Jie; Zhao, Wei; Li, Xichen; Wang, Ying; Jiang, Hua

    2016-03-15

    Aryl-triazole oligomers incorporating a pyridinium motif have been synthesized from their pyridine precursors. Anion binding studies show that methylation of the pyridine units can significantly enhance the halide anion affinities of the folded oligomers so that the foldamers are capable of binding halide anions in aqueous solutions. PMID:26933696

  2. 75 FR 5544 - Energy Conservation Program: Energy Conservation Standards for Metal Halide Lamp Fixtures: Public...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-03

    ... public meeting and availability of the Framework Document in the Federal Register (74 FR 69036) for... for Metal Halide Lamp Fixtures: Public Meeting and Availability of the Framework Document AGENCY... conservation standards for certain metal halide lamp fixtures. This document announces that the period...

  3. Thermal battery. [solid metal halide electrolytes with enhanced electrical conductance after a phase transition

    DOEpatents

    Carlsten, R.W.; Nissen, D.A.

    1973-03-06

    The patent describes an improved thermal battery whose novel design eliminates various disadvantages of previous such devices. Its major features include a halide cathode, a solid metal halide electrolyte which has a substantially greater electrical conductance after a phase transition at some temperature, and a means for heating its electrochemical cells to activation temperature.

  4. Method for producing hydrocarbon fuels and fuel gas from heavy polynuclear hydrocarbons by the use of molten metal halide catalysts

    DOEpatents

    Gorin, Everett

    1979-01-01

    In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst in a hydrocracking zone, thereafter separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide and thereafter regenerating the spent molten metal halide by incinerating the spent molten metal halide by combustion of carbon and sulfur compounds in the spent molten metal halide in an incineration zone, the improvement comprising: (a) contacting the heavy feedstocks and hydrogen in the presence of the molten metal halide in the hydrocracking zone at reaction conditions effective to convert from about 60 to about 90 weight percent of the feedstock to lighter hydrocarbon fuels; (b) separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide; (c) contacting the spent molten metal halide with oxygen in a liquid phase gasification zone at a temperature and pressure sufficient to vaporize from about 25 to about 75 weight percent of the spent metal halide, the oxygen being introduced in an amount sufficient to remove from about 60 to about 90 weight percent of the carbon contained in the spent molten metal halide to produce a fuel gas and regenerated metal halide; and (d) incinerating the spent molten metal halide by combusting carbon and sulfur compounds contained therein.

  5. Organizations.

    ERIC Educational Resources Information Center

    Aviation/Space, 1980

    1980-01-01

    This is a list of aerospace organizations and other groups that provides educators with assistance and information in specific areas. Both government and nongovernment organizations are included. (Author/SA)

  6. Methyl Halide Production by Periphyton Mats from the Florida Everglades

    NASA Astrophysics Data System (ADS)

    Raffel, A.; Jones, R. D.; Rice, A. L.; Scully, N. M.

    2012-12-01

    Methyl chloride and methyl bromide are trace gases with both natural and anthropogenic origins. Once generated these gases transport chlorine and bromine into the stratosphere, where they play an important role in atmospheric chemistry by participating in ozone depleting catalytic cycles. Coastal wetlands are one location where methyl halide emissions have been proposed to be elevated due to high primary production and ionic halogens. This region also provides a unique study environment due to salt water intrusions which occur during storm or low marsh water level-high tide events. The purpose of this research was to determine how varying concentrations of salinity affect methyl halide production originating from periphyton mats within the Florida Everglades. Florida Everglades periphyton (25 g/L) were exposed to continuous 12 hour dark/light cycles in varying concentrations of salt water (0, 0.1, 1.0, and 10‰). All water samples were analyzed to determine the concentration and production rate of methyl chloride and methyl bromide in periphyton samples using a gas chromatograph coupled with an electron capture detector. The concentration of methyl chloride increased by approximately 3.4 and 60 pM over a 0 to 72 hour range for 1‰ and 10 ‰ treatments respectively, and reached a steady state concentration after 24 hours. There was no significant production of methyl bromide for all treatments. These studies will be used to gain a better understanding of methyl halide production from periphyton mats in simulated natural conditions. This research was supported by the National Science Foundation Chemical Oceanography Program Award No. 1029710.

  7. New generation of medium wattage metal halide lamps and spectroscopic tools for their diagnostics

    NASA Astrophysics Data System (ADS)

    Dunaevsky, A.; Tu, J.; Gibson, R.; Steere, T.; Graham, K.; van der Eyden, J.

    2010-11-01

    A new generation of ceramic metal halide high intensity discharge (HID) lamps has achieved high efficiencies by implementing new design concepts. The shape of the ceramic burner is optimized to withstand high temperatures with minimal thermal stress. Corrosion processes with the ceramic walls are slowed down via adoption of non-aggressive metal halide chemistry. Light losses over life due to tungsten deposition on the walls are minimized by maintaining a self-cleaning chemical process, known as tungsten cycle. All these advancements have made the new ceramic metal halide lamps comparable to high pressure sodium lamps for luminous efficacy, life, and maintenance while providing white light with high color rendering. Direct replacement of quartz metal halide lamps and systems results in the energy saving from 18 up to 50%. High resolution spectroscopy remains the major non-destructive tool for the ceramic metal halide lamps. Approaches to reliable measurements of relative partial pressures of the arc species are discussed.

  8. Carbon Absorber Retrofit Equipment (CARE)

    SciTech Connect

    Klein, Eric

    2015-12-23

    During Project DE-FE0007528, CARE (Carbon Absorber Retrofit Equipment), Neumann Systems Group (NSG) designed, installed and tested a 0.5MW NeuStream® carbon dioxide (CO2) capture system using the patented NeuStream® absorber equipment and concentrated (6 molal) piperazine (PZ) as the solvent at Colorado Springs Utilities’ (CSU’s) Martin Drake pulverized coal (PC) power plant. The 36 month project included design, build and test phases. The 0.5MW NeuStream® CO2 capture system was successfully tested on flue gas from both coal and natural gas combustion sources and was shown to meet project objectives. Ninety percent CO2 removal was achieved with greater than 95% CO2product purity. The absorbers tested support a 90% reduction in absorber volume compared to packed towers and with an absorber parasitic power of less than 1% when configured for operation with a 550MW coal plant. The preliminary techno-economic analysis (TEA) performed by the Energy and Environmental Research Center (EERC) predicted an over-the-fence cost of $25.73/tonne of CO2 captured from a sub-critical PC plant.

  9. Mushroom plasmonic metamaterial infrared absorbers

    NASA Astrophysics Data System (ADS)

    Ogawa, Shinpei; Fujisawa, Daisuke; Hata, Hisatoshi; Uetsuki, Mitsuharu; Misaki, Koji; Kimata, Masafumi

    2015-01-01

    There has been a considerable amount of interest in the development of various types of electromagnetic wave absorbers for use in different wavelength ranges. In particular, infrared (IR) absorbers with wavelength selectivity can be applied to advanced uncooled IR sensors, which would be capable of identifying objects through their radiation spectrum. In the present study, mushroom plasmonic metamaterial absorbers (MPMAs) for the IR wavelength region were designed and fabricated. The MPMAs consist of a periodic array of thin metal micropatches connected to a thin metal plate with narrow silicon (Si) posts. A Si post height of 200 nm was achieved by isotropic XeF2 etching of a thin Si layer sandwiched between metal plates. This fabrication procedure is relatively simple and is consistent with complementary metal oxide semiconductor technology. The absorption spectra of the fabricated MPMAs were experimentally measured. In addition, theoretical calculations of their absorption properties were conducted using rigorous coupled wave analysis. Both the calculated and measured absorbance results demonstrated that these MPMAs can realize strong selective absorption at wavelengths beyond the period of the array by varying the micropatch width. Absorbance values greater than 90% were achieved. Dual- or single-mode absorption can also be selected by varying the width of the Si posts. Pixel structures using such MPMAs could be used as high responsivity, high resolution and fast uncooled IR sensors.

  10. Additive manufacturing of RF absorbers

    NASA Astrophysics Data System (ADS)

    Mills, Matthew S.

    The ability of additive manufacturing techniques to fabricate integrated electromagnetic absorbers tuned for specific radio frequency bands within structural composites allows for unique combinations of mechanical and electromagnetic properties. These composites and films can be used for RF shielding of sensitive electromagnetic components through in-plane and out-of-plane RF absorption. Structural composites are a common building block of many commercial platforms. These platforms may be placed in situations in which there is a need for embedded RF absorbing properties along with structural properties. Instead of adding radar absorbing treatments to the external surface of existing structures, which adds increased size, weight and cost; it could prove to be advantageous to integrate the microwave absorbing properties directly into the composite during the fabrication process. In this thesis, a method based on additive manufacturing techniques of composites structures with prescribed electromagnetic loss, within the frequency range 1 to 26GHz, is presented. This method utilizes screen printing and nScrypt micro dispensing to pattern a carbon based ink onto low loss substrates. The materials chosen for this study will be presented, and the fabrication technique that these materials went through to create RF absorbing structures will be described. The calibration methods used, the modeling of the RF structures, and the applications in which this technology can be utilized will also be presented.

  11. Mushroom plasmonic metamaterial infrared absorbers

    SciTech Connect

    Ogawa, Shinpei Fujisawa, Daisuke; Hata, Hisatoshi; Uetsuki, Mitsuharu; Misaki, Koji; Kimata, Masafumi

    2015-01-26

    There has been a considerable amount of interest in the development of various types of electromagnetic wave absorbers for use in different wavelength ranges. In particular, infrared (IR) absorbers with wavelength selectivity can be applied to advanced uncooled IR sensors, which would be capable of identifying objects through their radiation spectrum. In the present study, mushroom plasmonic metamaterial absorbers (MPMAs) for the IR wavelength region were designed and fabricated. The MPMAs consist of a periodic array of thin metal micropatches connected to a thin metal plate with narrow silicon (Si) posts. A Si post height of 200 nm was achieved by isotropic XeF{sub 2} etching of a thin Si layer sandwiched between metal plates. This fabrication procedure is relatively simple and is consistent with complementary metal oxide semiconductor technology. The absorption spectra of the fabricated MPMAs were experimentally measured. In addition, theoretical calculations of their absorption properties were conducted using rigorous coupled wave analysis. Both the calculated and measured absorbance results demonstrated that these MPMAs can realize strong selective absorption at wavelengths beyond the period of the array by varying the micropatch width. Absorbance values greater than 90% were achieved. Dual- or single-mode absorption can also be selected by varying the width of the Si posts. Pixel structures using such MPMAs could be used as high responsivity, high resolution and fast uncooled IR sensors.

  12. Nonventing, Regenerable, Lightweight Heat Absorber

    NASA Technical Reports Server (NTRS)

    Izenson, Michael G.; Chen, Weibo

    2008-01-01

    A lightweight, regenerable heat absorber (RHA), developed for rejecting metabolic heat from a space suit, may also be useful on Earth for short-term cooling of heavy protective garments. Unlike prior space-suit-cooling systems, a system that includes this RHA does not vent water. The closed system contains water reservoirs, tubes through which water is circulated to absorb heat, an evaporator, and an absorber/radiator. The radiator includes a solution of LiCl contained in a porous material in titanium tubes. The evaporator cools water that circulates through a liquid-cooled garment. Water vapor produced in the evaporator enters the radiator tubes where it is absorbed into the LiCl solution, releasing heat. Much of the heat of absorption is rejected to the environment via the radiator. After use, the RHA is regenerated by heating it to a temperature of 100 C for about 2 hours to drive the absorbed water back to the evaporator. A system including a prototype of the RHA was found to be capable of maintaining a temperature of 20 C while removing heat at a rate of 200 W for 6 hours.

  13. Absorbing-state phase transitions with extremal dynamics

    NASA Astrophysics Data System (ADS)

    Dickman, Ronald; Garcia, Guilherme J. M.

    2005-06-01

    Extremal dynamics represents a path to self-organized criticality in which the order parameter is tuned to a value of zero. The order parameter is associated with a phase transition to an absorbing state. Given a process that exhibits a phase transition to an absorbing state, we define an “extremal absorbing” process, providing the link to the associated extremal (nonabsorbing) process. Stationary properties of the latter correspond to those at the absorbing-state phase transition in the former. Studying the absorbing version of an extremal dynamics model allows to determine certain critical exponents that are not otherwise accessible. In the case of the Bak-Sneppen (BS) model, the absorbing version is closely related to the “ f -avalanche” introduced by Paczuski, Maslov, and Bak [Phys. Rev. E 53, 414 (1996)], or, in spreading simulations to the “BS branching process” also studied by these authors. The corresponding nonextremal process belongs to the directed percolation universality class. We revisit the absorbing BS model, obtaining refined estimates for the threshold and critical exponents in one dimension. We also study an extremal version of the usual contact process, using mean-field theory and simulation. The extremal condition slows the spread of activity and modifies the critical behavior radically, defining an “extremal directed percolation” universality class of absorbing-state phase transitions. Asymmetric updating is a relevant perturbation for this class, even though it is irrelevant for the corresponding nonextremal class.

