Lighting Systems For High Speed Photography Applying Special Metal Halide Discharge Lamps

NASA Astrophysics Data System (ADS)

Gillum, Keith M.; Steuernagel, K. H.

1983-03-01

High speed photography requires, in addition to a good color quality of the light source, a very high level of illumination. Conventional lighting systems utilizing incandescent lamps or other metal halide lamp types has inherent problems of inefficient light output or poor color quality. Heat generated by incandescent lamps and the power these sources require drive up operating and installation costs. A most economical and practical solution was devised by using the metal halide discharge lamp developed by OSRAM, GmbH of Munich, West Germany. This lamp trade marked the HMITM Metallogen was primarily developed for the needs of the television and motion picture film industry. Due to their high efficiency and other consistent operating qualities these lamps also fulfill the needs of high speed photography, e.g. in crash test facilities, when special engineering activities are carried out. The OSRAM HMITM lamp is an AC discharge metal halide lamp with rare earth additives to increase both the efficiency and light output qualities. Since the lamp is an AC source, a special method had to be developed to overcome the strobing effect, which is normal for AC lamps given their modulated light output, when used with high speed cameras, (e.g. with >1000 fps). This method is based on an increased frequency for the lamp supply voltage coupled with a mix of the light output achieved using a multiphase mains power supply. First developed in 1977, this system using the OSRAM HMITM lamps was installed in a crash test facility of a major automotive manufacturer in West Germany. The design resulted in the best lighting and performance ever experienced. Since that time several other motor companies have made use of this breakthrough. Industrial and scientific users are now considering additional applications use of this advanced high speed lighting system.

RARE-EARTH METAL FISSION PRODUCTS FROM LIQUID U-Bi

DOEpatents

Wiswall, R.H.

1960-05-10

Fission product metals can be removed from solution in liquid bismuth without removal of an appreciable quantity of uranium by contacting the liquid metal solution with fused halides, as for example, the halides of sodium, potassium, and lithium and by adding to the contacted phases a quantity of a halide which is unstable relative to the halides of the fission products, a specific unstable halide being MgCl/sub 3/.

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

...-2009-BT-STD-0018] RIN 1904-AC00 Energy Conservation Program: Energy Conservation Standards for Metal... certain metal halide lamp fixtures. This document announces that the period for submitting comments on the... identify the Framework Document for energy conservation standards for metal halide lamp fixtures and...

Steric engineering of metal-halide perovskites with tunable optical band gaps

NASA Astrophysics Data System (ADS)

Filip, Marina R.; Eperon, Giles E.; Snaith, Henry J.; Giustino, Feliciano

2014-12-01

Owing to their high energy-conversion efficiency and inexpensive fabrication routes, solar cells based on metal-organic halide perovskites have rapidly gained prominence as a disruptive technology. An attractive feature of perovskite absorbers is the possibility of tailoring their properties by changing the elemental composition through the chemical precursors. In this context, rational in silico design represents a powerful tool for mapping the vast materials landscape and accelerating discovery. Here we show that the optical band gap of metal-halide perovskites, a key design parameter for solar cells, strongly correlates with a simple structural feature, the largest metal-halide-metal bond angle. Using this descriptor we suggest continuous tunability of the optical gap from the mid-infrared to the visible. Precise band gap engineering is achieved by controlling the bond angles through the steric size of the molecular cation. On the basis of these design principles we predict novel low-gap perovskites for optimum photovoltaic efficiency, and we demonstrate the concept of band gap modulation by synthesising and characterising novel mixed-cation perovskites.

Method for hydrocracking a heavy polynuclear hydrocarbonaceous feedstock in the presence of a molten metal halide catalyst

DOEpatents

Gorin, Everett

1981-01-01

A method for hydrocracking a heavy polynuclear hydrocarbonaceous feedstock to produce lighter hydrocarbon fuels by contacting the feedstock with hydrogen in the presence of a molten metal halide catalyst, the method comprising: mixing the feedstock with a heavy naphtha fraction which has an initial boiling point from about 100.degree. to about 160.degree. C. with a boiling point difference between the initial boiling point and the final boiling point of no more than about 50.degree. C. to produce a mixture; thereafter contacting the mixture with partially spent molten metal halide and hydrogen under temperature and pressure conditions so that the temperature is near the critical temperature of the heavy naphtha fraction; separating at least a portion of the heavy naphtha fraction and lighter hydrocarbon fuels from the partially spent molten metal halide, unreacted feedstock and reaction products; thereafter contacting the partially spent molten metal halide, unreacted feedstock and reaction products with hydrogen and fresh molten metal halide in a hydrocracking zone to produce additional lighter hydrocarbon fuels and separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide.

Alkaline and alkaline earth metal phosphate halides and phosphors

DOEpatents

Lyons, Robert Joseph; Setlur, Anant Achyut; Cleaver, Robert John

2012-11-13

Compounds, phosphor materials and apparatus related to nacaphite family of materials are presented. Potassium and rubidium based nacaphite family compounds and phosphors designed by doping divalent rare earth elements in the sites of alkaline earth metals in the nacaphite material families are descried. An apparatus comprising the phosphors based on the nacaphite family materials are presented herein. The compounds presented is of formula A.sub.2B.sub.1-yR.sub.yPO.sub.4X where the elements A, B, R, X and suffix y are defined such that A is potassium, rubidium, or a combination of potassium and rubidium and B is calcium, strontium, barium, or a combination of any of calcium, strontium and barium. X is fluorine, chlorine, or a combination of fluorine and chlorine, R is europium, samarium, ytterbium, or a combination of any of europium, samarium, and ytterbium, and y ranges from 0 to about 0.1.

10 CFR 431.324 - Uniform test method for the measurement of energy efficiency of metal halide ballasts.

Code of Federal Regulations, 2010 CFR

2010-01-01

... efficiency of metal halide ballasts. 431.324 Section 431.324 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION ENERGY EFFICIENCY PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures Test Procedures § 431.324 Uniform test method for the measurement of energy efficiency of metal...

Advances in the growth of alkaline-earth halide single crystals for scintillator detectors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boatner, Lynn A; Ramey, Joanne Oxendine; Kolopus, James A

2014-01-01

Alkaline-earth scintillators such as strontium iodide and other alkaline-earth halides activated with divalent europium represent some of the most efficient and highest energy resolution scintillators for use as gamma-ray detectors in a wide range of applications. These applications include the areas of nuclear nonproliferation, homeland security, the detection of undeclared nuclear material, nuclear physics and materials science, medical diagnostics, space physics, high energy physics, and radiation monitoring systems for first responders, police, and fire/rescue personnel. Recent advances in the growth of large single crystals of these scintillator materials hold the promise of higher crystal yields and significantly lower detector productionmore » costs. In the present work, we describe new processing protocols that, when combined with our molten salt filtration methods, have led to advances in achieving a significant reduction of cracking effects during the growth of single crystals of SrI2:Eu2+. In particular, we have found that extended pumping on the molten crystal-growth charge under vacuum for time periods extending up to 48 hours is generally beneficial in compensating for variations in the alkaline-earth halide purity and stoichiometry of the materials as initially supplied by commercial sources. These melt-pumping and processing techniques are now being applied to the purification of CaI2:Eu2+ and some mixed-anion europium-doped alkaline-earth halides prior to single-crystal growth by means of the vertical Bridgman technique. The results of initial studies of the effects of aliovalent doping of SrI2:Eu2+ on the scintillation characteristics of this material are also described.« less

SEPARATION OF METAL SALTS BY ADSORPTION

DOEpatents

Gruen, D.M.

1959-01-20

It has been found that certain metal salts, particularly the halides of iron, cobalt, nickel, and the actinide metals, arc readily absorbed on aluminum oxide, while certain other salts, particularly rare earth metal halides, are not so absorbed. Use is made of this discovery to separate uranium from the rare earths. The metal salts are first dissolved in a molten mixture of alkali metal nitrates, e.g., the eutectic mixture of lithium nitrate and potassium nitrate, and then the molten salt solution is contacted with alumina, either by slurrying or by passing the salt solution through an absorption tower. The process is particularly valuable for the separation of actinides from lanthanum-group rare earths.

Metal halides vapor lasers with inner reactor and small active volume.

NASA Astrophysics Data System (ADS)

Shiyanov, D. V.; Sukhanov, V. B.; Evtushenko, G. S.

2018-04-01

Investigation of the energy characteristics of copper, manganese, lead halide vapor lasers with inner reactor and small active volume 90 cm3 was made. The optimal operating pulse repetition rates, temperatures, and buffer gas pressure for gas discharge tubes with internal and external electrodes are determined. Under identical pump conditions, such systems are not inferior in their characteristics to standard metal halide vapor lasers. It is shown that the use of a zeolite halogen generator provides lifetime laser operation.

Methods for producing single crystal mixed halide perovskites

DOEpatents

Zhu, Kai; Zhao, Yixin

2017-07-11

An aspect of the present invention is a method that includes contacting a metal halide and a first alkylammonium halide in a solvent to form a solution and maintaining the solution at a first temperature, resulting in the formation of at least one alkylammonium halide perovskite crystal, where the metal halide includes a first halogen and a metal, the first alkylammonium halide includes the first halogen, the at least one alkylammonium halide perovskite crystal includes the metal and the first halogen, and the first temperature is above about 21.degree. C.

Homoepitaxial growth of metal halide crystals investigated by reflection high-energy electron diffraction

DOE PAGES

Chen, Pei; Kuttipillai, Padmanaban S.; Wang, Lili; ...

2017-01-10

Here, we report the homoepitaxial growth of a metal halide on single crystals investigated with in situ reflection high-energy electron diffraction (RHEED) and ex situ atomic force microscopy (AFM). Epitaxial growth of NaCl on NaCl (001) is explored as a function of temperature and growth rate which provides the first detailed report of RHEED oscillations for metal halide growth. Layer-by-layer growth is observed at room temperature accompanied by clear RHEED oscillations while the growth mode transitions to an island (3D) mode at low temperature. At higher temperatures (>100 °C), RHEED oscillations and AFM data indicate a transition to a step-flowmore » growth mode. To show the importance of such metal halide growth, green organic light-emitting diodes (OLEDs) are demonstrated using a doped NaCl film with a phosphorescent emitter as the emissive layer. This study demonstrates the ability to perform in situ and non-destructive RHEED monitoring even on insulating substrates and could enable doped single crystals and crystalline substrates for a range of optoelectronic applications.« less

ELECTROLYTIC PROCESS FOR PRODUCING METALS

DOEpatents

Kopelman, B.; Holden, R.B.

1961-06-01

A method is described for reducing beryllium halides to beryllium. The beryllfum halide fs placed in an eutectic mixture of alkali halides and alkaline earth halides. The constituents of this eutectic bath are so chosen that it has a melting point less than the boiling point of mercury, which acts as a cathode for the system. The beryllium metal is then deposited in the mercury upon electrolysis.

Theory of metal atom-water interactions and alkali halide dimers

NASA Technical Reports Server (NTRS)

Jordan, K. D.; Kurtz, H. A.

1982-01-01

Theoretical studies of the interactions of metal atoms with water and some of its isoelectronic analogs, and of the properties of alkali halides and their aggregates are discussed. Results are presented of ab initio calculations of the heats of reaction of the metal-water adducts and hydroxyhydrides of Li, Be, B, Na, Mg, and Al, and of the bond lengths and angles an; the heats of reaction for the insertion of Al into HF, H2O, NH3, H2S and CH3OH, and Be and Mg into H2O. Calculations of the electron affinities and dipole moments and polarizabilities of selected gas phase alkali halide monomers and dimers are discussed, with particular attention given to results of calculations of the polarizability of LiF taking into account electron correlation effects, and the polarizability of the dimer (LiF)2.

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.

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.

Metal-halide mixtures for latent heat energy storage

NASA Astrophysics Data System (ADS)

Chen, K.; Manvi, R.

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.

Pressure-induced metallization of the halide perovskite (CH 3NH 3)PbI 3

DOE PAGES

Jaffe, Adam; Lin, Yu; Mao, Wendy L.; ...

2017-03-14

We report the metallization of the hybrid perovskite semiconductor (MA)PbI 3 (MA = CH 3NH 3 +) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI 3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study ofmore » metallic properties in oxide perovskites has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Lastly, pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.« less

Pressure-Induced Metallization of the Halide Perovskite (CH 3 NH 3 )PbI 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaffe, Adam; Lin, Yu; Mao, Wendy L.

We report the metallization of the hybrid perovskite semiconductor (MA)PbI3 (MA = CH3NH3+) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study of metallic properties in oxide perovskitesmore » has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.« less

Pressure-induced metallization of the halide perovskite (CH 3NH 3)PbI 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaffe, Adam; Lin, Yu; Mao, Wendy L.

We report the metallization of the hybrid perovskite semiconductor (MA)PbI 3 (MA = CH 3NH 3 +) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI 3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study ofmore » metallic properties in oxide perovskites has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Lastly, pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstrates the promise of the continued study of halide perovskites under a range of thermodynamic conditions, toward realizing wholly new electronic properties.« less

Parity-Forbidden Transitions and Their Impact on the Optical Absorption Properties of Lead-Free Metal Halide Perovskites and Double Perovskites.

PubMed

Meng, Weiwei; Wang, Xiaoming; Xiao, Zewen; Wang, Jianbo; Mitzi, David B; Yan, Yanfa

2017-07-06

Using density functional theory calculations, we analyze the optical absorption properties of lead (Pb)-free metal halide perovskites (AB 2+ X 3 ) and double perovskites (A 2 B + B 3+ X 6 ) (A = Cs or monovalent organic ion, B 2+ = non-Pb divalent metal, B + = monovalent metal, B 3+ = trivalent metal, X = halogen). We show that if B 2+ is not Sn or Ge, Pb-free metal halide perovskites exhibit poor optical absorptions because of their indirect band gap nature. Among the nine possible types of Pb-free metal halide double perovskites, six have direct band gaps. Of these six types, four show inversion symmetry-induced parity-forbidden or weak transitions between band edges, making them not ideal for thin-film solar cell applications. Only one type of Pb-free double perovskite shows optical absorption and electronic properties suitable for solar cell applications, namely, those with B + = In, Tl and B 3+ = Sb, Bi. Our results provide important insights for designing new metal halide perovskites and double perovskites for optoelectronic applications.

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 429.54 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION CERTIFICATION, COMPLIANCE, AND ENFORCEMENT FOR... and tested to ensure that: (i) Any represented value of estimated energy efficiency calculated as the...

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 429.54 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION CERTIFICATION, COMPLIANCE, AND ENFORCEMENT FOR... and tested to ensure that: (i) Any represented value of estimated energy efficiency calculated as the...

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 429.54 Energy DEPARTMENT OF ENERGY ENERGY CONSERVATION CERTIFICATION, COMPLIANCE, AND ENFORCEMENT FOR... and tested to ensure that: (i) Any represented value of estimated energy efficiency calculated as the...

Evaluation of Metal Halide, Plasma, and LED Lighting Technologies for a Hydrogen Fuel Cell Mobile Light (H 2 LT)

DOE PAGES

Miller, L. B.; Donohoe, S. P.; Jones, M. H.; ...

2015-04-22

This article reports on the testing and comparison of a prototype hydrogen fuel cell light tower (H2LT) and a conventional diesel-powered metal halide light trailer for use in road maintenance and construction activities. The prototype was originally outfitted with plasma lights and then with light-emitting diode (LED) luminaires. Light output and distribution, lighting energy efficiency (i.e., efficacy), power source thermal efficiency, and fuel costs are compared. The metal halide luminaires have 2.2 and 3.1 times more light output than the plasma and LED luminaires, respectively, but they require more power/lumen to provide that output. The LED luminaires have 1.6 timesmore » better light efficacy than either the metal halide or plasma luminaires. The light uniformity ratios produced by the plasma and LED towers are acceptable. The fuel cell thermal efficiency at the power required to operate the plasma lights is 48%, significantly higher than the diesel generator efficiency of 23% when operating the metal halide lights. Due to the increased efficiency of the fuel cell and the LED lighting, the fuel cost per lumen-hour of the H2LT is 62% of the metal halide diesel light tower assuming a kilogram of hydrogen is twice the cost of a gallon of diesel fuel.« less

Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: A Review

PubMed Central

Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

2018-01-01

Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical, and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter, or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article. PMID:29755967

Metal-Mediated Halogen Exchange in Aryl and Vinyl Halides: a Review

NASA Astrophysics Data System (ADS)

Evano, Gwilherm; Nitelet, Antoine; Thilmany, Pierre; Dewez, Damien F.

2018-04-01

Halogenated arenes and alkenes are of prime importance in many areas of science, especially in the pharmaceutical, agrochemical and chemical industries. While the simplest ones are commercially available, some of them are still hardly accessible depending on their substitution patterns and the nature of the halogen atom. Reactions enabling the selective and efficient replacement of the halogen atom of an aryl or alkenyl halide by another one, lighter or heavier, are therefore of major importance since they can be used for example to turn a less reactive aryl/alkenyl chloride into the more reactive iodinated derivatives or, in a reversed sense, to block an undesired reactivity, for late-stage modifications or for the introduction of a radionuclide. If some halogen exchange reactions are possible with activated substrates, they usually require catalysis with metal complexes. Remarkably efficient processes have been developed for metal-mediated halogen exchange in aryl and vinyl halides: they are overviewed, in a comprehensive manner, in this review article.

10 CFR Appendix C to Subpart S of... - Enforcement for Performance Standards; Compliance Determination Procedure for Metal Halide Lamp...

Code of Federal Regulations, 2011 CFR

2011-01-01

... Determination Procedure for Metal Halide Lamp Ballasts C Appendix C to Subpart S of Part 431 Energy DEPARTMENT... EQUIPMENT Metal Halide Lamp Ballasts and Fixtures Pt. 431, Subpt. S, App. C Appendix C to Subpart S of Part..., and n1 is the total number of tests. (c) Compute the standard deviation (S1) of the measured energy...

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.

Intriguing optoelectronic properties of metal halide perovskites

DOE PAGES

Manser, Joseph S.; Christians, Jeffrey A.; Kamat, Prashant V.

2016-06-21

Here, a new chapter in the long and distinguished history of perovskites is being written with the breakthrough success of metal halide perovskites (MHPs) as solution-processed photovoltaic (PV) absorbers. The current surge in MHP research has largely arisen out of their rapid progress in PV devices; however, these materials are potentially suitable for a diverse array of optoelectronic applications. Like oxide perovskites, MHPs have ABX 3 stoichiometry, where A and B are cations and X is a halide anion. Here, the underlying physical and photophysical properties of inorganic (A = inorganic) and hybrid organic-inorganic (A = organic) MHPs are reviewedmore » with an eye toward their potential application in emerging optoelectronic technologies. Significant attention is given to the prototypical compound methylammonium lead iodide (CH 3NH 3PbI 3) due to the preponderance of experimental and theoretical studies surrounding this material. We also discuss other salient MHP systems, including 2- dimensional compounds, where relevant. More specifically, this review is a critical account of the interrelation between MHP electronic structure, absorption, emission, carrier dynamics and transport, and other relevant photophysical processes that have propelled these materials to the forefront of modern optoelectronics research.« less

EPR study of electron bombarded alkali- and alkaline-earth halide crystal surfaces

NASA Technical Reports Server (NTRS)

Fryburg, G. C.; Lad, R. A.

1975-01-01

An EPR study of electron bombarded LiF, NaCl, KCl, CaF2 and BaF2 polycrystalline surfaces has shown that small metal particles are formed on the surfaces of the crystals. Identification was made from CESR signals. The symmetric line-shape of the signals, even at 77 K, indicated that the particles were less than 0.5 micron in diameter. Signals due to F centers were observed in LiF but not in the other halides. Implications to metal deposition are considered.

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.

Recycling of rare earth metals from rare earth-transition metal alloy scrap by liquid metal extraction

DOEpatents

Ellis, Timothy W.; Schmidt, Frederick A.