  14. Metal-halide mixtures for latent heat energy storage

    NASA Technical Reports Server (NTRS)

    Chen, K.; Manvi, R.

    1981-01-01

    Some candidates for alkali metal and alkali halide mixtures suitable for thermal energy storage at temperatures 600 C are identified. A solar thermal system application which offer advantages such as precipitation of salt crystals away from heat transfer surfaces, increased thermal conductivity of phase change materials, corrosion inhibition, and a constant monotectic temperature, independent of mixture concentrations. By using the lighters, metal rich phase as a heat transfer medium and the denser, salt rich phase as a phase change material for latent heat storage, undesirable solidification on the heat transfer surface may be prevented, is presented.

  15. Volatile species in halide-activated-diffusion coating packs

    NASA Technical Reports Server (NTRS)

    Bianco, Robert; Rapp, Robert A.; Jacobson, Nathan S.

    1992-01-01

    An atmospheric pressure sampling mass spectrometer was used to identify the vapor species generated in a halide-activated cementation pack. Pack powder mixtures containing a Cr-Al binary masteralloy powder, an NH4Cl activator salt, and either ZrO2 or Y2O3 (or neither) were analyzed at 1000 C. Both the equilibrium calculations for the pack and mass spectrometer results indicated that volatile AlCl(x) and CrCl(y) species were generated by the pack powder mixture; in packs containing the reactive element oxide, volatile ZrCl(z) and YCl(w) species were formed by the conversion of their oxide sources.

  16. Silylaryl Halides Can Replace Triflates as Aryne Precursors.

    PubMed

    Mesgar, Milad; Daugulis, Olafs

    2016-08-01

    Silylaryl bromides and iodides can be prepared in one step from commercially available starting materials. Arynes can be generated from these compounds under conditions nearly identical to those employed for silylaryl triflates. Three distinct transformations, ortho-arylation of N-tritylanilines, intermolecular addition of arynes to amides, and reaction of ureas with arynes, were shown to be successful for the new aryne precursors. The main advantage of silylaryl halides relative to silyl aryl triflates is their one-step preparation from commercially available starting materials. PMID:27415183

  17. Heavy ion passive dosimetry with silver halide single crystals

    NASA Technical Reports Server (NTRS)

    Childs, C. B.; Parnell, T. A.

    1972-01-01

    A method of detecting radiation damage tracks due to heavy particles in large single crystals of the silver halides is described. The tracks, when made visible with a simple electrical apparatus, appear similar to tracks in emulsions. The properties of the crystals, the technique of printing out the tracks, and evidence concerning the threshold energy for registering particles indicates that this method may find application in heavy ion dosimetry. The method has been found to be sensitive to stopping He nuclei and relativistic M group cosmic rays. Some impurities strongly influence the printout of the tracks, and the effects of these impurities are discussed.

  18. A new mechanism for radiation damage processes in alkali halides

    NASA Astrophysics Data System (ADS)

    Dubinko, V. I.; Turkin, A. A.; Vainshtein, D. I.; den Hartog, H. W.

    1999-12-01

    We present a theory of radiation damage formation in alkali halides based on a new mechanism of dislocation climb, which involves the production of VF centers (self-trapped hole neighboring a cation vacancy) as a result of the absorption of H centers of dislocation lines. We consider the evolution of all experimentally observed extended defects: metal colloids, gas bubbles, and vacancy voids. Voids are shown to arise and grow large due to the reaction between F and VF centers at the surface of halogen bubbles. Voids can ignite a back reaction between the radiolytic products resulting in decomposition of the irradiated material.

  19. Interfacial tension in immiscible mixtures of alkali halides.

    PubMed

    Lockett, Vera; Rukavishnikova, Irina V; Stepanov, Victor P; Tkachev, Nikolai K

    2010-02-01

    The interfacial tension of the liquid-phase interface in seven immiscible reciprocal ternary mixtures of lithium fluoride with the following alkali halides: CsCl, KBr, RbBr, CsBr, KI, RbI, and CsI was measured using the cylinder weighing method over a wide temperature range. It was shown that for all mixtures the interfacial tension gradually decreases with growing temperature. The interfacial tension of the reciprocal ternary mixtures at a given temperature increases both with the alkali cation radius (K(+) < Rb(+) < Cs(+)) and with the radius of the halogen anion (Cl(-) < Br(-) < I(-)). PMID:20094678

  20. Thermal conductivity of halide solid solutions: measurement and prediction.

    PubMed

    Gheribi, Aïmen E; Poncsák, Sándor; St-Pierre, Rémi; Kiss, László I; Chartrand, Patrice

    2014-09-14

    The composition dependence of the lattice thermal conductivity in NaCl-KCl solid solutions has been measured as a function of composition and temperature. Samples with systematically varied compositions were prepared and the laser flash technique was used to determine the thermal diffusivity from 373 K to 823 K. A theoretical model, based on the Debye approximation of phonon density of state (which contains no adjustable parameters) was used to predict the thermal conductivity of both stoichiometric compounds and fully disordered solid solutions. The predictions obtained with the model agree very well with our measurement. A general method for predicting the thermal conductivity of different halide systems is discussed. PMID:25217938

  1. Ferroelectricity and Rashba-type band splittings in metal halides

    NASA Astrophysics Data System (ADS)

    Kim, Minsung; Im, Jino; Freeman, Arthur; Ihm, Jisoon; Jin, Hosub

    2014-03-01

    In this study, we investigate Rashba-type band splittings in metal halides. We use a minimal tight-binding model and first principles calculations based on density functional theory to understand the electronic structures of the materials. We find that different types of Rashba bands occur in the conduction and valence band edges in terms of the angular momentum textures. Also, the characteristics of the band splittings will be discussed in connection with the ferroelectric property. Department of Physics and Astronomy, Seoul National University, Seoul 151-747, Korea.

  2. The Importance of Perovskite Pore Filling in Organometal Mixed Halide Sensitized TiO2-Based Solar Cells.

    PubMed

    Leijtens, Tomas; Lauber, Beat; Eperon, Giles E; Stranks, Samuel D; Snaith, Henry J

    2014-04-01

    Emerging from the field of dye-sensitized solar cells, organometal halide perovskite-based solar cells have recently attracted considerable attention. In these devices, the perovskite light absorbers can also be used as charge transporting materials, changing the requirements for efficient device architectures. The perovskite deposition can vary from merely sensitizing the TiO2 electron transporting scaffold as an endowment of small nanoparticles, to completely filling the pores where it acts as both light absorber and hole transporting material in one. By decreasing the TiO2 scaffold layer thickness, we change the solar cell architecture from perovskite-sensitized to completely perovskite-filled. We find that the latter case leads to improvements in device performance because higher electron densities can be sustained in the TiO2, improving electron transport rates and photovoltage. Importantly, the primary recombination pathway between the TiO2 and the hole transporting material is blocked by the perovskite itself. This understanding helps to rationalize the high voltages attainable on mesoporous TiO2-based perovskite solar cells. PMID:26274455

  3. Adaptive inertial shock-absorber

    NASA Astrophysics Data System (ADS)

    Faraj, Rami; Holnicki-Szulc, Jan; Knap, Lech; Seńko, Jarosław

    2016-03-01

    This paper introduces and discusses a new concept of impact absorption by means of impact energy management and storage in dedicated rotating inertial discs. The effectiveness of the concept is demonstrated in a selected case-study involving spinning management, a recently developed novel impact-absorber. A specific control technique performed on this device is demonstrated to be the main source of significant improvement in the overall efficiency of impact damping process. The influence of various parameters on the performance of the shock-absorber is investigated. Design and manufacturing challenges and directions of further research are formulated.

  4. Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects.

    PubMed

    Liu, Yuanyue; Xiao, Hai; Goddard, William A

    2016-05-11

    Two-dimensional (2D) halide perovskites are emerging as promising candidates for nanoelectronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g., transition metal dichalcogenides MX2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gap states. We show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX2. The donors tend to have high formation energies and the harmful defects are difficult to form at a low halide chemical potential. Thus, we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them. PMID:27100910

  5. Oxide Film Aging on Alloy 22 in Halide Containing Solutions

    SciTech Connect

    Rodriguez, Martin A.; Carranza, Ricardo M.; Rebak, Raul B.

    2007-07-01

    Passive and corrosion behaviors of Alloy 22 in chloride and fluoride containing solutions, changing the heat treatment of the alloy, the halide concentration and the pH of the solutions at 90 deg. C, was investigated. The study was implemented using electrochemical techniques, which included open circuit potential monitoring over time, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements carried out at open circuit and at passivity potentials. Corrosion rates obtained by EIS measurements after 24 h immersion in naturally aerated solutions were below 0.5 {mu}m/year. The corrosion rates were practically independent of solution pH, alloy heat treatment and halide ion nature and concentration. EIS low frequency resistance values increased with applied potential in the passive domain and with polarization time in pH 6 - 1 M NaCl at 90 deg. C. This effect was attributed to an increase in the oxide film thickness and oxide film aging. High frequency capacitance measurements indicated that passive oxide on Alloy 22 presented a double n-type/p-type semiconductor behavior in the passive potential range. (authors)

  6. Tunable Near-Infrared Luminescence in Tin Halide Perovskite Devices.

    PubMed

    Lai, May L; Tay, Timothy Y S; Sadhanala, Aditya; Dutton, Siân E; Li, Guangru; Friend, Richard H; Tan, Zhi-Kuang

    2016-07-21

    Infrared emitters are reasonably rare in solution-processed materials. Recently, research into hybrid organo-lead halide perovskite, originally popular in photovoltaics,1-3 has gained traction in light-emitting diodes (LED) due to their low-cost solution processing and good performance.4-9 The lead-based electroluminescent materials show strong colorful emission in the visible region, but lack emissive variants further in the infrared. The concerns with the toxicity of lead may, additionally, limit their wide-scale applications. Here, we demonstrate tunable near-infrared electroluminescence from a lead-free organo-tin halide perovskite, using an ITO/PEDOT:PSS/CH3NH3Sn(Br1-xIx)3/F8/Ca/Ag device architecture. In our tin iodide (CH3NH3SnI3) LEDs, we achieved a 945 nm near-infrared emission with a radiance of 3.4 W sr(-1) m(-2) and a maximum external quantum efficiency of 0.72%, comparable with earlier lead-based devices. Increasing the bromide content in these tin perovskite devices widens the semiconductor bandgap and leads to shorter wavelength emissions, tunable down to 667 nm. These near-infrared LEDs could find useful applications in a range of optical communication, sensing and medical device applications. PMID:27336412

  7. Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects

    NASA Astrophysics Data System (ADS)

    Liu, Yuanyue; Xiao, Hai; Goddard, William A., III

    2016-05-01

    Two-dimensional (2D) halide perovskites are emerging as promising candidates for nano-electronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g. transition metal dichalcogenides MX2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation, one can change the synthesis conditions to convert a line defect (edge or grain boundary) from electron acceptor to inactive site without deep gap states. We show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX2. The donors tend to have high formation energies, and the harmful defects are difficult to form at a low halide chemical potential. Thus we unveil unique properties of defects in 2D perovskites and suggest practical routes to improve them.

  8. Subsurface Ectomycorrhizal Fungi: A New Source of Atmospheric Methyl Halides?

    NASA Astrophysics Data System (ADS)

    Treseder, K. K.; Redeker, K. R.; Allen, M. F.

    2001-12-01

    Incomplete source budgets for methyl halides---compounds that release inorganic halogen radicals which, in turn, catalyze atmospheric ozone depletion---limit our abilities to predict the fate of the stratospheric ozone layer. We tested the ability ectomycorrhizal fungi to produce methyl bromide and methyl iodide. These fungi are abundant in temperate forests, where they colonize tree roots and provide nutrients to their symbiotic plants in exchange for carbon compounds. The observed range of emissions from seven different species in culture is 0.001- to 100-μ g g-1 fungi d-1 for methyl bromide, and 0.5- to 500-μ g g-1 fungi d-1 for methyl iodide. While methyl chloride was not specifically tested, large emissions were observed from several species with little to no emissions observed from others. Further analyses of the effects of substrate concentration, headspace concentration, and temperature were performed on the species Cenococcum geophilum, one of the most abundant ectomycorrhizal fungi. Our results suggest that subsurface fungal emissions may be a significant global source of methyl halides.

  9. Photocrystallographic Observation of Halide-Bridged Intermediates in Halogen Photoeliminations

    PubMed Central

    2015-01-01

    Polynuclear transition metal complexes, which frequently constitute the active sites of both biological and chemical catalysts, provide access to unique chemical transformations that are derived from metal–metal cooperation. Reductive elimination via ligand-bridged binuclear intermediates from bimetallic cores is one mechanism by which metals may cooperate during catalysis. We have established families of Rh2 complexes that participate in HX-splitting photocatalysis in which metal–metal cooperation is credited with the ability to achieve multielectron photochemical reactions in preference to single-electron transformations. Nanosecond-resolved transient absorption spectroscopy, steady-state photocrystallography, and computational modeling have allowed direct observation and characterization of Cl-bridged intermediates (intramolecular analogues of classical ligand-bridged intermediates in binuclear eliminations) in halogen elimination reactions. On the basis of these observations, a new class of Rh2 complexes, supported by CO ligands, has been prepared, allowing for the isolation and independent characterization of the proposed halide-bridged intermediates. Direct observation of halide-bridged structures establishes binuclear reductive elimination as a viable mechanism for photogenerating energetic bonds. PMID:25264809

  10. A new polarizable force field for alkali and halide ions

    SciTech Connect

    Kiss, Péter T.; Baranyai, András

    2014-09-21

    We developed transferable potentials for alkali and halide ions which are consistent with our recent model of water [P. T. Kiss and A. Baranyai, J. Chem. Phys. 138, 204507 (2013)]. Following the approach used for the water potential, we applied Gaussian charge distributions, exponential repulsion, and r{sup −6} attraction. One of the two charges of the ions is fixed to the center of the particle, while the other is connected to this charge by a harmonic spring to express polarization. Polarizability is taken from quantum chemical calculations. The repulsion between different species is expressed by the combining rule of Kong [J. Chem. Phys. 59, 2464 (1972)]. Our primary target was the hydration free energy of ions which is correct within the error of calculations. We calculated water-ion clusters up to 6 water molecules, and, as a crosscheck, we determined the density and internal energy of alkali-halide crystals at ambient conditions with acceptable accuracy. The structure of hydrated ions was also discussed.

  11. A new polarizable force field for alkali and halide ions

    NASA Astrophysics Data System (ADS)

    Kiss, Péter T.; Baranyai, András

    2014-09-01

    We developed transferable potentials for alkali and halide ions which are consistent with our recent model of water [P. T. Kiss and A. Baranyai, J. Chem. Phys. 138, 204507 (2013)]. Following the approach used for the water potential, we applied Gaussian charge distributions, exponential repulsion, and r-6 attraction. One of the two charges of the ions is fixed to the center of the particle, while the other is connected to this charge by a harmonic spring to express polarization. Polarizability is taken from quantum chemical calculations. The repulsion between different species is expressed by the combining rule of Kong [J. Chem. Phys. 59, 2464 (1972)]. Our primary target was the hydration free energy of ions which is correct within the error of calculations. We calculated water-ion clusters up to 6 water molecules, and, as a crosscheck, we determined the density and internal energy of alkali-halide crystals at ambient conditions with acceptable accuracy. The structure of hydrated ions was also discussed.

  12. Counterflow absorber for an absorption refrigeration system

    DOEpatents

    Reimann, Robert C.

    1984-01-01

    An air-cooled, vertical tube absorber for an absorption refrigeration system is disclosed. Strong absorbent solution is supplied to the top of the absorber and refrigerant vapor is supplied to the bottom of the absorber to create a direct counterflow of refrigerant vapor and absorbent solution in the absorber. The refrigeration system is designed so that the volume flow rate of refrigerant vapor in the tubes of the absorber is sufficient to create a substantially direct counterflow along the entire length of each tube in the absorber. This provides several advantages for the absorber such as higher efficiency and improved heat transfer characteristics, and allows improved purging of non-condensibles from the absorber.

  13. Oil and fat absorbing polymers

    NASA Technical Reports Server (NTRS)

    Marsh, H. E., Jr. (Inventor)

    1977-01-01

    A method is described for forming a solid network polymer having a minimal amount of crosslinking for use in absorbing fats and oils. The polymer remains solid at a swelling ratio in oil or fat of at least ten and provides an oil absorption greater than 900 weight percent.

  14. Organics.

    ERIC Educational Resources Information Center

    Chian, Edward S. K.; DeWalle, Foppe B.

    1978-01-01

    Presents water analysis literature for 1978. This review is concerned with organics, and it covers: (1) detergents and surfactants; (2) aliphatic and aromatic hydrocarbons; (3) pesticides and chlorinated hydrocarbons; and (4) naturally occurring organics. A list of 208 references is also presented. (HM)

  15. Organizers.

    ERIC Educational Resources Information Center

    Callison, Daniel

    2000-01-01

    Focuses on "organizers," tools or techniques that provide identification and classification along with possible relationships or connections among ideas, concepts, and issues. Discusses David Ausubel's research and ideas concerning advance organizers; the implications of Ausubel's theory to curriculum and teaching; "webbing," a specific…

  16. Formability of ABX3 (X = F, Cl, Br, I) halide perovskites.

    PubMed

    Li, Chonghea; Lu, Xionggang; Ding, Weizhong; Feng, Liming; Gao, Yonghui; Guo, Ziming

    2008-12-01

    In this study a total of 186 complex halide systems were collected; the formabilities of ABX3 (X = F, Cl, Br and I) halide perovskites were investigated using the empirical structure map, which was constructed by Goldschmidt's tolerance factor and the octahedral factor. A model for halide perovskite formability was built up. In this model obtained, for all 186 complex halides systems, only one system (CsF-MnF2) without perovskite structure and six systems (RbF-PbF2, CsF-BeF2, KCl-FeCl2, TlI-MnI2, RbI-SnI2, TlI-PbI2) with perovskite structure were wrongly classified, so its predicting accuracy reaches 96%. It is also indicated that both the tolerance factor and the octahedral factor are a necessary but not sufficient condition for ABX3 halide perovskite formability, and a lowest limit of the octahedral factor exists for halide perovskite formation. This result is consistent with our previous report for ABO3 oxide perovskite, and may be helpful to design novel halide materials with the perovskite structure. PMID:19029699

  17. Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution.

    PubMed

    Doane, Tennyson L; Ryan, Kayla L; Pathade, Laxmikant; Cruz, Kevin J; Zang, Huidong; Cotlet, Mircea; Maye, Mathew M

    2016-06-28

    The ability of cesium lead halide (CsPbX3; X = Cl(-), Br(-), I(-)) perovskite nanoparticles (P-NPs) to participate in halide exchange reactions, to catalyze Finkelstein organohalide substitution reactions, and to colorimetrically monitor chemical reactions and detect anions in real time is described. With the use of tetraoctylammonium halide salts as a starting point, halide exchange with the P-NPs was performed to calibrate reactivity, stability, and extent of ion exchange. The exchange of CsPbI3 with Cl(-) or Br(-) causes a significant blue-shift in absorption and photoluminescence, whereas reacting I(-) with CsPbBr3 causes a red-shift of similar magnitudes. With the high local halide concentrations and the facile nature of halide exchange in mind, we then explored the ability of P-NPs to catalyze organohalide exchange in Finkelstein like reactions. Results indicate that the P-NPs serve as excellent halide reservoirs for substitution of organohalides in nonpolar media, leading to not only different organohalide products, but also a complementary color change over the course of the reaction, which can be used to monitor kinetics in a precise manner. The merits of using P-NP as spectrochemical probes for real time assaying is then expanded to other anions which can react with, or result in unique, classes of perovskites. PMID:27149396

  18. [Study of new blended chemical absorbents to absorb CO2].

    PubMed

    Wang, Jin-Lian; Fang, Meng-Xiang; Yan, Shui-Ping; Luo, Zhong-Yang; Cen, Ke-Fa

    2007-11-01

    Three kinds of blended absorbents were investigated on bench-scale experimental bench according to absorption rate and regeneration grade to select a reasonable additive concentration. The results show that, among methyldiethanolamine (MDEA) and piperazine (PZ) mixtures, comparing MDEA : PZ = 1 : 0.4 (m : m) with MDEA : PZ = 1 : 0.2 (m : m), the absorption rate is increased by about 70% at 0.2 mol x mol(-1). When regeneration lasting for 40 min, regeneration grade of blended absorbents with PZ concentration of 0.2, 0.4, and 0.8 is decreased to 83.06%, 77.77% and 76.67% respectively while 91.04% for PZ concentration of 0. MDEA : PZ = 1 : 0.4(m : m) is a suitable ratio for MDEA/PZ mixtures as absorption and regeneration properties of the blended absorbents are all improved. The aqueous blends with 10% primary amines and 2% tertiary amines could keep high CO2 absorption rate, and lower regeneration energy consumption. Adding 2% 2-Amino-2-methyl-1-propanol (AMP) to 10% diethanolamine (DEA), the blended amine solvents have an advantage in absorption and regeneration properties over other DEA/AMP mixtures. Blended solvents, which consist of a mixture of primary amines with a small amount of tertiary amines, have the highest absorption rate among the three. And mixed absorbents of secondary amines and a small amount of sterically hindered amines have the best regeneration property. To combine absorption and regeneration properties, blends with medium activator addition to tertiary amines are competitive. PMID:18290495

  19. Metal Halide Solid-State Surface Treatment for High Efficiency PbS and PbSe QD Solar Cells

    SciTech Connect

    Crisp, R. W.; Kroupa, D. M.; Marshall, A. R.; Miller, E. M.; Zhang, J.; Beard, M. C.; Luther, J. M.

    2015-04-24

    We developed a layer-by-layer method of preparing PbE (E = S or Se) quantum dot (QD) solar cells using metal halide (PbI2, PbCl2, CdI2, or CdCl2) salts dissolved in dimethylformamide to displace oleate surface ligands and form conductive QD solids. The resulting QD solids have a significant reduction in the carbon content compared to films treated with thiols and organic halides. We find that the PbI2 treatment is the most successful in removing alkyl surface ligands and also replaces most surface bound Cl- with I-. The treatment protocol results in PbS QD films exhibiting a deeper work function and band positions than other ligand exchanges reported previously. The method developed here produces solar cells that perform well even at film thicknesses approaching a micron, indicating improved carrier transport in the QD films. We demonstrate QD solar cells based on PbI2 with power conversion efficiencies above 7%.

  20. Tunable room-temperature spin-selective optical Stark effect in solution-processed layered halide perovskites

    PubMed Central

    Giovanni, David; Chong, Wee Kiang; Dewi, Herlina Arianita; Thirumal, Krishnamoorthy; Neogi, Ishita; Ramesh, Ramamoorthy; Mhaisalkar, Subodh; Mathews, Nripan; Sum, Tze Chien

    2016-01-01

    Ultrafast spin manipulation for opto–spin logic applications requires material systems that have strong spin-selective light-matter interaction. Conventional inorganic semiconductor nanostructures [for example, epitaxial II to VI quantum dots and III to V multiple quantum wells (MQWs)] are considered forerunners but encounter challenges such as lattice matching and cryogenic cooling requirements. Two-dimensional halide perovskite semiconductors, combining intrinsic tunable MQW structures and large oscillator strengths with facile solution processability, can offer breakthroughs in this area. We demonstrate novel room-temperature, strong ultrafast spin-selective optical Stark effect in solution-processed (C6H4FC2H4NH3)2PbI4 perovskite thin films. Exciton spin states are selectively tuned by ~6.3 meV using circularly polarized optical pulses without any external photonic cavity (that is, corresponding to a Rabi energy of ~55 meV and equivalent to applying a 70 T magnetic field), which is much larger than any conventional system. The facile halide and organic replacement in these perovskites affords control of the dielectric confinement and thus presents a straightforward strategy for tuning light-matter coupling strength. PMID:27386583

  1. Tunable room-temperature spin-selective optical Stark effect in solution-processed layered halide perovskites.

    PubMed

    Giovanni, David; Chong, Wee Kiang; Dewi, Herlina Arianita; Thirumal, Krishnamoorthy; Neogi, Ishita; Ramesh, Ramamoorthy; Mhaisalkar, Subodh; Mathews, Nripan; Sum, Tze Chien

    2016-06-01

    Ultrafast spin manipulation for opto-spin logic applications requires material systems that have strong spin-selective light-matter interaction. Conventional inorganic semiconductor nanostructures [for example, epitaxial II to VI quantum dots and III to V multiple quantum wells (MQWs)] are considered forerunners but encounter challenges such as lattice matching and cryogenic cooling requirements. Two-dimensional halide perovskite semiconductors, combining intrinsic tunable MQW structures and large oscillator strengths with facile solution processability, can offer breakthroughs in this area. We demonstrate novel room-temperature, strong ultrafast spin-selective optical Stark effect in solution-processed (C6H4FC2H4NH3)2PbI4 perovskite thin films. Exciton spin states are selectively tuned by ~6.3 meV using circularly polarized optical pulses without any external photonic cavity (that is, corresponding to a Rabi energy of ~55 meV and equivalent to applying a 70 T magnetic field), which is much larger than any conventional system. The facile halide and organic replacement in these perovskites affords control of the dielectric confinement and thus presents a straightforward strategy for tuning light-matter coupling strength. PMID:27386583

  2. Metal Halide Solid-State Surface Treatment for High Efficiency PbS and PbSe QD Solar Cells

    DOE PAGESBeta

    Crisp, R. W.; Kroupa, D. M.; Marshall, A. R.; Miller, E. M.; Zhang, J.; Beard, M. C.; Luther, J. M.