1995-08-01

Method of treating rare earth metal-bearing scrap, waste or other material (e.g. Nd--Fe--B or Dy--Tb--Fe scrap) to recover the rare earth metal comprising melting the rare earth metal-bearing material, melting a Group IIA metal extractant, such as Mg, Ca, or Ba, in which the rare earth is soluble in the molten state, and contacting the melted material and melted extractant at a temperature and for a time effective to extract the rare earth from the melted material into the melted extractant. The rare earth metal is separated from the extractant metal by vacuum sublimation or distillation.

Recycling of rare earth metals from rare earth-transition metal alloy scrap by liquid metal extraction

DOEpatents

Ellis, T.W.; Schmidt, F.A.

1995-08-01

A method is described for treating rare earth metal-bearing scrap, waste or other material (e.g. Nd--Fe--B or Dy--Tb--Fe scrap) to recover the rare earth metal comprising melting the rare earth metal-bearing material, melting a Group IIA metal extractant, such as Mg, Ca, or Ba, in which the rare earth is soluble in the molten state, and contacting the melted material and melted extractant at a temperature and for a time effective to extract the rare earth from the melted material into the melted extractant. The rare earth metal is separated from the extractant metal by vacuum sublimation or distillation. 2 figs.

Europium-activated phosphors containing oxides of rare-earth and group-IIIB metals and method of making the same

DOEpatents

Comanzo, Holly Ann; Setlur, Anant Achyut; Srivastava, Alok Mani

2006-04-04

Europium-activated phosphors comprise oxides of at least a rare-earth metal selected from the group consisting of gadolinium, yttrium, lanthanum, and combinations thereof and at least a Group-IIIB metal selected from the group consisting of aluminum, gallium, indium, and combinations thereof. A method for making such phosphors comprises adding at least a halide of at least one of the selected Group-IIIB metals in a starting mixture. The method further comprises firing the starting mixture in an oxygen-containing atmosphere. The phosphors produced by such a method exhibit improved absorption in the UV wavelength range and improved quantum efficiency.

Europium-activated phosphors containing oxides of rare-earth and group-IIIB metals and method of making the same

DOEpatents

Comanzo, Holly Ann; Setlur, Anant Achyut; Srivastava, Alok Mani; Manivannan, Venkatesan

2004-07-13

Europium-activated phosphors comprise oxides of at least a rare-earth metal selected from the group consisting of gadolinium, yttrium, lanthanum, and combinations thereof and at least a Group-IIIB metal selected from the group consisting of aluminum, gallium, indium, and combinations thereof. A method for making such phosphors comprises adding at least a halide of at least one of the selected Group-IIIB metals in a starting mixture. The method further comprises firing the starting mixture in an oxygen-containing atmosphere. The phosphors produced by such a method exhibit improved absorption in the UV wavelength range and improved quantum efficiency.

Highly Efficient Broadband Yellow Phosphor Based on Zero-Dimensional Tin Mixed-Halide Perovskite.

PubMed

Zhou, Chenkun; Tian, Yu; Yuan, Zhao; Lin, Haoran; Chen, Banghao; Clark, Ronald; Dilbeck, Tristan; Zhou, Yan; Hurley, Joseph; Neu, Jennifer; Besara, Tiglet; Siegrist, Theo; Djurovich, Peter; Ma, Biwu

2017-12-27

Organic-inorganic hybrid metal halide perovskites have emerged as a highly promising class of light emitters, which can be used as phosphors for optically pumped white light-emitting diodes (WLEDs). By controlling the structural dimensionality, metal halide perovskites can exhibit tunable narrow and broadband emissions from the free-exciton and self-trapped excited states, respectively. Here, we report a highly efficient broadband yellow light emitter based on zero-dimensional tin mixed-halide perovskite (C 4 N 2 H 14 Br) 4 SnBr x I 6-x (x = 3). This rare-earth-free ionically bonded crystalline material possesses a perfect host-dopant structure, in which the light-emitting metal halide species (SnBr x I 6-x 4- , x = 3) are completely isolated from each other and embedded in the wide band gap organic matrix composed of C 4 N 2 H 14 Br - . The strongly Stokes-shifted broadband yellow emission that peaked at 582 nm from this phosphor, which is a result of excited state structural reorganization, has an extremely large full width at half-maximum of 126 nm and a high photoluminescence quantum efficiency of ∼85% at room temperature. UV-pumped WLEDs fabricated using this yellow emitter together with a commercial europium-doped barium magnesium aluminate blue phosphor (BaMgAl 10 O 17 :Eu 2+ ) can exhibit high color rendering indexes of up to 85.

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

Code of Federal Regulations, 2011 CFR

2011-01-01

... main functions. Ballast means a device used with an electric discharge lamp to obtain necessary circuit... purpose of controlling the ballast and putting the ballast in standby mode. Electronic ballast means a... instead starts lamps with high ballast open circuit voltage. Pulse-start metal halide ballast means an...

Highly tunable colloidal perovskite nanoplatelets through variable cation, metal, and halide composition

DOE PAGES

Weidman, Mark C.; Seitz, Michael; Stranks, Samuel D.; ...

2016-07-29

Here, 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 L 2[ABX 3] n-1BX 4, 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),more » 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.« less

METAL SURFACE TREATMENT

DOEpatents

Eubank, L.D.

1958-08-12

Improved flux baths are described for use in conjunction with hot dipped coatings for uranium. The flux bath consists of molten alkali metal, or alkaline earth metal halides. One preferred embodiment comprises a bath containing molten KCl, NaCl, and LiCl in proportions approximating the triple eutectic.

PROCESS OF PRODUCING ACTINIDE METALS

DOEpatents

Magel, T.T.

1959-07-14

The preparation of actinide metals in workable, coherent form is described. In general, the objects of the invention are achieved by heating a mixture of an oxide and a halide of an actinide metal such as uranium with an alkali metal on alkaline earth metal reducing agent in the presence of iodine.

Pd-Metalated Conjugated Nanoporous Polycarbazoles for Additive-Free Cyanation of Aryl Halides: Boosting Catalytic Efficiency through Spatial Modulation

DOE PAGES

Ding, Shunmin; Tian, Chengcheng; Zhu, Xiang; ...

2017-03-23

Transition-metal-catalyzed cyanation of aryl halides is a common route to benzonitriles, which are integral to many industrial procedures. However, traditional homogeneous catalysts for such processes are expensive and suffer poor recyclability, so a heterogeneous analogue is highly desired. A novel spatial modulation approach has been developed in this paper to fabricate a heterogeneous Pd-metalated nanoporous polymer, which catalyzes the cyanation of aryl halides without need for ligands. Finally, the catalyst displays high activity in the synthesis of benzonitriles, including high product yields, excellent stability and recycling, and broad functional-group tolerance.

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.

A Liquid Chromatography Detector for Transition and Rare-Earth Metal Ions Based on a Cupric Ion-Selective Electrode

DTIC Science & Technology

1981-05-01

RARE-EARTH METAL IONS BASED ON A CUPRIC ION-SELECTIVE ELECTRODE By - 4 R. CAMERON DOREY TECHNICAL REPORT FJSRL-TR-81-0005 MAY 1981 Approved for public...FORM . REPORT NUMBER 12. GOVT ACCESSION NO. 3. RECIPIENT’S CATALOG NUMBER FJSRL-TR-81-0005BO CO ENGO 4 . TITLE (and Subtitle) 5. TYPE OF REPORT & PERIOD...common anions, including halide ions, is shown, and the advantages and limitations of the system are discussed. II ’ 4 UNCLASSIFIED SECURITY

Infrared Dielectric Screening Determines the Low Exciton Binding Energy of Metal-Halide Perovskites.

PubMed

Umari, Paolo; Mosconi, Edoardo; De Angelis, Filippo

2018-02-01

The performance of lead-halide perovskites in optoelectronic devices is due to a unique combination of factors, including highly efficient generation, transport, and collection of photogenerated charge carriers. The mechanism behind efficient charge generation in lead-halide perovskites is still largely unknown. Here, we investigate the factors that influence the exciton binding energy (E b ) in a series of metal-halide perovskites using accurate first-principles calculations based on solution of the Bethe-Salpeter equation, coupled to ab initio molecular dynamics simulations. We find that E b is strongly modulated by screening from low-energy phonons, which account for a factor ∼2 E b reduction, while dynamic disorder and rotational motion of the organic cations play a minor role. We calculate E b = 15 meV for MAPbI 3 , in excellent agreement with recent experimental estimates. We then explore how different material combinations (e.g., replacing Pb → Pb:Sn→ Sn; and MA → FA → Cs) may lead to different E b values and highlight the mechanisms underlying E b tuning.

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.

NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shmyreva, Anna A.; Safdari, Majid; Furó, István

2016-06-14

Orders of magnitude decrease of {sup 207}Pb and {sup 199}Hg NMR longitudinal relaxation times T{sub 1} upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX{sub 2} (Me = Pb, Hg and X = Cl, Br, I). In lead(II) halides, the most dramatic decrease of T{sub 1} relative to that in a static sample is in PbI{sub 2}, while it is smaller but still significant in PbBr{sub 2}, and not detectable in PbCl{sub 2}. The effect is magnetic-field dependent but independent of the spinning speed in the range 200–15 000 Hz. The observed relaxation enhancementmore » is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.« less

The Role of Metal Halide Perovskites in Next-Generation Lighting Devices.

PubMed

Lozano, Gabriel

2018-06-28

The development of smart illumination sources represents a central challenge of the current technology. In this context, the quest for novel materials that enable efficient light generation is essential. Metal halide compounds with perovskite crystalline structure (ABX3) have gained tremendous interest in the last five years since they come as easy-to-prepare high performance semiconductors. Perovskite absorbers are driving the power-conversion-efficiencies of thin film photovoltaics to unprecedented values. Nowadays, mixed-cation mixed-halide lead perovskite solar cells reach efficiencies consistently over 20% and promise to get close to 30% in multi-junction devices when combined with silicon cells at no surcharge. Nonetheless, perovskites' fame extends further since extensive research on these novel semiconductors has also revealed their brightest side. Soon after their irruption in the photovoltaic scenario, demonstration of efficient color tunable -with high color purity- perovskite emitters has opened new avenues for light generation applications that are timely to discuss herein.

A Kirkwood-Buff derived force field for alkaline earth halide salts

NASA Astrophysics Data System (ADS)

Naleem, Nawavi; Bentenitis, Nikolaos; Smith, Paul E.

2018-06-01

The activity and function of many macromolecules in cellular environments are coupled with the binding of divalent ions such as calcium or magnesium. In principle, computer simulations can be used to understand the molecular level aspects of how many important macromolecules interact with ions. However, most of the force fields currently available often fail to accurately reproduce the properties of divalent ions in aqueous environments. Here we develop classical non-polarizable force fields for the aqueous alkaline earth metal halides (MX2), where M = Mg2+, Ca2+, Sr2+, Ba2+ and X = Cl-, Br-, I-, which can be used in bimolecular simulations and which are compatible with the Simple Point Charge/Extended (SPC/E) water model. The force field parameters are specifically developed to reproduce the experimental Kirkwood-Buff integrals for aqueous solutions and thereby the experimental activity derivatives, partial molar volumes, and excess coordination numbers. This ensures that a reasonable balance between ion-ion, ion-water, and water-water distributions is obtained. However, this requires a scaling of the cation to water oxygen interaction strength in order to accurately reproduce the integrals. The scaling factors developed for chloride salts are successfully transferable to the bromide and iodide salts. Use of these new models leads to reasonable diffusion constants and dielectric decrements. However, the performance of the models decreases with increasing salt concentration (>4m), and simulations of the pure crystals exhibited unstable behavior.

A Kirkwood-Buff derived force field for alkaline earth halide salts.

PubMed

Naleem, Nawavi; Bentenitis, Nikolaos; Smith, Paul E

2018-06-14

The activity and function of many macromolecules in cellular environments are coupled with the binding of divalent ions such as calcium or magnesium. In principle, computer simulations can be used to understand the molecular level aspects of how many important macromolecules interact with ions. However, most of the force fields currently available often fail to accurately reproduce the properties of divalent ions in aqueous environments. Here we develop classical non-polarizable force fields for the aqueous alkaline earth metal halides (MX 2 ), where M = Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ and X = Cl - , Br - , I - , which can be used in bimolecular simulations and which are compatible with the Simple Point Charge/Extended (SPC/E) water model. The force field parameters are specifically developed to reproduce the experimental Kirkwood-Buff integrals for aqueous solutions and thereby the experimental activity derivatives, partial molar volumes, and excess coordination numbers. This ensures that a reasonable balance between ion-ion, ion-water, and water-water distributions is obtained. However, this requires a scaling of the cation to water oxygen interaction strength in order to accurately reproduce the integrals. The scaling factors developed for chloride salts are successfully transferable to the bromide and iodide salts. Use of these new models leads to reasonable diffusion constants and dielectric decrements. However, the performance of the models decreases with increasing salt concentration (>4m), and simulations of the pure crystals exhibited unstable behavior.

Unraveling luminescence mechanisms in zero-dimensional halide perovskites

DOE PAGES

Han, Dan; Shi, Hongliang; Ming, Wenmei; ...

2018-01-01

Zero-dimensional (0D) halides perovskites, in which anionic metal-halide octahedra (MX 6 ) 4− are separated by organic or inorganic countercations, have recently shown promise as excellent luminescent materials.

Unraveling luminescence mechanisms in zero-dimensional halide perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Han, Dan; Shi, Hongliang; Ming, Wenmei

Zero-dimensional (0D) halides perovskites, in which anionic metal-halide octahedra (MX 6 ) 4− are separated by organic or inorganic countercations, have recently shown promise as excellent luminescent materials.

Unraveling luminescence mechanisms in zero-dimensional halide perovskites

DOE PAGES

Han, Dan; Shi, Hongliang; Ming, Wenmei; ...

2018-05-18

Here, zero-dimensional (0D) halides perovskites, in which anionic metal-halide octahedra (MX 6) 4– are separated by organic or inorganic countercations, have recently shown promise as excellent luminescent materials.

The impacts of new street light technologies: experimentally testing the effects on bats of changing from low-pressure sodium to white metal halide

PubMed Central

Stone, Emma Louise; Wakefield, Andrew; Harris, Stephen; Jones, Gareth

2015-01-01

Artificial light at night is a major feature of anthropogenic global change and is increasingly recognized as affecting biodiversity, often negatively. On a global scale, newer technology white lights are replacing orange sodium lights to reduce energy waste. In 2009, Cornwall County Council (UK) commenced replacement of existing low-pressure sodium (LPS) high intensity discharge (HID) street lights with new Phillips CosmoPolis white ceramic metal halide street lights to reduce energy wastage. This changeover provided a unique collaborative opportunity to implement a before-after-control-impact field experiment to investigate the ecological effects of newly installed broad spectrum light technologies. Activity of the bat species Pipistrellus pipistrellus, P. pygmaeus and Nyctalus/Eptesicus spp. was significantly higher at metal halide than LPS lights, as found in other studies of bat activity at old technology (i.e. mercury vapour) white light types. No significant difference was found in feeding attempts per bat pass between light types, though more passes overall were recorded at metal halide lights. Species-specific attraction of bats to the metal halide lights could have cascading effects at lower trophic levels. We highlight the need for further research on possible ecosystem-level effects of light technologies before they are installed on a wide scale. PMID:25780239

Direct Evidence of Exciton-Exciton Annihilation in Single-Crystalline Organic Metal Halide Nanotube Assemblies.

PubMed

Ma, Ying-Zhong; Lin, Haoran; Du, Mao-Hua; Doughty, Benjamin; Ma, Biwu

2018-05-03

Excitons in low-dimensional organic-inorganic metal halide hybrid structures are commonly thought to undergo rapid self-trapping following creation due to strong quantum confinement and exciton-phonon interaction. Here we report an experimental study probing the dynamics of these self-trapped excitons in the single-crystalline bulk assemblies of 1D organic metal halide nanotubes, (C 6 H 13 N 4 ) 3 Pb 2 Br 7 . Through time-resolved photoluminescence (PL) measurements at different excitation intensities, we observed a marked variation in the PL decay behavior that is manifested by an accelerated decay rate with increasing excitation fluence. Our results offer direct evidence of the occurrence of an exciton-exciton annihilation process, a nonlinear relaxation phenomenon that takes place only when some of the self-trapped excitons become mobile and can approach either each other or those trapped excitons. We further identify a fast and dominant PL decay component with a lifetime of ∼2 ns with a nearly invariant relative area for all acquired PL kinetics, suggesting that this rapid relaxation process is intrinsic.

Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals

PubMed Central

2018-01-01

We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic–inorganic lead halide perovskite nanocrystals (NCs). The main limitation of the protocols that are currently in use, such as the hot injection and the ligand-assisted reprecipitation routes, is that they employ PbX2 (X = Cl, Br, or I) salts as both lead and halide precursors. This imposes restrictions on being able to precisely tune the amount of reaction species and, consequently, on being able to regulate the composition of the final NCs. In order to overcome this issue, we show here that benzoyl halides can be efficiently used as halide sources to be injected in a solution of metal cations (mainly in the form of metal carboxylates) for the synthesis of APbX3 NCs (in which A = Cs+, CH3NH3+, or CH(NH2)2+). In this way, it is possible to independently tune the amount of both cations and halide precursors in the synthesis. The APbX3 NCs that were prepared with our protocol show excellent optical properties, such as high photoluminescence quantum yields, low amplified spontaneous emission thresholds, and enhanced stability in air. It is noteworthy that CsPbI3 NCs, which crystallize in the cubic α phase, are stable in air for weeks without any postsynthesis treatment. The improved properties of our CsPbX3 perovskite NCs can be ascribed to the formation of lead halide terminated surfaces, in which Cs cations are replaced by alkylammonium ions. PMID:29378131

Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals.

PubMed

Imran, Muhammad; Caligiuri, Vincenzo; Wang, Mengjiao; Goldoni, Luca; Prato, Mirko; Krahne, Roman; De Trizio, Luca; Manna, Liberato

2018-02-21

We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic-inorganic lead halide perovskite nanocrystals (NCs). The main limitation of the protocols that are currently in use, such as the hot injection and the ligand-assisted reprecipitation routes, is that they employ PbX 2 (X = Cl, Br, or I) salts as both lead and halide precursors. This imposes restrictions on being able to precisely tune the amount of reaction species and, consequently, on being able to regulate the composition of the final NCs. In order to overcome this issue, we show here that benzoyl halides can be efficiently used as halide sources to be injected in a solution of metal cations (mainly in the form of metal carboxylates) for the synthesis of APbX 3 NCs (in which A = Cs + , CH 3 NH 3 + , or CH(NH 2 ) 2 + ). In this way, it is possible to independently tune the amount of both cations and halide precursors in the synthesis. The APbX 3 NCs that were prepared with our protocol show excellent optical properties, such as high photoluminescence quantum yields, low amplified spontaneous emission thresholds, and enhanced stability in air. It is noteworthy that CsPbI 3 NCs, which crystallize in the cubic α phase, are stable in air for weeks without any postsynthesis treatment. The improved properties of our CsPbX 3 perovskite NCs can be ascribed to the formation of lead halide terminated surfaces, in which Cs cations are replaced by alkylammonium ions.

10 CFR Appendix A to Subpart S of... - Compliance Statement for Metal Halide Lamp Ballasts

Code of Federal Regulations, 2011 CFR

2011-01-01

... Equipment: Metal Halide Lamp Ballasts Manufacturer's or Private Labeler's Name and Address: [Company name] (“the company”) submits this Compliance Statement under 10 CFR Part 431 (Energy Efficiency Program for... Reports submitted by or on behalf of this company. All information in such Certification Report(s) and in...

The impacts of new street light technologies: experimentally testing the effects on bats of changing from low-pressure sodium to white metal halide.