    2015-04-24

    We developed a layer-by-layer method of preparing PbE (E = S or Se) quantum dot (QD) solar cells using metal halide (PbI2, PbCl2, CdI2, or CdCl2) salts dissolved in dimethylformamide to displace oleate surface ligands and form conductive QD solids. The resulting QD solids have a significant reduction in the carbon content compared to films treated with thiols and organic halides. We find that the PbI2 treatment is the most successful in removing alkyl surface ligands and also replaces most surface bound Cl- with I-. The treatment protocol results in PbS QD films exhibiting a deeper work function and bandmore » positions than other ligand exchanges reported previously. The method developed here produces solar cells that perform well even at film thicknesses approaching a micron, indicating improved carrier transport in the QD films. We demonstrate QD solar cells based on PbI2 with power conversion efficiencies above 7%.« less

  3. Mesoscopic photosystems for solar light harvesting and conversion: facile and reversible transformation of metal-halide perovskites.

    PubMed

    Harms, Hauke Arne; Tétreault, Nicolas; Pellet, Norman; Bensimon, Michaël; Grätzel, Michael

    2014-01-01

    Recently, hybrid organic-inorganic metal halide perovskites have gained prominence as potent light harvesters in thin film solid-state photovoltaics. In particular the solar-to-electric power conversion efficiency (PCE) of devices using CH(3)NH(3)PbI(3) as sensitizer has increased from 3 to 20.1% within only a few years. This key material can be prepared by solution processing from PbI(2) and CH(3)NH(3)I in one step or by sequential deposition. In the latter case an electron capturing support such as TiO(2) is first covered with PbI(2), which upon exposure to a CH(3)NH(3)I solution is converted to the perovskite. Here we apply for the first time quartz crystal microbalance (QCMD) measurements in conjunction with X-ray diffraction and scanning electron microscopy to analyse the dynamics of the conversion of PbI(2) to CH(3)NH(3)PbI(3). Employing 200 nm thick PbI(2) films as substrates we discover that the CH(3)NH(3)I insertion in the PbI(2) is reversible, with the extraction into the solvent isopropanol occurring on the same time scale of seconds as the intercalation process. This offers an explanation for the strikingly rapid and facile exchange of halide ions in CH(3)NH(3)PbX(3) by solution processing at room temperature. PMID:25643832

  4. Low-pressure indium-halide discharges for fluorescent illumination applications

    NASA Astrophysics Data System (ADS)

    Hayashi, Daiyu; Hilbig, Rainer; Körber, Achim; Schwan, Stefan; Scholl, Robert; Boerger, Martin; Huppertz, Maria

    2010-02-01

    Low-pressure gas discharges of molecular radiators were studied for fluorescent lighting applications with a goal of reducing the energy loss due to the large Stokes shift in phosphors of conventional mercury-based fluorescent lamp technology. Indium halides (InCl, InBr, and InI) were chosen as the molecular radiators that generate ultraviolet to blue light emissions. The electrical characteristics and optical emission intensities were measured in discharges containing gaseous indium halides (InCl, InBr, and InI) as molecular radiators. The low-pressure discharges in indium halide vapor showed potential as a highly efficient gas discharge system for fluorescent lighting application.

  5. High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites.

    PubMed

    Sutter-Fella, Carolin M; Li, Yanbo; Amani, Matin; Ager, Joel W; Toma, Francesca M; Yablonovitch, Eli; Sharp, Ian D; Javey, Ali

    2016-01-13

    Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH3NH3PbI3-xBrx perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamic range. The internal luminescence quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ Eg ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells. PMID:26691065

  6. Pressure-Induced Structural and Optical Properties of Organometal Halide Perovskite-Based Formamidinium Lead Bromide.

    PubMed

    Wang, Lingrui; Wang, Kai; Zou, Bo

    2016-07-01

    Organometal halide perovskites (OMHPs) are attracting an ever-growing scientific interest as photovoltaic materials with moderate cost and compelling properties. In this Letter, pressure-induced optical and structural changes of OMHP-based formamidinium lead bromide (FAPbBr3) were systematically investigated. We studied the pressure dependence of optical absorption and photoluminescence, both of which showed piezochromism. Synchrotron X-ray diffraction indicated that FAPbBr3 underwent two phase transitions and subsequent amorphization, leading directly to the bandgap evolution with redshift followed by blueshift during compression. Raman experiments illustrated the high pressure behavior of organic cation and the surrounding inorganic octahedra. Additionally, the effect of cation size and the different intermolecular interactions between organic cation and inorganic octahedra result in the fact that FAPbBr3 is less compressible than the reported methylammonium lead bromide (MAPbBr3). High pressure studies of the structural evolution and optical properties of OMHPs provide important clues in optimizing photovoltaic performance and help to design novel OMHPs with higher stimuli-resistant ability. PMID:27321024

  7. Vaporisation and thermal decomposition of dialkylimidazolium halide ion ionic liquids.

    PubMed

    Lovelock, Kevin R J; Armstrong, James P; Licence, Peter; Jones, Robert G

    2014-01-28

    Vaporisation and liquid phase thermal decomposition, TD, of two halide ion ionic liquids, 1-octyl-3-methylimidazolium chloride, [C8C1Im]Cl, and 1-octyl-3-methylimidazolium iodide, [C8C1Im]I, are investigated using temperature programmed desorption (TPD) line of sight mass spectrometry (LOSMS) at ultra-high vacuum (UHV). The ability to use MS to distinguish between vaporisation and TD allows the thermodynamics/kinetics of both vaporisation and TD to be investigated within the same experiments. Vaporisation of both halide ion ionic liquids is demonstrated. For both [C8C1Im]Cl and [C8C1Im]I the vapour is shown to be composed of neutral ion pairs (NIPs). The enthalpy of vaporisation at temperature T, ΔvapHT, was experimentally determined as ΔvapH455 = 151 ± 10 kJ mol(-1) for [C8C1Im]Cl and ΔvapH480 = 149 ± 8 kJ mol(-1) for [C8C1Im]I. Extrapolation of ΔvapHT to the reference temperature, 298 K, gave ΔvapH298 = 166 ± 10 kJ mol(-1) for [C8C1Im]Cl and ΔvapH298 = 167 ± 8 kJ mol(-1) for [C8C1Im]I, higher than most ΔvapH298 values measured to date for other [C8C1Im](+)-containing ionic liquids. In addition, predictions of ΔvapH298 for other halide ion ionic liquids are made. Liquid phase TD is shown to proceed via nucleophilic substitution to give two sets of products: 1-octylimidazole and methylhalide, and 1-methylimidazole and 1-octylhalide. The activation energy of TD at a temperature T, Ea,TD,T, is measured for the nucleophilic substitution of [C8C1Im]I to give methyliodide; Ea,TD,480 = 136 ± 15 kJ mol(-1). Ea,TD,T is measured for the nucleophilic substitution of [C8C1Im]Cl to give methylchloride; Ea,TD,455 = 132 ± 10 kJ mol(-1). The fact that ΔvapHT and Ea,TD,T are the same (within error) for both ionic liquids is commented upon, and conclusions are drawn as to the thermal stability of these ionic liquids. PMID:24105256

  8. Decreased UV absorbance as an indicator of micropollutant removal efficiency in wastewater treated with ozone.

    PubMed

    Wittmer, A; Heisele, A; McArdell, C S; Böhler, M; Longree, P; Siegrist, H

    2015-01-01

    Ozone transforms various organic compounds that absorb light within the UV and visible spectra. UV absorbance can therefore be used to detect the transformation of chemicals during ozonation. In wastewater, decolourisation can be observed after ozonation. This study investigates the correlation of the UV absorbance difference between the ozonation inlet and outlet and the removal efficiency of micropollutants in wastewater. The absorbance at 254 and 366 nm was measured at the ozonation inlet and outlet, as was the concentration of 24 representative micropollutants and the dissolved organic carbon (DOC). The results clearly showed that the relative decrease of absorbance (ΔAbs) is positively correlated with the relative removal efficiency of micropollutants. We therefore suggest that UV absorbance can be used as a feedback control parameter to achieve optimal ozone dosage in wastewater treatment plants and to gain a fast insight into the process efficiency and stability of the ozonation. PMID:25860699

  9. Ambient-pressure organic superconductor

    DOEpatents

    Williams, Jack M.; Wang, Hsien-Hau; Beno, Mark A.

    1986-01-01

    A new class of organic superconductors having the formula (ET).sub.2 MX.sub.2 wherein ET represents bis(ethylenedithio)-tetrathiafulvalene, M is a metal such as Au, Ag, In, Tl, Rb, Pd and the like and X is a halide. The superconductor (ET).sub.2 AuI.sub.2 exhibits a transition temperature of 5 K which is high for organic superconductors.

  10. Energy-Absorbing, Lightweight Wheels

    NASA Technical Reports Server (NTRS)

    Waydo, Peter

    2003-01-01

    Improved energy-absorbing wheels are under development for use on special-purpose vehicles that must traverse rough terrain under conditions (e.g., extreme cold) in which rubber pneumatic tires would fail. The designs of these wheels differ from those of prior non-pneumatic energy-absorbing wheels in ways that result in lighter weights and more effective reduction of stresses generated by ground/wheel contact forces. These wheels could be made of metals and/or composite materials to withstand the expected extreme operating conditions. As shown in the figure, a wheel according to this concept would include an isogrid tire connected to a hub via spring rods. The isogrid tire would be a stiff, lightweight structure typically made of aluminum. The isogrid aspect of the structure would both impart stiffness and act as a traction surface. The hub would be a thin-walled body of revolution having a simple or compound conical or other shape chosen for structural efficiency. The spring rods would absorb energy and partially isolate the hub and the supported vehicle from impact loads. The general spring-rod configuration shown in the figure was chosen because it would distribute contact and impact loads nearly evenly around the periphery of the hub, thereby helping to protect the hub against damage that would otherwise be caused by large loads concentrated onto small portions of the hub.

  11. Potential function and dissociation energy of alkali halide

    NASA Astrophysics Data System (ADS)

    Srivastava, Abhay P.; Pandey, Anjani K.; Pandey, Brijesh K.

    2016-05-01

    Dissociation energy of some alkali halides have been calculated by using different interaction potential function such as Born-Mayer, Varshani-Shukla and L5 potential model. The theoretical calculation is compared with experimental values. The Result shows that the values of dissociation energy as calculated by using different potential models have an equal amount of deviation with experimental values. The above said deviation with experimental values can be explained by consideration of rotational-vibrational coupling between the constituents of molecules in the limelight of molecular spectroscopy. Findings of present work suggest that the existing potential model need to be reviewed in view of the correction factors solely depending on the rotational, vibrational and electronic coupling between the constituents of molecules.

  12. Fabrication of alkali halide UV photocathodes by pulsed laser deposition

    SciTech Connect

    Brendel', V M; Bukin, V V; Garnov, Sergei V; Bagdasarov, V Kh; Denisov, N N; Garanin, Sergey G; Terekhin, V A; Trutnev, Yurii A

    2012-12-31

    A technique has been proposed for the fabrication of atmospheric corrosion resistant alkali halide UV photocathodes by pulsed laser deposition. We produced photocathodes with a highly homogeneous photoemissive layer well-adherent to the substrate. The photocathodes were mounted in a vacuum photodiode, and a tungsten grid was used as an anode. Using pulsed UV lasers, we carried out experiments aimed at evaluating the quantum efficiency of the photocathodes. With a dc voltage applied between the photocathode and anode grid, we measured a shunt signal proportional to the total charge emitted by the cathode exposed to UV laser light. The proposed deposition technique enables one to produce photocathodes with photoemissive layers highly uniform in quantum efficiency, which is its main advantage over thin film growth by resistive evaporation. (laser technologies)

  13. Direct current ballast circuit for metal halide lamp

    NASA Technical Reports Server (NTRS)

    Lutus, P. (Inventor)

    1981-01-01

    A direct current ballast circuit for a two electrode metal halide lamp is described. Said direct current ballast circuit includes a low voltage DC input and a high frequency power amplifier and power transformer for developing a high voltage output. The output voltage is rectified by diodes and filtered by inductor and capacitor to provide a regulated DC output through commutating diodes to one terminal of the lamp at the output terminal. A feedback path from the output of the filter capacitor through the bias resistor to power the high frequency circuit which includes the power amplifier and the power transformer for sustaining circuit operations during low voltage transients on the input DC supply is described. A current sensor connected to the output of the lamp through terminal for stabilizing lamp current following breakdown of the lamp is described.