PubMed

Stone, Emma Louise; Wakefield, Andrew; Harris, Stephen; Jones, Gareth

2015-05-05

Artificial light at night is a major feature of anthropogenic global change and is increasingly recognized as affecting biodiversity, often negatively. On a global scale, newer technology white lights are replacing orange sodium lights to reduce energy waste. In 2009, Cornwall County Council (UK) commenced replacement of existing low-pressure sodium (LPS) high intensity discharge (HID) street lights with new Phillips CosmoPolis white ceramic metal halide street lights to reduce energy wastage. This changeover provided a unique collaborative opportunity to implement a before-after-control-impact field experiment to investigate the ecological effects of newly installed broad spectrum light technologies. Activity of the bat species Pipistrellus pipistrellus, P. pygmaeus and Nyctalus/Eptesicus spp. was significantly higher at metal halide than LPS lights, as found in other studies of bat activity at old technology (i.e. mercury vapour) white light types. No significant difference was found in feeding attempts per bat pass between light types, though more passes overall were recorded at metal halide lights. Species-specific attraction of bats to the metal halide lights could have cascading effects at lower trophic levels. We highlight the need for further research on possible ecosystem-level effects of light technologies before they are installed on a wide scale. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Sub-millimeter Spectroscopy of Astrophysically Important Molecules and Ions: Metal Hydrides, Halides, and Cyanides

NASA Technical Reports Server (NTRS)

Ziurys, L. M.; Flory, M. A.; Halfen, D. T.

2006-01-01

With the advent of SOFIA, Herschel, and SAFIR, new wavelength regions will become routinely accessible for astronomical spectroscopy, particularly at submm frequencies (0.5-1.1 THz). Molecular emission dominates the spectra of dense interstellar gas at these wavelengths. Because heterodyne detectors are major instruments of these missions, accurate knowledge of transition frequencies is crucial for their success. The Ziurys spectroscopy laboratory has been focusing on the measurement of the pure rotational transitions of astrophysically important molecules in the sub-mm regime. Of particular interest have been metal hydride species and their ions, as well as metal halides and cyanides. A new avenue of study has included metal bearing molecular ions.

Recovering heavy rare earth metals from magnet scrap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ott, Ryan T.; McCallum, Ralph W.; Jones, Lawrence L.

A method of treating rare earth metal-bearing permanent magnet scrap, waste or other material in a manner to recover the heavy rare earth metal content separately from the light rare earth metal content. The heavy rare earth metal content can be recovered either as a heavy rare earth metal-enriched iron based alloy or as a heavy rare earth metal based alloy.

Divergent electronic structures of isoelectronic metalloclusters: tungsten(II) halides and rhenium(III) chalcogenide halides.

PubMed

Gray, Thomas G

2009-03-02

Same but different: DFT calculations on hexanuclear tungsten(II) halide clusters [W(6)X(8)X'(6)](2-) (X, X'=Cl, Br, I) indicate a breakdown in the isoelectronic analogy between themselves and the isostructural rhenium(III) chalcogenide clusters [Re(6)S(8)X(6)](4-) (see figure).The hexanuclear tungsten(II) halide clusters and the sulfido-halide clusters of rhenium(III) are subsets of a broad system of 24-electron metal-metal bonded assemblies that share a common structure. Tungsten(II) halide clusters and rhenium(III) sulfide clusters luminesce from triplet excited states upon ultraviolet or visible excitation; emission from both cluster series has been extensively characterized elsewhere. Reported here are density-functional theory studies of the nine permutations of [W(6)X(8)X'(6)](2-) (X, X'=Cl, Br, I). Ground-state properties including geometries, harmonic vibrational frequencies, and orbital energy-level diagrams, have been calculated. Comparison is made to the sulfide clusters of rhenium(III), of which [Re(6)S(8)Cl(6)](4-) is representative. [W(6)X(8)X'(6)](2-) and [Re(6)S(8)Cl(6)](4-) possess disparate electronic structures owing to the greater covalency of the metal-sulfur bond and hence of the [Re(6)S(8)](2+) core. Low-lying virtual orbitals are raised in energy in [Re(6)S(8)Cl(6)](4-) with the result that the LUMO+7 (or LUMO+8 in some cases) of tungsten(II) halide clusters is the LUMO of [Re(6)S(8)Cl(6)](4-) species. An inversion of the HOMO and HOMO-1 between the two cluster series also occurs. Time-dependent density-functional calculations using asymptotically correct functionals do not recapture the experimentally observed periodic trend in [W(6)X(14)](2-) luminescence (E(em) increasing in the order [W(6)Cl(14)](2-) < [W(6)Br(14)](2-) < [W(6)I(14)](2-)), predicting instead that emission energies decrease with incorporation of the heavier halides. This circumstance is either a gross failure of the time-dependent formalism of DFT or it indicates extensive

B-Site Metal Cation Exchange in Halide Perovskites

DOE PAGES

Eperon, Giles E.; Ginger, David S.

2017-05-02

Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation ofmore » the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.« less

B-Site Metal Cation Exchange in Halide Perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eperon, Giles E.; Ginger, David S.

Here, we demonstrate exchange of the B-site metal cation in hybrid organic-inorganic halide perovskite thin films. We exchange tin in formamidinium tin triiodide (NH 2) 2SnI 3' or FASnI 3) with lead at controllable levels, forming (CH- (NH 2) 2SnI xPB 1-xI 3 alloys with partial substitution and fully converting the film to CH(NH 2) 2PbI 3 with a large excess of Pb 2+. We observe no evidence for phase segregation or bilayered films, indicating that conversion is uniform throughout the film. This facile technique provides a new way to control composition independently from the crystallization processes, allowing formation ofmore » the black phase of CH(NH 2) 2PbI 3 at much lower temperatures than those previously reported while also opening the door to new morphology-composition combinations. The surprising observation that the B-site metal cations are mobile may also provide insight into the nature of transient processes in these materials, suggesting that they may be involved in ionic conduction, and will be a critical consideration for long-term stability.« less

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.

Direct Evidence of Exciton–Exciton Annihilation in Single-Crystalline Organic Metal Halide Nanotube Assemblies

DOE PAGES

Ma, Ying -Zhong; Lin, Haoran; Du, Mao -Hua; ...

2018-04-11

Excitons in low-dimensional organic–inorganic metal halide hybrid structures are commonly thought to undergo rapid self-trapping following creation due to strong quantum confinement and exciton–phonon interaction. Here we report an experimental study probing the dynamics of these self-trapped excitons in the single-crystalline bulk assemblies of 1D organic metal halide nanotubes, (C 6H 13N 4) 3Pb 2Br 7. Through time-resolved photoluminescence (PL) measurements at different excitation intensities, we observed a marked variation in the PL decay behavior that is manifested by an accelerated decay rate with increasing excitation fluence. Our results offer direct evidence of the occurrence of an exciton–exciton annihilation process,more » a nonlinear relaxation phenomenon that takes place only when some of the self-trapped excitons become mobile and can approach either each other or those trapped excitons. As a result, we further identify a fast and dominant PL decay component with a lifetime of ~2 ns with a nearly invariant relative area for all acquired PL kinetics, suggesting that this rapid relaxation process is intrinsic.« less

Direct Evidence of Exciton–Exciton Annihilation in Single-Crystalline Organic Metal Halide Nanotube Assemblies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, Ying -Zhong; Lin, Haoran; Du, Mao -Hua

Excitons in low-dimensional organic–inorganic metal halide hybrid structures are commonly thought to undergo rapid self-trapping following creation due to strong quantum confinement and exciton–phonon interaction. Here we report an experimental study probing the dynamics of these self-trapped excitons in the single-crystalline bulk assemblies of 1D organic metal halide nanotubes, (C 6H 13N 4) 3Pb 2Br 7. Through time-resolved photoluminescence (PL) measurements at different excitation intensities, we observed a marked variation in the PL decay behavior that is manifested by an accelerated decay rate with increasing excitation fluence. Our results offer direct evidence of the occurrence of an exciton–exciton annihilation process,more » a nonlinear relaxation phenomenon that takes place only when some of the self-trapped excitons become mobile and can approach either each other or those trapped excitons. As a result, we further identify a fast and dominant PL decay component with a lifetime of ~2 ns with a nearly invariant relative area for all acquired PL kinetics, suggesting that this rapid relaxation process is intrinsic.« less

Noble metal superparticles and methods of preparation thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Yugang; Hu, Yongxing

A method comprises heating an aqueous solution of colloidal silver particles. A soluble noble metal halide salt is added to the aqueous solution which undergoes a redox reaction on a surface of the silver particles to form noble metal/silver halide SPs, noble metal halide/silver halide SPs or noble metal oxide/silver halide SPs on the surface of the silver particles. The heat is maintained for a predetermined time to consume the silver particles and release the noble metal/silver halide SPs, the noble metal halide/silver halide SPs or the noble metal oxide/silver halide SPs into the aqueous solution. The aqueous solution ismore » cooled. The noble metal/silver halide SPs, the noble metal halide/silver halide SPs or noble metal oxide/silver halide SPs are separated from the aqueous solution. The method optionally includes adding a soluble halide salt to the aqueous solution.« less

Ionic behavior of organic-inorganic metal halide perovskite based metal-oxide-semiconductor capacitors.

PubMed

Wang, Yucheng; Zhang, Yuming; Pang, Tiqiang; Xu, Jie; Hu, Ziyang; Zhu, Yuejin; Tang, Xiaoyan; Luan, Suzhen; Jia, Renxu

2017-05-24

Organic-inorganic metal halide perovskites are promising semiconductors for optoelectronic applications. Despite the achievements in device performance, the electrical properties of perovskites have stagnated. Ion migration is speculated to be the main contributing factor for the many unusual electrical phenomena in perovskite-based devices. Here, to understand the intrinsic electrical behavior of perovskites, we constructed metal-oxide-semiconductor (MOS) capacitors based on perovskite films and performed capacitance-voltage (C-V) and current-voltage (I-V) measurements of the capacitors. The results provide direct evidence for the mixed ionic-electronic transport behavior within perovskite films. In the dark, there is electrical hysteresis in both the C-V and I-V curves because the mobile negative ions take part in charge transport despite frequency modulation. However, under illumination, the large amount of photoexcited free carriers screens the influence of the mobile ions with a low concentration, which is responsible for the normal C-V properties. Validation of ion migration for the gate-control ability of MOS capacitors is also helpful for the investigation of perovskite MOS transistors and other gate-control photovoltaic devices.

Dimming of metal halide lamps

NASA Astrophysics Data System (ADS)

Schurer, Kees

1994-03-01

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.

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.

Metal-Halide Perovskites for Gate Dielectrics in Field-Effect Transistors and Photodetectors Enabled by PMMA Lift-Off Process.

PubMed

Daus, Alwin; Roldán-Carmona, Cristina; Domanski, Konrad; Knobelspies, Stefan; Cantarella, Giuseppe; Vogt, Christian; Grätzel, Michael; Nazeeruddin, Mohammad Khaja; Tröster, Gerhard

2018-06-01

Metal-halide perovskites have emerged as promising materials for optoelectronics applications, such as photovoltaics, light-emitting diodes, and photodetectors due to their excellent photoconversion efficiencies. However, their instability in aqueous solutions and most organic solvents has complicated their micropatterning procedures, which are needed for dense device integration, for example, in displays or cameras. In this work, a lift-off process based on poly(methyl methacrylate) and deep ultraviolet lithography on flexible plastic foils is presented. This technique comprises simultaneous patterning of the metal-halide perovskite with a top electrode, which results in microscale vertical device architectures with high spatial resolution and alignment properties. Hence, thin-film transistors (TFTs) with methyl-ammonium lead iodide (MAPbI 3 ) gate dielectrics are demonstrated for the first time. The giant dielectric constant of MAPbI 3 (>1000) leads to excellent low-voltage TFT switching capabilities with subthreshold swings ≈80 mV decade -1 over ≈5 orders of drain current magnitude. Furthermore, vertically stacked low-power Au-MAPbI 3 -Au photodetectors with close-to-ideal linear response (R 2 = 0.9997) are created. The mechanical stability down to a tensile radius of 6 mm is demonstrated for the TFTs and photodetectors, simultaneously realized on the same flexible plastic substrate. These results open the way for flexible low-power integrated (opto-)electronic systems based on metal-halide perovskites. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solubility of alkali metal halides in the ionic liquid [C4C1im][OTf].

PubMed

Kuzmina, O; Bordes, E; Schmauck, J; Hunt, P A; Hallett, J P; Welton, T

2016-06-28

The solubilities of the metal halides LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbCl, CsCl, CsI, were measured at temperatures ranging from 298.15 to 378.15 K in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4C1im][OTf]). Li(+), Na(+) and K(+) salts with anions matching the ionic liquid have also been investigated to determine how well these cations dissolve in [C4C1im][OTf]. This study compares the influence of metal cation and halide anion on the solubility of salts within this ionic liquid. The highest solubility found was for iodide salts, and the lowest solubility for the three fluoride salts. There is no outstanding difference in the solubility of salts with matching anions in comparison to halide salts. The experimental data were correlated employing several phase equilibria models, including ideal mixtures, van't Hoff, the λh (Buchowski) equation, the modified Apelblat equation, and the non-random two-liquid model (NRTL). It was found that the van't Hoff model gave the best correlation results. On the basis of the experimental data the thermodynamic dissolution parameters (ΔH, ΔS, and ΔG) were determined for the studied systems together with computed gas phase metathesis parameters. Dissolution depends on the energy difference between enthalpies of fusion and dissolution of the solute salt. This demonstrates that overcoming the lattice energy of the solid matrix is the key to the solubility of inorganic salts in ionic liquids.

Metal-halide perovskites for photovoltaic and light-emitting devices.

PubMed

Stranks, Samuel D; Snaith, Henry J

2015-05-01

Metal-halide perovskites are crystalline materials originally developed out of scientific curiosity. Unexpectedly, solar cells incorporating these perovskites are rapidly emerging as serious contenders to rival the leading photovoltaic technologies. Power conversion efficiencies have jumped from 3% to over 20% in just four years of academic research. Here, we review the rapid progress in perovskite solar cells, as well as their promising use in light-emitting devices. In particular, we describe the broad tunability and fabrication methods of these materials, the current understanding of the operation of state-of-the-art solar cells and we highlight the properties that have delivered light-emitting diodes and lasers. We discuss key thermal and operational stability challenges facing perovskites, and give an outlook of future research avenues that might bring perovskite technology to commercialization.

Rare Earth Metals: Resourcefulness and Recovery

NASA Astrophysics Data System (ADS)

Wang, Shijie

2013-10-01

When we appreciate the digital revolution carried over from the twentieth century with mobile communication and the Internet, and when we enjoy our high-tech lifestyle filled with iDevices, hybrid cars, wind turbines, and solar cells in this new century, we should also appreciate that all of these advanced products depend on rare earth metals to function. Although there are only 136,000 tons of annual worldwide demand, (Cho, Rare Earth Metals, Will We Have Enough?)1 rare earth metals are becoming such hot commodities on international markets, due to not only to their increasing uses, including in most critical military hardware, but also to Chinese growth, which accounts for 95% of global rare earth metal production. Hence, the 2013 technical calendar topic, planned by the TMS/Hydrometallurgy and Electrometallurgy Committee, is particularly relevant, with four articles (including this commentary) contributed to the JOM October Issue discussing rare earth metals' resourcefulness and recovery.

Development of processes for the production of solar grade silicon from halides and alkali metals

NASA Technical Reports Server (NTRS)

Dickson, C. R.; Gould, R. K.

1980-01-01

High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon in volume at low cost were studied. Experiments were performed to evaluate product separation and collection processes, measure heat release parameters for scaling purposes, determine the effects of reactants and/or products on materials of reactor construction, and make preliminary engineering and economic analyses of a scaled-up process.

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.

Visualizing Carrier Transport in Metal Halide Perovskite Nanoplates via Electric Field Modulated Photoluminescence Imaging.

PubMed

Hu, Xuelu; Wang, Xiao; Fan, Peng; Li, Yunyun; Zhang, Xuehong; Liu, Qingbo; Zheng, Weihao; Xu, Gengzhao; Wang, Xiaoxia; Zhu, Xiaoli; Pan, Anlian

2018-05-09

Metal halide perovskite nanostructures have recently been the focus of intense research due to their exceptional optoelectronic properties and potential applications in integrated photonics devices. Charge transport in perovskite nanostructure is a crucial process that defines efficiency of optoelectronic devices but still requires a deep understanding. Herein, we report the study of the charge transport, particularly the drift of minority carrier in both all-inorganic CsPbBr 3 and organic-inorganic hybrid CH 3 NH 3 PbBr 3 perovskite nanoplates by electric field modulated photoluminescence (PL) imaging. Bias voltage dependent elongated PL emission patterns were observed due to the carrier drift at external electric fields. By fitting the drift length as a function of electric field, we obtained the carrier mobility of about 28 cm 2 V -1 S -1 in the CsPbBr 3 perovskite nanoplate. The result is consistent with the spatially resolved PL dynamics measurement, confirming the feasibility of the method. Furthermore, the electric field modulated PL imaging is successfully applied to the study of temperature-dependent carrier mobility in CsPbBr 3 nanoplates. This work not only offers insights for the mobile carrier in metal halide perovskite nanostructures, which is essential for optimizing device design and performance prediction, but also provides a novel and simple method to investigate charge transport in many other optoelectronic materials.

Octahedral tilting instabilities in inorganic halide perovskites

NASA Astrophysics Data System (ADS)

Bechtel, Jonathon S.; Van der Ven, Anton

2018-02-01

Dynamic instabilities, stabilized by anharmonic interactions in cubic and tetragonal halide perovskites at high temperature, play a role in the electronic structure and optoelectronic properties of halide perovskites. In particular, inorganic and hybrid perovskite materials undergo structural phase transitions associated with octahedral tilts of the metal-halide octahedra. We investigate the structural instabilities present in inorganic Cs M X3 perovskites with Pb or Sn on the metal site and Br or I on the X site. Defining primary order parameters in terms of symmetry-adapted collective displacement modes and secondary order parameters in terms of symmetrized Hencky strain components, we unravel the coupling between octahedral tilt modes and macroscopic strains as well as the role of A -site displacements in perovskite phase stability. Symmetry-allowed secondary strain order parameters are enumerated for the 14 unique perovskite tilt systems. Using first-principles calculations to explore the Born-Oppenheimer energy surface in terms of symmetrized order parameters, we find coupling between octahedral tilting and A -site displacements is necessary to stabilize P n m a ground states. Additionally, we show that the relative stability of an inorganic halide perovskite tilt system correlates with the volume decrease from the high-symmetry cubic phase to the low-symmetry distorted phase.

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)

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.

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.

Confining metal-halide perovskites in nanoporous thin films

PubMed Central

Demchyshyn, Stepan; Roemer, Janina Melanie; Groiß, Heiko; Heilbrunner, Herwig; Ulbricht, Christoph; Apaydin, Dogukan; Böhm, Anton; Rütt, Uta; Bertram, Florian; Hesser, Günter; Scharber, Markus Clark; Sariciftci, Niyazi Serdar; Nickel, Bert; Bauer, Siegfried; Głowacki, Eric Daniel; Kaltenbrunner, Martin

2017-01-01

Controlling the size and shape of semiconducting nanocrystals advances nanoelectronics and photonics. Quantum-confined, inexpensive, solution-derived metal halide perovskites offer narrowband, color-pure emitters as integral parts of next-generation displays and optoelectronic devices. We use nanoporous silicon and alumina thin films as templates for the growth of perovskite nanocrystallites directly within device-relevant architectures without the use of colloidal stabilization. We find significantly blue-shifted photoluminescence emission by reducing the pore size; normally infrared-emitting materials become visibly red, and green-emitting materials become cyan and blue. Confining perovskite nanocrystals within porous oxide thin films drastically increases photoluminescence stability because the templates auspiciously serve as encapsulation. We quantify the template-induced size of the perovskite crystals in nanoporous silicon with microfocus high-energy x-ray depth profiling in transmission geometry, verifying the growth of perovskite nanocrystals throughout the entire thickness of the nanoporous films. Low-voltage electroluminescent diodes with narrow, blue-shifted emission fabricated from nanocrystalline perovskites grown in embedded nanoporous alumina thin films substantiate our general concept for next-generation photonic devices. PMID:28798959

PROCESSING OF URANIUM-METAL-CONTAINING FUEL ELEMENTS

DOEpatents

Moore, R.H.