  14. Metal halide arc discharge lamp having short arc length

    NASA Technical Reports Server (NTRS)

    Muzeroll, Martin E. (Inventor)

    1994-01-01

    A metal halide arc discharge lamp includes a sealed light-transmissive outer jacket, a light-transmissive shroud located within the outer jacket and an arc tube assembly located within the shroud. The arc tube assembly includes an arc tube, electrodes mounted within the arc tube and a fill material for supporting an arc discharge. The electrodes have a spacing such that an electric field in a range of about 60 to 95 volts per centimeter is established between the electrodes. The diameter of the arc tube and the spacing of the electrodes are selected to provide an arc having an arc diameter to arc length ratio in a range of about 1.6 to 1.8. The fill material includes mercury, sodium iodide, scandium tri-iodide and a rare gas, and may include lithium iodide. The lamp exhibits a high color rendering index, high lumen output and high color temperature.

  15. Enhanced quantum efficiency from hybrid cesium halide/copper photocathodes

    NASA Astrophysics Data System (ADS)

    Kong, Lingmei; Joly, Alan G.; Droubay, Timothy C.; Gong, Yu; Hess, Wayne P.

    2014-04-01

    The quantum efficiency (QE) of Cu is found to increase dramatically when coated by a CsI film and then irradiated by a UV laser. Over three orders of magnitude quantum efficiency enhancement at 266 nm is observed in CsI/Cu(100), indicating potential application in future photocathode devices. Upon laser irradiation, a large work function reduction to a value less than 2 eV is also observed, significantly greater than for similarly treated CsBr/Cu(100). The initial QE enhancement, prior to laser irradiation, is attributed to interface interaction and the intrinsic properties of the Cs halide film. Further QE enhancement following activation is attributed to formation of inter-band states and Cs metal accumulation at the interface induced by laser irradiation.

  16. Recent progress and challenges of organometal halide perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Yang, Liyan; Barrows, Alexander T.; Lidzey, David G.; Wang, Tao

    2016-02-01

    We review recent progress in the development of organometal halide perovskite solar cells. We discuss different compounds used to construct perovskite photoactive layers, as well as the optoelectronic properties of this system. The factors that affect the morphology of the perovskite active layer are explored, e.g. material composition, film deposition methods, casting solvent and various post-treatments. Different strategies are reviewed that have recently emerged to prepare high performing perovskite films, creating polycrystalline films having either large or small grain size. Devices that are constructed using meso-superstructured and planar architectures are summarized and the impact of the fabrication process on operational efficiency is discussed. Finally, important research challenges (hysteresis, thermal and moisture instability, mechanical flexibility, as well as the development of lead-free materials) in the development of perovskite solar cells are outlined and their potential solutions are discussed.

  17. Active terahertz device based on optically controlled organometal halide perovskite

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Lv, Longfeng; He, Ting; Chen, Tianji; Zang, Mengdi; Zhong, Liang; Wang, Xinke; Shen, Jingling; Hou, Yanbing

    2015-08-01

    An active all-optical high-efficiency broadband terahertz device based on an organometal halide perovskite (CH3NH3PbI3, MAPbI3)/inorganic (Si) structure is investigated. Spectrally broadband modulation of the THz transmission is obtained in the frequency range from 0.2 to 2.6 THz, and a modulation depth of nearly 100% can be achieved with a low-level photoexcitation power (˜0.4 W/cm2). Both THz transmission and reflection were suppressed in the MAPbI3/Si structure by an external continuous-wave (CW) laser. Enhancement of the charge carrier density at the MAPbI3/Si interface is crucial for photo-induced absorption. The results show that the proposed high-efficiency broadband optically controlled terahertz device based on the MAPbI3/Si structure has been realized.

  18. Mechanical properties of silver halide core/clad IR fibers

    NASA Astrophysics Data System (ADS)

    Shalem, Shaul; German, Alla; Moser, Frank; Katzir, Abraham

    1996-04-01

    We have developed core/clad polycrystalline silver halide optical fibers with a loss of roughly 0.3 dB/m at 10.6 micrometers. Such fibers, with core diameters 0.3 - 0.6 mm and lengths of 1 to 2 meters are capable of continuously delivering output power densities as high as 14 KW/cm2. The fibers were repetitively bent in the plastic and elastic regimes and the optical transmission monitored during bending. The mechanical properties of the core/clad fibers and of the core only fibers are similar. It was also demonstrated that the 'bending' properties of the core/clad fibers are determined by the cladding material. Our investigations suggest that proper design of the core/clad structure may give significant improvement in mechanical properties such as more cycles to optical failure. This will be very important especially for endoscopic laser surgery and other medical applications.

  19. Enhanced Quantum Efficiency From Hybrid Cesium Halide/Copper Photocathode

    SciTech Connect

    Kong, Lingmei; Joly, Alan G.; Droubay, Timothy C.; Gong, Yu; Hess, Wayne P.

    2014-04-28

    The quantum efficiency of Cu is found to increase dramatically when coated by a CsI film and then irradiated by a UV laser. Over three orders of magnitude quantum efficiency enhancement at 266 nm is observed in CsI/Cu(100), indicating potential application in future photocathode devices. Upon laser irradiation, a large work function reduction to a value less than 2 eV is also observed, significantly greater than for similarly treated CsBr/Cu(100). The initial QE enhancement, prior to laser irradiation, is attributed to interface interaction, surface cleanliness and the intrinsic properties of the Cs halide film. Further QE enhancement following activation is attributed to formation of inter-band states and Cs metal accumulation at the interface induced by laser irradiation.

  20. Large Magnetoresistance Effects in Novel Layered Rare Earth Halides

    NASA Astrophysics Data System (ADS)

    Kremer, R. K.; Ryazanov, M.; Simon, A.

    We give a survey of the structures, electric, magnetic and magnetoresistance properties of the two novel low dimensional rare-earth halide systems, GdI2 and GdIHy (2/3 < y ≤ 1). The large magnetoresistance e.ect observed for GdI2 can be understood on the basis of a conventional spin disorder scattering mechanism, however, strongly magni.ed by the structural anisotropy and the special topology of the Fermi surface. Bound magnetic polarons are formed in GdIHy leading to a metal insulator transition below ~ 30 K. The mobility of the magnetic polarons can be e.ectively modi.ed by external magnetic .fields resulting in the large experimentally found magnetoresistance.

  1. Enhanced quantum efficiency from hybrid cesium halide/copper photocathodes

    SciTech Connect

    Kong, Lingmei; Joly, Alan G.; Droubay, Timothy C.; Gong, Yu; Hess, Wayne P.

    2014-04-28

    The quantum efficiency (QE) of Cu is found to increase dramatically when coated by a CsI film and then irradiated by a UV laser. Over three orders of magnitude quantum efficiency enhancement at 266 nm is observed in CsI/Cu(100), indicating potential application in future photocathode devices. Upon laser irradiation, a large work function reduction to a value less than 2 eV is also observed, significantly greater than for similarly treated CsBr/Cu(100). The initial QE enhancement, prior to laser irradiation, is attributed to interface interaction and the intrinsic properties of the Cs halide film. Further QE enhancement following activation is attributed to formation of inter-band states and Cs metal accumulation at the interface induced by laser irradiation.

  2. Fast Photoconductive Responses in Organometal Halide Perovskite Photodetectors.

    PubMed

    Wang, Fei; Mei, Jingjing; Wang, Yunpeng; Zhang, Ligong; Zhao, Haifeng; Zhao, Dongxu

    2016-02-01

    Inorganic semiconductor-based photodetectors have been suffering from slow response speeds, which are caused by the persistent photoconductivity of semiconductor materials. For realizing high speed optoelectronic devices, the organometal halide perovskite thin films were applied onto the interdigitated (IDT) patterned Au electrodes, and symmetrical structured photoconductive detectors were achieved. The detectors were sensitive to the incident light signals, and the photocurrents of the devices were 2-3 orders of magnitude higher than dark currents. The responsivities of the devices could reach up to 55 mA W(1-). Most importantly, the detectors have a fast response time of less than 20 μs. The light and bias induced dipole rearrangement in organometal perovskite thin films has resulted in the instability of photocurrents, and Ag nanowires could quicken the process of dipole alignment and stabilize the photocurrents of the devices. PMID:26796674

  3. Venus: Halide cloud condensation and volatile element inventories

    NASA Technical Reports Server (NTRS)

    Lewis, J. S.; Fegley, B., Jr.

    1982-01-01

    Several Venus cloud condensates, including A12C16 as well as halides, oxides and sulfides of arsenic and antimony, are assessed for their thermodynamic and geochemical plausibility. Aluminum chloride can confidently be ruled out, and condensation of arsenic sulfides on the surface will cause arsenic compounds to be too rare to produce the observed clouds. Antimony may conceivably be sufficiently volatile, but the expected molecular form is gaseous SbS, not the chloride. Arsenic and antimony compounds in the atmosphere will be regulated at very low levels by sulfide precipitation, irrespective of the planetary inventory of As and Sb. Thus the arguments for a volatile-deficient origin for Venus based on the depletion of water and mercury (relative to Earth) cannot be tested by a search for atmospheric arsenic or antimony.

  4. Material Innovation in Advancing Organometal Halide Perovskite Functionality.

    PubMed

    Zheng, Fan; Saldana-Greco, Diomedes; Liu, Shi; Rappe, Andrew M

    2015-12-01

    Organometal halide perovskites (OMHPs) have garnered much attention recently for their unprecedented rate of increasing power conversion efficiency (PCE), positioning them as a promising basis for the next-generation photovoltaic devices. However, the gap between the rapid increasing PCE and the incomplete understanding of the structure-property-performance relationship prevents the realization of the true potential of OMHPs. This Perspective aims to provide a concise overview of the current status of OMHP research, highlighting the unique properties of OMHPs that are critical for solar applications but still not adequately explained. Stability and performance challenges of OMHP solar cells are discussed, calling upon combined experimental and theoretical efforts to address these challenges for pioneering commercialization of OMHP solar cells. Various material innovation strategies for improving the performance and stability of OMHPs are surveyed, showing that the OMHP architecture can serve as a promising and robust platform for the design and optimization of materials with desired functionalities. PMID:26631361

  5. Interactions between halide anions and a molecular hydrophobic interface.

    PubMed

    Rankin, Blake M; Hands, Michael D; Wilcox, David S; Fega, K Rebecca; Slipchenko, Lyudmila V; Ben-Amotz, Dor

    2013-01-01

    Interactions between halide ions (fluoride and iodide) and t-butyl alcohol (TBA) dissolved in water are probed using a recently developed hydration-shell spectroscopic technique and theoretical cluster and liquid calculations. High ignal-to-noise Raman spectroscopic measurements are combined with multivariate curve resolution (Raman-MCR) to reveal that while there is little interaction between aqueous fluoride ions and TBA, iodide ions break down the tetrahedral hydration-shell structure of TBA and produce a red-shift in its CH stretch frequency, in good agreement with the theoretical effective fragment potential (EFP) molecular dynamics simulations and hybrid quantum/EFP frequency calculations. The results imply that there is a significantly larger probability of finding iodide than fluoride in the first hydration shell of TBA, although the local iodide concentration is apparently not as high as in the surrounding bulk aqueous NaI solution. PMID:23795504

  6. Semiphysical development of holograms recorded in silver halide emulsions

    NASA Astrophysics Data System (ADS)

    Banyasz, Istvan; Belendez, Augusto; Pascual, Inmaculada V.; Fimia, Antonio

    2000-10-01

    In the course of experiments on measurement of the effects of processing on nonlinear characteristics of silver halide holograms recorded in Agfa-gevaert 8E75HD emulsions we found that, under certain circumstances, the AAC developer acted as a semi-physical developer instead of the normal chemical developing action. The developed and fixed holograms were of low optical density (<0.5) and of high diffraction efficiency (up to 15%). Phase contrast microscopy revealed that very clean phase gratings were obtained. This effect of the AAC developer was due to the replacement of one of its components, sodium carbonate of purest grade with that of for analysis grade of the same company.