1962-10-01

A process is given for recovering uranium from neutronbombarded uranium- aluminum alloys. The alloy is dissolved in an aluminum halide--alkali metal halide mixture in which the halide is a mixture of chloride and bromide, the aluminum halide is present in about stoichiometric quantity as to uranium and fission products and the alkali metal halide in a predominant quantity; the uranium- and electropositive fission-products-containing salt phase is separated from the electronegative-containing metal phase; more aluminum halide is added to the salt phase to obtain equimolarity as to the alkali metal halide; adding an excess of aluminum metal whereby uranium metal is formed and alloyed with the excess aluminum; and separating the uranium-aluminum alloy from the fission- productscontaining salt phase. (AEC)

Anion-π interaction in metal-organic networks formed by metal halides and tetracyanopyrazine

NASA Astrophysics Data System (ADS)

Rosokha, Sergiy V.; Kumar, Amar

2017-06-01

Co-crystallization of tetracyanopyrazine, TCP, with the tetraalkylammonium salts of linear [CuBr2]-, planar [PtCl4]2- or [Pt2Br6]2-, or octahedral [PtBr6]2- complexes resulted in formation of the alternating [MlXn]m-/TCP stacks separated by the Alk4N+ cations. These hybrid stacks showed multiple short contacts between halide ligands of the [MlXn]m- complexes and carbon atoms of the TCP acceptor indicating strong anion-π bonding between these species. It confirmed that the anion-π interaction is sufficiently strong to bring together such disparate components as ionic metal complexes and neutral aromatic molecules regardless of the geometry of the coordination compound. Structural features of the solid-state stacks and [MlXn]m-·TCP dyads resulted from the quantum-mechanical computations suggests that the molecular-orbital (weakly-covalent) component play an important role in association of the [MlXn]m- complexes with the TCP acceptor.

Transition metal-substituted lead halide perovskite absorbers

DOE PAGES

Sampson, M. D.; Park, J. S.; Schaller, R. D.; ...

2017-01-27

Here, lead halide perovskites have proven to be a versatile class of visible light absorbers that allow rapid access to the long minority carrier lifetimes and diffusion lengths desirable for traditional single-junction photovoltaics. We explore the extent to which the attractive features of these semiconductors may be extended to include an intermediate density of states for future application in multi-level solar energy conversion systems capable of exceeding the Shockley–Queisser limit. We computationally and experimentally explore the substitution of transition metals on the Pb site of MAPbX 3 (MA = methylammonium, X = Br or Cl) to achieve a tunable densitymore » of states within the parent gap. Computational screening identified both Fe- and Co-substituted MAPbBr 3 as promising absorbers with a mid-gap density of states, and the later films were synthesized via conventional solution-based processing techniques. First-principles density functional theory (DFT) calculations support the existence of mid-gap states upon Co incorporation and enhanced sub-gap absorption, which are consistent with UV-visible-NIR absorption spectroscopy. Strikingly, steady state and time-resolved PL studies reveal no sign of self-quenching for Co-substitution up to 25%, which suggest this class of materials to be a worthy candidate for future application in intermediate band photovoltaics.« less

Metal Hydride and Alkali Halide Opacities in Extrasolar Giant Planets and Cool Stellar Atmospheres

NASA Technical Reports Server (NTRS)

Weck, Philippe F.; Stancil, Phillip C.; Kirby, Kate; Schweitzer, Andreas; Hauschildt, Peter H.

2006-01-01

The lack of accurate and complete molecular line and continuum opacity data has been a serious limitation to developing atmospheric models of cool stars and Extrasolar Giant Planets (EGPs). We report our recent calculations of molecular opacities resulting from the presence of metal hydrides and alkali halides. The resulting data have been included in the PHOENIX stellar atmosphere code (Hauschildt & Baron 1999). The new models, calculated using spherical geometry for all gravities considered, also incorporate our latest database of nearly 670 million molecular lines, and updated equations of state.

The effect of illumination on the formation of metal halide perovskite films

NASA Astrophysics Data System (ADS)

Ummadisingu, Amita; Steier, Ludmilla; Seo, Ji-Youn; Matsui, Taisuke; Abate, Antonio; Tress, Wolfgang; Grätzel, Michael

2017-04-01

Optimizing the morphology of metal halide perovskite films is an important way to improve the performance of solar cells when these materials are used as light harvesters, because film homogeneity is correlated with photovoltaic performance. Many device architectures and processing techniques have been explored with the aim of achieving high-performance devices, including single-step deposition, sequential deposition and anti-solvent methods. Earlier studies have looked at the influence of reaction conditions on film quality, such as the concentration of the reactants and the reaction temperature. However, the precise mechanism of the reaction and the main factors that govern it are poorly understood. The consequent lack of control is the main reason for the large variability observed in perovskite morphology and the related solar-cell performance. Here we show that light has a strong influence on the rate of perovskite formation and on film morphology in both of the main deposition methods currently used: sequential deposition and the anti-solvent method. We study the reaction of a metal halide (lead iodide) with an organic compound (methylammonium iodide) using confocal laser scanning fluorescence microscopy and scanning electron microscopy. The lead iodide crystallizes before the intercalation of methylammonium iodide commences, producing the methylammonium lead iodide perovskite. We find that the formation of perovskite via such a sequential deposition is much accelerated by light. The influence of light on morphology is reflected in a doubling of solar-cell efficiency. Conversely, using the anti-solvent method to form methyl ammonium lead iodide perovskite in a single step from the same starting materials, we find that the best photovoltaic performance is obtained when films are produced in the dark. The discovery of light-activated crystallization not only identifies a previously unknown source of variability in opto-electronic properties, but also opens up

Theoretical study of mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes.

PubMed

Groen, C P; Oskam, A; Kovács, A

2000-12-25

The structure, bonding and vibrational properties of the mixed LiLnX4 (Ln = La, Dy; X = F, Cl, Br, I) rare earth/alkali halide complexes were studied using various quantum chemical methods (HF, MP2 and the Becke3-Lee-Yang-Parr exchange-correlation density functional) in conjunction with polarized triple-zeta valence basis sets and quasi-relativistic effective core potentials for the heavy atoms. Our comparative study indicated the superiority of MP2 theory while the HF and B3-LYP methods as well as less sophisticated basis sets failed for the correct energetic relations. In particular, f polarization functions on Li and X proved to be important for the Li...X interaction in the complexes. From the three characteristic structures of such complexes, possessing 1-(C3v), 2-(C2v), or 3-fold coordination (C3v) between the alkali metal and the bridging halide atoms, the bi- and tridentate forms are located considerably lower on the potential energy surface then the monodentate isomer. Therefore only the bi- and tridentate isomers have chemical relevance. The monodentate isomer is only a high-lying local minimum in the case of X = F. For X = Cl, Br, and I this structure is found to be a second-order saddle point. The bidentate structure was found to be the global minimum for the systems with X = F, Cl, and Br. However, the relative stability with respect to the tridentate structure is very small (1-5 kJ/mol) for the heavier halide derivatives and the relative order is reversed in the case of the iodides. The energy difference between the three structures and the dissociation energy decrease in the row F to I. The ionic bonding in the complexes was characterized by natural charges and a topological analysis of the electron density distribution according to Bader's theorem. Variation of the geometrical and bonding characteristics between the lanthanum and dysprosium complexes reflects the effect of "lanthanide contraction". The calculated vibrational data indicate that

Origin of Light Induced Photophysical Effects in Organic Metal Halide Perovskites in the Presence of Oxygen.

PubMed

Anaya, Miguel; Galisteo-López, Juan F; Calvo, Mauricio Ernesto; Espinos, Juan P; Miguez, Hernan

2018-06-21

Herein we present a combined study of the evolution of both the photoluminescence and the surface chemical structure of organic metal halide perovskites as environmental oxygen pressure rises from ultra-high vacuum up to a few thousandths of an atmosphere. Analyzing the changes occurring at the semiconductor surface upon photo-excitation under controlled oxygen atmosphere in an X-ray photoelectron spectroscopy (XPS) chamber, we can rationalize the rich variety of photophysical phenomena observed and provide a plausible explanation for light-induced ion migration, one of the most conspicuous and debated concomitant effects detected during photoexcitation. We find direct evidence of the formation of a superficial layer of negatively charged oxygen species capable of repelling the halide anions away from the surface and towards the bulk. The reported photoluminescence (PL) transient dynamics, the partial recovery of the initial state when photoexcitation stops and the eventual degradation after intense exposure times can thus be rationalized.

Near-Earth asteroids: Metals occurrence, extraction, and fabrication

NASA Astrophysics Data System (ADS)

Westfall, Richard

Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength

Near-Earth asteroids: Metals occurrence, extraction, and fabrication

NASA Technical Reports Server (NTRS)

Westfall, Richard

1991-01-01

Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength

Charge-separated and molecular heterobimetallic rare earth-rare earth and alkaline earth-rare earth aryloxo complexes featuring intramolecular metal-pi-arene interactions.