  7. Fabrication of alkali halide UV photocathodes by pulsed laser deposition

    NASA Astrophysics Data System (ADS)

    Brendel', V. M.; Bukin, V. V.; Garnov, Sergei V.; Bagdasarov, V. Kh; Denisov, N. N.; Garanin, Sergey G.; Terekhin, V. A.; Trutnev, Yurii A.

    2012-12-01

    A technique has been proposed for the fabrication of atmospheric corrosion resistant alkali halide UV photocathodes by pulsed laser deposition. We produced photocathodes with a highly homogeneous photoemissive layer well-adherent to the substrate. The photocathodes were mounted in a vacuum photodiode, and a tungsten grid was used as an anode. Using pulsed UV lasers, we carried out experiments aimed at evaluating the quantum efficiency of the photocathodes. With a dc voltage applied between the photocathode and anode grid, we measured a shunt signal proportional to the total charge emitted by the cathode exposed to UV laser light. The proposed deposition technique enables one to produce photocathodes with photoemissive layers highly uniform in quantum efficiency, which is its main advantage over thin film growth by resistive evaporation.

  8. Theoretical study of the scandium and yttrium halides

    NASA Technical Reports Server (NTRS)

    Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Partridge, Harry

    1988-01-01

    The X1Sigma(+) ground states and a3Delta excited states of the diatomic halides of Sc and Y are characterized theoretically, using the SDCI coupled-pair functional method and the state-averaged CASSCF method to determine the spectroscopic constants and related properties. The techniques employed are discussed, and the results are presented in extensive tables. The dissociation energies are given as D0 = 6.00 eV for ScF, 4.55 eV for ScCl, 3.90 eV for ScBr, 6.72 eV for YF, 5.36 eV for YCl, and 4.74 eV for YBr.

  9. Bright light-emitting diodes based on organometal halide perovskite

    NASA Astrophysics Data System (ADS)

    Tan, Zhi-Kuang; Moghaddam, Reza Saberi; Lai, May Ling; Docampo, Pablo; Higler, Ruben; Deschler, Felix; Price, Michael; Sadhanala, Aditya; Pazos, Luis M.; Credgington, Dan; Hanusch, Fabian; Bein, Thomas; Snaith, Henry J.; Friend, Richard H.

    2014-09-01

    Solid-state light-emitting devices based on direct-bandgap semiconductors have, over the past two decades, been utilized as energy-efficient sources of lighting. However, fabrication of these devices typically relies on expensive high-temperature and high-vacuum processes, rendering them uneconomical for use in large-area displays. Here, we report high-brightness light-emitting diodes based on solution-processed organometal halide perovskites. We demonstrate electroluminescence in the near-infrared, green and red by tuning the halide compositions in the perovskite. In our infrared device, a thin 15 nm layer of CH3NH3PbI3-xClx perovskite emitter is sandwiched between larger-bandgap titanium dioxide (TiO2) and poly(9,9‧-dioctylfluorene) (F8) layers, effectively confining electrons and holes in the perovskite layer for radiative recombination. We report an infrared radiance of 13.2 W sr-1 m-2 at a current density of 363 mA cm-2, with highest external and internal quantum efficiencies of 0.76% and 3.4%, respectively. In our green light-emitting device with an ITO/PEDOT:PSS/CH3NH3PbBr3/F8/Ca/Ag structure, we achieved a luminance of 364 cd m-2 at a current density of 123 mA cm-2, giving external and internal quantum efficiencies of 0.1% and 0.4%, respectively. We show, using photoluminescence studies, that radiative bimolecular recombination is dominant at higher excitation densities. Hence, the quantum efficiencies of the perovskite light-emitting diodes increase at higher current densities. This demonstration of effective perovskite electroluminescence offers scope for developing this unique class of materials into efficient and colour-tunable light emitters for low-cost display, lighting and optical communication applications.

  10. Photochemical Reaction Dynamics of Halooxides and Nitrosyl Halides

    NASA Astrophysics Data System (ADS)

    Reid, Philip

    2004-03-01

    Recent progress in understanding the environment-dependent reactivity of halooxides and nitrosyl halides is presented. Time-resolved resonance Raman and transient infrared absorption studies of chlorine dioxide (OClO) photochemistry in solution are presented. These studies demonstrate that geminate recombination of the primary ClO and O photofragments results in the reformation of ground-state OClO on the sub-picosecond timescale. These studies also demonstrate that a fraction of photoexcited OClO undergoes photoisomerization to produce ClOO on the tens-of-picoseconds timescale, with ground-state thermal decomposition of this species providing for Cl production on the sub-nanosecond timescale. The discrepancy in formation times for ground-state OClO and ClOO demonstrates that the photoisomer is not produced by geminate recombination, and possible mechanisms for the formation of this intermediate are presented. The excited-state reaction dynamics of nitrosyl chloride (ClNO) that occur following photoexcitation resonant with the "A band" are determined using absolute resonance Raman intensity analysis (RRIA). These studies demonstrate that photoexcitation of solution-phase ClNO promotes evolution along the N-Cl stretch coordinate consistent with N-Cl bond dissociation. Comparative RRIA studies of ClNO dissolved in cyclohexane and acetonitrile reveal that the excited-state structural evolution is solvent dependent; however, the origin of this dependence is related to modification of the ground-state equilibrium geometry with solvent. Finally, femtosecond transient absorption studies reveal that in condensed environments, photoexcitation of ClNO also results in photoisomerization to produce the intermediate species ClON on the picosecond timescale. This observation suggests that photoisomerization is a general feature of halooxide and nitrosyl halide chemistry in condensed environments.

  11. High-Pressure Studies of the Hydrogen Halides

    NASA Astrophysics Data System (ADS)

    Katz, Allen Israel

    This dissertation presents an experimental study of hydrogen bonding in the solid hydrogen halides under high pressure. The high pressures were obtained with a diamond-anvil high pressure cell. Raman scattering experiments were performed on hydrogen bromide and hydrogen fluoride under pressures up to 200 kilobars. Powder x-ray diffraction experiments were performed on hydrogen bromide under pressures up to 220 kilobars. All measurements were performed at low-temperature (approximately 20 Kelvin) in the ordered orthorhombic phase III consisting of planar zig-zag chains of hydrogen bonded molecules. In the x-ray measurements on hydrogen bromide, all three orthorhombic lattice parameters were measured. The out-of-plane c-lattice parameter decreased initially much faster than the b-lattice parameter which is in the direction of the zig-zag hydrogen bonded chains. This is expected due to the weak interchain forces as opposed to the much stronger hydrogen and molecular bond forces in the chain. Surprisingly, the a and b-lattice parameters have the same pressure dependence. Raman spectra were taken of both the high frequency molecular stretching modes and the lattice modes. The stretching mode frequencies of all three hydrogen halides decrease with increasing pressure, indicative of charge transfer out of the molecular bond and into the hydrogen bond. The stretching frequency of hydrogen fluoride was observed to decrease at the greatest rate with increasing pressure. In hydrogen bromide, the two lowest frequency librational modes crossed frequencies at about 50 kilobars. After this crossing, the lower frequency mode exhibited an unusual lack of pressure dependence and an unusually large intensity. The hydrogen fluoride lattice mode frequencies all appear flat with very little pressure dependence. The ambient temperature ruby pressure scale, used for all pressure measurements in this dissertation, was calibrated at 20 Kelvin by comparison to the equation -of-state for gold

  12. Development of New Absorber Materials to Achieve Organic Photovoltaic Commercial Modules with 15% Efficiency and 20 Years Lifetime: Cooperative Research and Development Final Report, CRADA Number CRD-12-498

    SciTech Connect

    Olson, D.

    2014-08-01

    Under this CRADA the parties will develop intermediates or materials that can be employed as the active layer in dye sensitized solar cells printed polymer systems, or small molecule organic photovoltaics.

  13. Methods for synthesizing alane without the formation of adducts and free of halides

    DOEpatents

    Zidan, Ragaiy; Knight, Douglas A; Dinh, Long V

    2013-02-19

    A process is provided to synthesize an alane without the formation of alane adducts as a precursor. The resulting product is a crystallized .alpha.-alane and is a highly stable product and is free of halides.

  14. Reactivity of halide and pseudohalide ligands in transition-metal complexes

    SciTech Connect

    Kukushkin, Yu.N.; Kukushkin, V.Yu.

    1985-10-01

    The experimental material on the reactions of coordinated halide ligands, as well as cyanide, azido, thiocyanato, and cyanato ligands, in transition-metal complexes has been generalized in this review.

  15. Nickel-Catalyzed Cross-Electrophile Coupling with Organic Reductants in Non-Amide Solvents.

    PubMed

    Anka-Lufford, Lukiana L; Huihui, Kierra M M; Gower, Nicholas J; Ackerman, Laura K G; Weix, Daniel J

    2016-08-01

    Cross-electrophile coupling of aryl halides with alkyl halides has thus far been primarily conducted with stoichiometric metallic reductants in amide solvents. This report demonstrates that the use of tetrakis(dimethylamino)ethylene (TDAE) as an organic reductant enables the use of non-amide solvents, such as acetonitrile or propylene oxide, for the coupling of benzyl chlorides and alkyl iodides with aryl halides. Furthermore, these conditions work for several electron-poor heterocycles that are easily reduced by manganese. Finally, we demonstrate that TDAE addition can be used as a control element to 'hold' a reaction without diminishing yield or catalyst activity. PMID:27273457

  16. Structural and electronic properties of organo-halide hybrid perovskites from ab initio molecular dynamics.

    PubMed

    Quarti, Claudio; Mosconi, Edoardo; De Angelis, Filippo

    2015-04-14

    The last two years have seen the unprecedentedly rapid emergence of a new class of solar cells, based on hybrid organic-inorganic halide perovskites. The success of this class of materials is due to their outstanding photoelectrochemical properties coupled to their low cost, mainly solution-based, fabrication techniques. Solution processed materials are however often characterized by an inherent flexible structure, which is hardly mapped into a single local minimum energy structure. In this perspective, we report on the interplay between structural and electronic properties of hybrid lead iodide perovskites investigated using ab initio molecular dynamics (AIMD) simulations, which allow the dynamical simulation of disordered systems at finite temperature. We compare the prototypical MAPbI3 (MA = methylammonium) perovskite in its cubic and tetragonal structure with the trigonal phase of FAPbI3 (FA = formamidinium), investigating different starting arrangements of the organic cations. Despite the relatively short time scale amenable to AIMD, typically a few tens of ps, this analysis demonstrates the sizable structural flexibility of this class of materials, showing that the instantaneous structure could significantly differ from the time and thermal averaged structure. We also highlight the importance of the organic-inorganic interactions in determining the fluxional properties of this class of materials. A peculiar spatial localization of the valence and conduction band edges is also found, with a dynamics in the range of 0.1 ps, which is associated with the positional dynamics of the organic cations within the cubo-octahedral perovskite cage. This asymmetry in the spatial localization of the band edges is expected to ease exciton dissociation and assist the initial stages of charge separation, possibly constituting one of the key factors for the impressive photovoltaic performances of hybrid lead-iodide perovskites. PMID:25766785

  17. Broad Wavelength Tunable Robust Lasing from Single-Crystal Nanowires of Cesium Lead Halide Perovskites (CsPbX3, X = Cl, Br, I).

    PubMed

    Fu, Yongping; Zhu, Haiming; Stoumpos, Constantinos C; Ding, Qi; Wang, Jue; Kanatzidis, Mercouri G; Zhu, Xiaoyang; Jin, Song

    2016-08-23

    Lead halide perovskite nanowires (NWs) are emerging as a class of inexpensive semiconductors with broad bandgap tunability for optoelectronics, such as tunable NW lasers. Despite exciting progress, the current organic-inorganic hybrid perovskite NW lasers suffer from limited tunable wavelength range and poor material stability. Herein, we report facile solution growth of single-crystal NWs of inorganic perovskite CsPbX3 (X = Br, Cl) and their alloys [CsPb(Br,Cl)3] and a low-temperature vapor-phase halide exchange method to convert CsPbBr3 NWs into perovskite phase CsPb(Br,I)3 alloys and metastable CsPbI3 with well-preserved perovskite crystal lattice and NW morphology. These single crystalline NWs with smooth end facets and subwavelength dimensions are ideal Fabry-Perot cavities for NW lasers. Optically pumped tunable lasing across the entire visible spectrum (420-710 nm) is demonstrated at room temperature from these NWs with low lasing thresholds and high-quality factors. Such highly efficient lasing similar to what can be achieved with organic-inorganic hybrid perovskites indicates that organic cation is not essential for light emission application from these lead halide perovskite materials. Furthermore, the CsPbBr3 NW lasers show stable lasing emission with no measurable degradation after at least 8 h or 7.2 × 10(9) laser shots under continuous illumination, which are substantially more robust than their organic-inorganic counterparts. The Cs-based perovskites offer a stable material platform for tunable NW lasers and other nanoscale optoelectronic devices. PMID:27437566

  18. Difference of solvation site between halide ions and electrons in an alkylammonium ionic liquid

    NASA Astrophysics Data System (ADS)

    Katoh, Ryuzi

    2009-11-01

    The difference of solvation site between halide ions and electrons in an alkylammonium ionic liquid is discussed on the basis of spectroscopic data. The data indicate that the halide ions replaced the anions of the ionic liquid and were fully solvated by the ammonium cations. In contrast, the solvated electrons were less solvated, suggesting that they were located near the region of the alkyl chain of the cations.

  19. Oxidation of hydrogen halides to elemental halogens with catalytic molten salt mixtures

    DOEpatents

    Rohrmann, Charles A.

    1978-01-01

    A process for oxidizing hydrogen halides by means of a catalytically active molten salt is disclosed. The subject hydrogen halide is contacted with a molten salt containing an oxygen compound of vanadium and alkali metal sulfates and pyrosulfates to produce an effluent gas stream rich in the elemental halogen. The reduced vanadium which remains after this contacting is regenerated to the active higher valence state by contacting the spent molten salt with a stream of oxygen-bearing gas.

  20. Shock absorber operates over wide range

    NASA Technical Reports Server (NTRS)

    Creasy, W. K.; Jones, J. C.

    1965-01-01

    Piston-type hydraulic shock absorber, with a metered damping system, operates over a wide range of kinetic energy loading rates. It is used for absorbing shock and vibration on mounted machinery and heavy earth-moving equipment.

  1. Spectral sensitization with dyes of core-silver halide shell microsystems

    NASA Astrophysics Data System (ADS)

    Tyurin, A. V.; Zhukov, S. A.; Churashov, V. P.

    2015-09-01

    We have studied spectral sensitization with anionic dyes of core-silver halide shell microsystems cores of which can be either nonsilver or silver halide compounds. Conditions under which dye sensitizers, being adsorbed on cores, remain under silver halide shells after their growing are considered. Comparison of results of sensitometric and low-temperature ( T = 77 K) luminescent measurements have shown that these conditions are determined by the charge state of cations of microsystem cores. If the shell contains the same univalent component in its composition as the core does, as in the case in which the core is a silver halide compound, the anionic dye is displaced to the outer surface of the shell. If the core contains a divalent cationic component, as in the case in which the core is a nonsilver compound, the dye remains under the silver halide shell; i.e., it is overgrown by the shell. We have shown that the charge state of core cations affects the character of the core interaction with anionic dyes, which ensures differences in the spectral sensitization of core-silver halide shell microsystems, as well as differences in the dye photoexcitation relaxation in them.

  2. Fluorescence-Based Bacterial Bioreporter for Specific Detection of Methyl Halide Emissions in the Environment

    PubMed Central

    Farhan Ul Haque, Muhammad; Nadalig, Thierry; Bringel, Françoise; Schaller, Hubert

    2013-01-01

    Methyl halides are volatile one-carbon compounds responsible for substantial depletion of stratospheric ozone. Among them, chloromethane (CH3Cl) is the most abundant halogenated hydrocarbon in the atmosphere. Global budgets of methyl halides in the environment are still poorly understood due to uncertainties in their natural sources, mainly from vegetation, and their sinks, which include chloromethane-degrading bacteria. A bacterial bioreporter for the detection of methyl halides was developed on the basis of detailed knowledge of the physiology and genetics of Methylobacterium extorquens CM4, an aerobic alphaproteobacterium which utilizes chloromethane as the sole source of carbon and energy. A plasmid construct with the promoter region of the chloromethane dehalogenase gene cmuA fused to a promotorless yellow fluorescent protein gene cassette resulted in specific methyl halide-dependent fluorescence when introduced into M. extorquens CM4. The bacterial whole-cell bioreporter allowed detection of methyl halides at femtomolar levels and quantification at concentrations above 10 pM (approximately 240 ppt). As shown for the model chloromethane-producing plant Arabidopsis thaliana in particular, the bioreporter may provide an attractive alternative to analytical chemical methods to screen for natural sources of methyl halide emissions. PMID:23956392

  3. Fluorescence-based bacterial bioreporter for specific detection of methyl halide emissions in the environment.

    PubMed

    Farhan Ul Haque, Muhammad; Nadalig, Thierry; Bringel, Françoise; Schaller, Hubert; Vuilleumier, Stéphane

    2013-11-01

    Methyl halides are volatile one-carbon compounds responsible for substantial depletion of stratospheric ozone. Among them, chloromethane (CH3Cl) is the most abundant halogenated hydrocarbon in the atmosphere. Global budgets of methyl halides in the environment are still poorly understood due to uncertainties in their natural sources, mainly from vegetation, and their sinks, which include chloromethane-degrading bacteria. A bacterial bioreporter for the detection of methyl halides was developed on the basis of detailed knowledge of the physiology and genetics of Methylobacterium extorquens CM4, an aerobic alphaproteobacterium which utilizes chloromethane as the sole source of carbon and energy. A plasmid construct with the promoter region of the chloromethane dehalogenase gene cmuA fused to a promotorless yellow fluorescent protein gene cassette resulted in specific methyl halide-dependent fluorescence when introduced into M. extorquens CM4. The bacterial whole-cell bioreporter allowed detection of methyl halides at femtomolar levels and quantification at concentrations above 10 pM (approximately 240 ppt). As shown for the model chloromethane-producing plant Arabidopsis thaliana in particular, the bioreporter may provide an attractive alternative to analytical chemical methods to screen for natural sources of methyl halide emissions. PMID:23956392

  4. Monte Carlo calculation of specific absorbed fractions: variance reduction techniques

    NASA Astrophysics Data System (ADS)

    Díaz-Londoño, G.; García-Pareja, S.; Salvat, F.; Lallena, A. M.

    2015-04-01

    The purpose of the present work is to calculate specific absorbed fractions using variance reduction techniques and assess the effectiveness of these techniques in improving the efficiency (i.e. reducing the statistical uncertainties) of simulation results in cases where the distance between the source and the target organs is large and/or the target organ is small. The variance reduction techniques of interaction forcing and an ant colony algorithm, which drives the application of splitting and Russian roulette, were applied in Monte Carlo calculations performed with the code penelope for photons with energies from 30 keV to 2 MeV. In the simulations we used a mathematical phantom derived from the well-known MIRD-type adult phantom. The thyroid gland was assumed to be the source organ and urinary bladder, testicles, uterus and ovaries were considered as target organs. Simulations were performed, for each target organ and for photons with different energies, using these variance reduction techniques, all run on the same processor and during a CPU time of 1.5 · 105 s. For energies above 100 keV both interaction forcing and the ant colony method allowed reaching relative uncertainties of the average absorbed dose in the target organs below 4% in all studied cases. When these two techniques were used together, the uncertainty was further reduced, by a factor of 0.5 or less. For photons with energies below 100 keV, an adapted initialization of the ant colony algorithm was required. By using interaction forcing and the ant colony algorithm, realistic values of the specific absorbed fractions can be obtained with relative uncertainties small enough to permit discriminating among simulations performed with different Monte Carlo codes and phantoms. The methodology described in the present work can be employed to calculate specific absorbed fractions for arbitrary arrangements, i.e. energy spectrum of primary radiation, phantom model and source and target organs.

  5. Monte Carlo calculation of specific absorbed fractions: variance reduction techniques.

    PubMed

    Díaz-Londoño, G; García-Pareja, S; Salvat, F; Lallena, A M

    2015-04-01

    The purpose of the present work is to calculate specific absorbed fractions using variance reduction techniques and assess the effectiveness of these techniques in improving the efficiency (i.e. reducing the statistical uncertainties) of simulation results in cases where the distance between the source and the target organs is large and/or the target organ is small. The variance reduction techniques of interaction forcing and an ant colony algorithm, which drives the application of splitting and Russian roulette, were applied in Monte Carlo calculations performed with the code penelope for photons with energies from 30 keV to 2 MeV. In the simulations we used a mathematical phantom derived from the well-known MIRD-type adult phantom. The thyroid gland was assumed to be the source organ and urinary bladder, testicles, uterus and ovaries were considered as target organs. Simulations were performed, for each target organ and for photons with different energies, using these variance reduction techniques, all run on the same processor and during a CPU time of 1.5 · 10(5) s. For energies above 100 keV both interaction forcing and the ant colony method allowed reaching relative uncertainties of the average absorbed dose in the target organs below 4% in all studied cases. When these two techniques were used together, the uncertainty was further reduced, by a factor of 0.5 or less. For photons with energies below 100 keV, an adapted initialization of the ant colony algorithm was required. By using interaction forcing and the ant colony algorithm, realistic values of the specific absorbed fractions can be obtained with relative uncertainties small enough to permit discriminating among simulations performed with different Monte Carlo codes and phantoms. The methodology described in the present work can be employed to calculate specific absorbed fractions for arbitrary arrangements, i.e. energy spectrum of primary radiation, phantom model and source and target organs. PMID

  6. 21 CFR 872.6050 - Saliva absorber.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Saliva absorber. 872.6050 Section 872.6050 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL... absorber is a device made of paper or cotton intended to absorb moisture from the oral cavity during...

  7. 21 CFR 872.6050 - Saliva absorber.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Saliva absorber. 872.6050 Section 872.6050 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL... absorber is a device made of paper or cotton intended to absorb moisture from the oral cavity during...

  8. Improving the laboratory monitoring of absorbent oil

    SciTech Connect

    V.S. Shved; S.S. Sychev; I.V. Safina; S.A. Klykov

    2009-05-15

    The performance of absorbent coal tar oil is analyzed as a function of the constituent and group composition. The qualitative and quantitative composition of the oil that ensures the required absorbent properties is determined. Operative monitoring may be based on absorbent characteristics that permit regulation of the beginning and end of regeneration.

  9. Embedded absorbers for helicopter rotor lag damping

    NASA Astrophysics Data System (ADS)

    Byers, Lynn; Gandhi, Farhan

    2009-09-01

    Radial and chordwise damped vibration absorbers embedded in the rotor blade are compared for rotor lag damping augmentation. Results show that the radial absorber is more effective in transferring damping to the rotor blade lag mode. The chordwise absorber needs to be at a more outboard location and have a larger mass to introduce levels of lag damping comparable to that introduced by the radial absorber. The 1/rev amplitude of a chordwise absorber at the blade tip, per degree of blade lead-lag motion in forward flight, is of the order of 35% of the blade chord, and such a stroke might be difficult to accommodate. The 1/rev amplitude of a radial absorber at 70% span (having significantly lower mass than the chordwise absorber and producing comparable lag damping) is of the order of 4% of the rotor blade span. The static displacement of the radial absorber under centrifugal load needs to be limited using a frequency-dependent (high static stiffness, low dynamic stiffness) or nonlinear spring. The chordwise absorber can also undergo a large static displacement under the chordwise component of the centrifugal load if there is an offset from the feather axis, and this would again have to be limited using a strategy such as a frequency-dependent spring. Significant advantages of the radial absorber are—higher lag damping, lower absorber mass, space for absorber mass travel, and no chordwise travel of blade center of gravity reducing susceptibility to aeroelastic instability and dynamic pitch-link loads.

  10. One-Pot Ketone Synthesis with Alkylzinc Halides Prepared from Alkyl Halides via a Single Electron Transfer (SET) Process: New Extension of Fukuyama Ketone Synthesis.

    PubMed

    Lee, Jung Hwa; Kishi, Yoshito

    2016-06-01

    One-pot ketone synthesis has been developed with in situ activation of alkyl halides to alkylzinc halides in the presence of thioesters and Pd-catalyst. The new method provides us with a reliable option for a coupling at a late stage in a convergent synthesis of complex molecules, with use of a near 1:1 molar ratio of coupling partners. First, two facile, orthogonal methods have been developed for preparation of alkylzinc halides: (1) direct insertion of zinc dust to 1°- and 2°-alkyl halides in the presence of LiI in DMI and (2) early transition-metal assisted activation of alkyl halides via a single electron transfer (SET) process. CrCl2 has been found as an unprecedented, inevitable mediator for preparation of alkylzinc halides from alkyl halides, where CrCl2 likely functions to trap R·, generated via a SET process, and transfer it to Zn(II) to form RZnX. In addition to a commonly used CoPc, a new radical initiator NbCpCl4 has been discovered through the study. Second, with use of the two orthogonal methods, three sets of coupling conditions have been developed to complete one-pot ketone synthesis, with Condition A (Pd2dba3, PR3, Zn, LiI, TESCl, DMI), Condition B (A + CrCl2), and Condition C (B + NbCpCl4 or CoPc) being useful for simple linear and α-substituted substrates, simple linear and β-substituted substrates, and complex substrates, respectively. Condition C is applicable to the broadest range of substrates. Overall, one-pot ketone synthesis gives excellent yields, with good functional group tolerance. Controlled formation of alkylzinc halides by a combination of CrCl2 and NbCpCl4 or CoPc is crucial for its application to complex substrates. Interestingly, one-pot ketone synthesis does not suffer from the chemical instability due to the inevitable radical pathway(s), for example a 1,5-H shift. Notably, even with the increase in molecular size, no significant decrease in coupling efficiency has been noticed. To illustrate the synthetic value at a late

  11. Observation of vapor pressure enhancement of rare-earth metal-halide salts in the temperature range relevant to metal-halide lamps

    SciTech Connect

    Curry, J. J.; Henins, A.; Hardis, J. E.; Estupinan, E. G.; Lapatovich, W. P.; Shastri, S. D.

    2012-02-20

    Total vapor-phase densities of Dy in equilibrium with a DyI{sub 3}/InI condensate and Tm in equilibrium with a TmI{sub 3}/TlI condensate have been measured for temperatures between 900 K and 1400 K. The measurements show strong enhancements in rare-earth vapor densities compared to vapors in equilibrium with the pure rare-earth metal-halides. The measurements were made with x-ray induced fluorescence on the sector 1-ID beam line at the Advanced Photon Source. The temperature range and salt mixtures are relevant to the operation of metal-halide high-intensity discharge lamps.

  12. Porcelain enamel neutron absorbing material

    DOEpatents

    Iverson, Daniel C.

    1990-02-06

    A porcelain enamel composition as a neutron absorbing material can be prepared of a major proportion by weight of a cadmium compound and a minor proportion of compounds of boron, lithium and silicon. These compounds in the form of a porcelain enamel coating or layer on several alloys has been found to be particularly effective in enhancing the nuclear safety of equipment for use in the processing and storage of fissile material. The composition of the porcelain enamel coating can be tailored to match the coefficient of thermal expansion of the equipment to be coated and excellent coating adhesion can be achieved.

  13. Porcelain enamel neutron absorbing material

    DOEpatents

    Iverson, D.C.

    1987-11-20

    A porcelain enamel composition as a neutron absorbing material can be prepared of a major proportion by weight of a cadmium compound and a minor proportion of compound of boron, lithium and silicon. These compounds in the form of a porcelain enamel coating or layer on several alloys has been found to be particularly effective in enhancing the nuclear safety of equipment for use in the processing and storage of fissile material. The composition of the porcelain enamel coating can be tailored to match the coefficient of thermal expansion of the equipment to be coated and excellent coating adhesion can be achieved. 2 figs.

  14. Porcelain enamel neutron absorbing material

    DOEpatents

    Iverson, Daniel C.

    1990-01-01

    A porcelain enamel composition as a neutron absorbing material can be prepared of a major proportion by weight of a cadmium compound and a minor proportion of compounds of boron, lithium and silicon. These compounds in the form of a porcelain enamel coating or layer on several alloys has been found to be particularly effective in enhancing the nuclear safety of equipment for use in the processing and storage of fissile material. The composition of the porcelain enamel coating can be tailored to match the coefficient of thermal expansion of the equipment to be coated and excellent coating adhesion can be achieved.

  15. Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria

    USGS Publications Warehouse

    Miller, L.G.; Kalin, Robert M.; McCauley, S.E.; Hamilton, John T.G.; Harper, D.B.; Millet, D.B.; Oremland, R.S.; Goldstein, Allen H.

    2001-01-01

    The largest biological fractionations of stable carbon isotopes observed in nature occur during production of methane by methanogenic archaea. These fractionations result in substantial (as much as ???70???) shifts in ??13C relative to the initial substrate. We now report that a stable carbon isotopic fractionation of comparable magnitude (up to 70???) occurs during oxidation of methyl halides by methylotrophic bacteria. We have demonstrated biological fractionation with whole Cells of three methylotrophs (strain IMB-1, strain CC495, and strain MB2) and, to a lesser extent, with the purified cobalamin-dependent methyltransferase enzyme obtained from strain CC495. Thus, the genetic similarities recently reported between methylotrophs, and methanogens with respect to their pathways for C1-unit metabolism are also reflected in the carbon isotopic fractionations achieved by these organisms. We found that only part of the observed fractionation of carbon isotopes could be accounted for by the activity of the corrinoid methyltransferase enzyme, suggesting fractionation by enzymes further along the degradation pathway. These observations are of potential biogeochemical significance in the application of stable carbon isotope ratios to constrain the tropospheric budgets for the ozone-depleting halocarbons, methyl bromide and methyl chloride.

  16. Halides with Fifteen Aliphatic C-H···Anion Interaction Sites.

    PubMed

    Shi, Genggongwo; Aliakbar Tehrani, Zahra; Kim, Dongwook; Cho, Woo Jong; Youn, Il-Seung; Lee, Han Myoung; Yousuf, Muhammad; Ahmed, Nisar; Shirinfar, Bahareh; Teator, Aaron J; Lastovickova, Dominika N; Rasheed, Lubna; Lah, Myoung Soo; Bielawski, Christopher W; Kim, Kwang S

    2016-01-01

    Since the aliphatic C-H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C-H (Cali-H) groups has generally been considered not possible without the presence of additional binding sites that contain stronger interactions to the anion. Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic Cali-H groups. An X-ray structure of imidazolium-based scaffolds using Cali-H···A(-) interactions (A(-) = anion) shows that a halide anion is directly interacting with fifteen Cali-H groups (involving eleven hydrogen bonds, two bidentate hydrogen-bond-type binding interactions and two weakly hydrogen-bonding-like binding interactions). Additional supporting interactions and/or other binding sites are not observed. We note that such types of complexes may not be rare since such high numbers of binding sites for an anion are also found in analogous tetraalkylammonium complexes. The Cali-H···A(-) interactions are driven by the formation of a near-spherical dipole layer shell structure around the anion. The alternating layers of electrostatic charge around the anion arise because the repulsions between weakly positively charged H atoms are reduced by the presence of the weakly negatively charged C atoms connected to H atoms. PMID:27444513

  17. Ag-doped carbon aerogels for removing halide ions in water treatment.

    PubMed

    Sánchez-Polo, M; Rivera-Utrilla, J; Salhi, E; von Gunten, U

    2007-03-01

    The objective of this study was to analyze the efficiency of silver(Ag)-doped carbon aerogels for the removal of bromide (Br(-)) and iodide (I(-)) from drinking waters. Textural characterization of Ag-doped aerogels showed that an increase in the Ag dose added during the preparation process produced: (i) a reduction in the surface area (S(BET)) and (ii) an increase in mesopore (V(2)) and macropore (V(3)) volumes. Chemical characterization of the materials revealed an acidic surface (pH of point of zero charge, pH(PZC)=4.5, O(surface)=20%). The oxidation state of Ag was +1 and the surface concentration of this element ranged from 4% to 10%. The adsorption capacity (X(m)) and affinity of adsorbent (BX(m)) increased with a reduction in the radius of the halogenide. Furthermore, an increase in the adsorption capacity was observed with higher Ag concentrations on the aerogel surface. The high adsorption capacity of the aerogel may be due to the presence of Ag(I) on its surface, with the formation of the corresponding Ag halides. Our observations indicate that the halogenides adsorption on commercial activated carbon (Sorbo-Norit) is much lower than that of the Ag-doped carbon aerogels. The presence of chloride and natural organic matter (NOM) in the medium reduced the adsorption capacity of Br(-) and I(-) on Ag carbon aerogels. PMID:16970974

  18. Halides with Fifteen Aliphatic C–H···Anion Interaction Sites

    NASA Astrophysics Data System (ADS)

    Shi, Genggongwo; Aliakbar Tehrani, Zahra; Kim, Dongwook; Cho, Woo Jong; Youn, Il-Seung; Lee, Han Myoung; Yousuf, Muhammad; Ahmed, Nisar; Shirinfar, Bahareh; Teator, Aaron J.; Lastovickova, Dominika N.; Rasheed, Lubna; Lah, Myoung Soo; Bielawski, Christopher W.; Kim, Kwang S.

    2016-07-01

    Since the aliphatic C–H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C–H (Cali–H) groups has generally been considered not possible without the presence of additional binding sites that contain stronger interactions to the anion. Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic Cali–H groups. An X-ray structure of imidazolium-based scaffolds using Cali–H···A‑ interactions (A‑ = anion) shows that a halide anion is directly interacting with fifteen Cali–H groups (involving eleven hydrogen bonds, two bidentate hydrogen-bond-type binding interactions and two weakly hydrogen-bonding-like binding interactions). Additional supporting interactions and/or other binding sites are not observed. We note that such types of complexes may not be rare since such high numbers of binding sites for an anion are also found in analogous tetraalkylammonium complexes. The Cali–H···A‑ interactions are driven by the formation of a near-spherical dipole layer shell structure around the anion. The alternating layers of electrostatic charge around the anion arise because the repulsions between weakly positively charged H atoms are reduced by the presence of the weakly negatively charged C atoms connected to H atoms.

  19. High Photoluminescence Efficiency and Optically Pumped Lasing in Solution-Processed Mixed Halide Perovskite Semiconductors.

    PubMed

    Deschler, Felix; Price, Michael; Pathak, Sandeep; Klintberg, Lina E; Jarausch, David-Dominik; Higler, Ruben; Hüttner, Sven; Leijtens, Tomas; Stranks, Samuel D; Snaith, Henry J; Atatüre, Mete; Phillips, Richard T; Friend, Richard H

    2014-04-17

    The study of the photophysical properties of organic-metallic lead halide perovskites, which demonstrate excellent photovoltaic performance in devices with electron- and hole-accepting layers, helps to understand their charge photogeneration and recombination mechanism and unravels their potential for other optoelectronic applications. We report surprisingly high photoluminescence (PL) quantum efficiencies, up to 70%, in these solution-processed crystalline films. We find that photoexcitation in the pristine CH3NH3PbI3-xClx perovskite results in free charge carrier formation within 1 ps and that these free charge carriers undergo bimolecular recombination on time scales of 10s to 100s of ns. To exemplify the high luminescence yield of the CH3NH3PbI3-xClx perovskite, we construct and demonstrate the operation of an optically pumped vertical cavity laser comprising a layer of perovskite between a dielectric mirror and evaporated gold top mirrors. These long carrier lifetimes together with exceptionally high luminescence yield are unprecedented in such simply prepared inorganic semiconductors, and we note that these properties are ideally suited for photovoltaic diode operation. PMID:26269988

  20. Halides with Fifteen Aliphatic C–H···Anion Interaction Sites

    PubMed Central

    Shi, Genggongwo; Aliakbar Tehrani, Zahra; Kim, Dongwook; Cho, Woo Jong; Youn, Il-Seung; Lee, Han Myoung; Yousuf, Muhammad; Ahmed, Nisar; Shirinfar, Bahareh; Teator, Aaron J.; Lastovickova, Dominika N.; Rasheed, Lubna; Lah, Myoung Soo; Bielawski, Christopher W.; Kim, Kwang S.

    2016-01-01

    Since the aliphatic C–H···anion interaction is relatively weak, anion binding using hydrophobic aliphatic C–H (Cali–H) groups has generally been considered not possible without the presence of additional binding sites that contain stronger interactions to the anion. Herein, we report X-ray structures of organic crystals that feature a chloride anion bound exclusively by hydrophobic Cali–H groups. An X-ray structure of imidazolium-based scaffolds using Cali–H···A− interactions (A− = anion) shows that a halide anion is directly interacting with fifteen Cali–H groups (involving eleven hydrogen bonds, two bidentate hydrogen-bond-type binding interactions and two weakly hydrogen-bonding-like binding interactions). Additional supporting interactions and/or other binding sites are not observed. We note that such types of complexes may not be rare since such high numbers of binding sites for an anion are also found in analogous tetraalkylammonium complexes. The Cali–H···A− interactions are driven by the formation of a near-spherical dipole layer shell structure around the anion. The alternating layers of electrostatic charge around the anion arise because the repulsions between weakly positively charged H atoms are reduced by the presence of the weakly negatively charged C atoms connected to H atoms. PMID:27444513