PubMed

Deacon, Glen B; Junk, Peter C; Moxey, Graeme J; Ruhlandt-Senge, Karin; St Prix, Courtney; Zuniga, Maria F

2009-01-01

Treatment of a rare earth metal (Ln) and a potential divalent rare earth metal (Ln') or an alkaline earth metal (Ae) with 2,6-diphenylphenol (HOdpp) at elevated temperatures (200-250 degrees C) afforded heterobimetallic aryloxo complexes, which were structurally characterised. A charge-separated species [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] was obtained for a range of metals, demonstrating the similarities between the chemistry of the divalent rare earth metals and the alkaline earth metals. The [(Ln'/Ae)(2)(Odpp)(3)](+) cation in the heterobimetallic structures is unusual in that it consists solely of bridging aryloxide ligands. A molecular heterobimetallic species [AeEu(Odpp)(4)] (Ae = Ca, Sr, Ba) was obtained by treating an alkaline earth metal and Eu metal with HOdpp at elevated temperatures. Similarly, [BaSr(Odpp)(4)] was prepared by treating Ba metal and Sr metal with HOdpp. Treatment of [Ba(2)(Odpp)(4)] with [Mg(Odpp)(2)(thf)(2)] in toluene afforded [Ba(2)(Odpp)(3)][Mg(Odpp)(3)(thf)]. Analogous solution-based syntheses were not possible for [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] complexes, for which the free-metal route was essential. As a result of the absence of additional donor ligands, the crystal structures of the heterobimetallic complexes feature extensive pi-Ph-metal interactions involving the pendant phenyl groups of the Odpp ligands, thus enabling the large electropositive metal atoms to attain coordination saturation. The charge-separated heterobimetallic species were purified by extraction with toluene/thf mixtures at ambient temperature (Ba-containing compounds) or by extraction with toluene under pressure above the boiling point of the solvent (other products). In donor solvents, heterobimetallic complexes other than those containing barium were found to fragment into homometallic species.

Highly Efficient Light-Emitting Diodes of Colloidal Metal-Halide Perovskite Nanocrystals beyond Quantum Size.

PubMed

Kim, Young-Hoon; Wolf, Christoph; Kim, Young-Tae; Cho, Himchan; Kwon, Woosung; Do, Sungan; Sadhanala, Aditya; Park, Chan Gyung; Rhee, Shi-Woo; Im, Sang Hyuk; Friend, Richard H; Lee, Tae-Woo

2017-07-25

Colloidal metal-halide perovskite quantum dots (QDs) with a dimension less than the exciton Bohr diameter D B (quantum size regime) emerged as promising light emitters due to their spectrally narrow light, facile color tuning, and high photoluminescence quantum efficiency (PLQE). However, their size-sensitive emission wavelength and color purity and low electroluminescence efficiency are still challenging aspects. Here, we demonstrate highly efficient light-emitting diodes (LEDs) based on the colloidal perovskite nanocrystals (NCs) in a dimension > D B (regime beyond quantum size) by using a multifunctional buffer hole injection layer (Buf-HIL). The perovskite NCs with a dimension greater than D B show a size-irrespective high color purity and PLQE by managing the recombination of excitons occurring at surface traps and inside the NCs. The Buf-HIL composed of poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonate) (PEDOT:PSS) and perfluorinated ionomer induces uniform perovskite particle films with complete film coverage and prevents exciton quenching at the PEDOT:PSS/perovskite particle film interface. With these strategies, we achieved a very high PLQE (∼60.5%) in compact perovskite particle films without any complex post-treatments and multilayers and a high current efficiency of 15.5 cd/A in the LEDs of colloidal perovskite NCs, even in a simplified structure, which is the highest efficiency to date in green LEDs that use colloidal organic-inorganic metal-halide perovskite nanoparticles including perovskite QDs and NCs. These results can help to guide development of various light-emitting optoelectronic applications based on perovskite NCs.

Effects of Rare Earth Metals on Steel Microstructures

PubMed Central

Pan, Fei; Zhang, Jian; Chen, Hao-Long; Su, Yen-Hsun; Kuo, Chia-Liang; Su, Yen-Hao; Chen, Shin-Hau; Lin, Kuan-Ju; Hsieh, Ping-Hung; Hwang, Weng-Sing

2016-01-01

Rare earth metals are used in semiconductors, solar cells and catalysts. This review focuses on the background of oxide metallurgy technologies, the chemical and physical properties of rare earth (RE) metals, the background of oxide metallurgy, the functions of RE metals in steelmaking, and the influences of RE metals on steel microstructures. Future prospects for RE metal applications in steelmaking are also presented. PMID:28773545

Rare earth metal-containing ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prodius, Denis; Mudring, Anja-Verena

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Rare earth metal-containing ionic liquids

DOE PAGES

Prodius, Denis; Mudring, Anja-Verena

2018-03-07

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Rare earth gas laser

DOEpatents

Krupke, W.F.

1975-10-31

A high energy gas laser with light output in the infrared or visible region of the spectrum is described. Laser action is obtained by generating vapors of rare earth halides, particularly neodymium iodide or, to a lesser extent, neodymium bromide, and disposing the rare earth vapor medium in a resonant cavity at elevated temperatures; e.g., approximately 1200/sup 0/ to 1400/sup 0/K. A particularly preferred gaseous medium is one involving a complex of aluminum chloride and neodymium chloride, which exhibits tremendously enhanced vapor pressure compared to the rare earth halides per se, and provides comparable increases in stored energy densities.

Photocrystallographic observation of halide-bridged intermediates in halogen photoeliminations.

PubMed

Powers, David C; Anderson, Bryce L; Hwang, Seung Jun; Powers, Tamara M; Pérez, Lisa M; Hall, Michael B; Zheng, Shao-Liang; Chen, Yu-Sheng; Nocera, Daniel G

2014-10-29

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.

Uranium chloride extraction of transuranium elements from LWR fuel

DOEpatents

Miller, William E.; Ackerman, John P.; Battles, James E.; Johnson, Terry R.; Pierce, R. Dean

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels containing rare earth and noble metal fission products as well as other fission products is disclosed. The oxide fuel is reduced with Ca metal in the presence of Ca chloride and a U-Fe alloy which is liquid at about 800.degree. C. to dissolve uranium metal and the noble metal fission product metals and transuranium actinide metals and rare earth fission product metals leaving Ca chloride having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein. The Ca chloride and CaO and the fission products contained therein are separated from the U-Fe alloy and the metal values dissolved therein. The U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel is contacted with a mixture of one or more alkali metal or alkaline earth metal halides selected from the class consisting of alkali metal or alkaline earth metal and Fe or U halide or a combination thereof to transfer transuranium actinide metals and rare earth metals to the halide salt leaving the uranium and some noble metal fission products in the U-Fe alloy and thereafter separating the halide salt and the transuranium metals dissolved therein from the U-Fe alloy and the metals dissolved therein.

Uranium chloride extraction of transuranium elements from LWR fuel

DOEpatents

Miller, W.E.; Ackerman, J.P.; Battles, J.E.; Johnson, T.R.; Pierce, R.D.

1992-08-25

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels containing rare earth and noble metal fission products as well as other fission products is disclosed. The oxide fuel is reduced with Ca metal in the presence of Ca chloride and a U-Fe alloy which is liquid at about 800 C to dissolve uranium metal and the noble metal fission product metals and transuranium actinide metals and rare earth fission product metals leaving Ca chloride having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein. The Ca chloride and CaO and the fission products contained therein are separated from the U-Fe alloy and the metal values dissolved therein. The U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel is contacted with a mixture of one or more alkali metal or alkaline earth metal halides selected from the class consisting of alkali metal or alkaline earth metal and Fe or U halide or a combination thereof to transfer transuranium actinide metals and rare earth metals to the halide salt leaving the uranium and some noble metal fission products in the U-Fe alloy and thereafter separating the halide salt and the transuranium metals dissolved therein from the U-Fe alloy and the metals dissolved therein. 1 figure.

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2014 CFR

2014-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... hydrogen halide and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this...) of this section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you...

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2013 CFR

2013-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... hydrogen halide and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this...) of this section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you...

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2012 CFR

2012-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... hydrogen halide and halogen HAP or HAP metals? (a) You must meet each emission limit in Table 3 to this...) of this section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you...

Metal halide solid-state surface treatment for high efficiency PbS and PbSe QD solar cells.

PubMed

Crisp, Ryan W; Kroupa, Daniel M; Marshall, Ashley R; Miller, Elisa M; Zhang, Jianbing; Beard, Matthew C; Luther, Joseph 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%.

Metal Halide Solid-State Surface Treatment for High Efficiency PbS and PbSe QD Solar Cells

DOE PAGES

Crisp, R. W.; Kroupa, D. M.; Marshall, A. R.; ...

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 (PbI 2, PbCl 2, CdI 2, or CdCl 2) 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 PbI 2 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 amore » 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 PbI 2 with power conversion efficiencies above 7%.« less

Metal Halide Solid-State Surface Treatment for High Efficiency PbS and PbSe QD Solar Cells

PubMed Central

Crisp, Ryan W.; Kroupa, Daniel M.; Marshall, Ashley R.; Miller, Elisa M.; Zhang, Jianbing; Beard, Matthew C.; Luther, Joseph M.

2015-01-01

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%. PMID:25910183

Antimicrobial properties of metal and metal-halide nanoparticles and their potential applications

NASA Astrophysics Data System (ADS)

Torrey, Jason Robert

Heavy metals, including silver and copper, have been known to possess antimicrobial properties against bacterial, fungal, and viral pathogens. Metal nanoparticles (aggregations of metal atoms 1-200 nm in size) have recently become the subject of intensive study for their increased antimicrobial properties. In the current studies, metal and metal-halide nanoparticles were evaluated for their antibacterial efficacy. Silver (Ag), silver bromide (AgBr), silver iodide (AgI), and copper iodide (CuI) nanoparticles significantly reduced bacterial numbers of the Gram-negative Pseudomonas aeruginosa and the Gram-positive Staphylococcus aureus within 24 hours and were more effective against P. aeruginosa. CuI nanoparticles were found to be highly effective, reducing both organisms by >4.43 log 10 within 15 minutes at 60 ppm Cu. CuI nanoparticles formulated with different stabilizers (sodium dodecyl sulfate, SDS; polyvinyl pyrrolidone, PVP) were further tested against representative Gram-positive and Gram-negative bacteria, Mycobacteria, a fungus (Candida albicans ), and a non-enveloped virus (poliovirus). Both nanoparticles caused significant reductions in most of the Gram-negative bacteria within five minutes (>5.09-log10). The Gram-positive bacterial species and C. albicans were more sensitive to the CuI-SDS than the CuI-PVP nanoparticles. In contrast, the acid-fast Mycobacterium smegmatis was more resistant to CuI-SDS than CuI-PVP nanoparticles. Poliovirus was more resistant than the other organisms tested except for Mycobacterium fortuitum, which displayed the greatest resistance to CuI nanoparticles. As an example of a real world antimicrobial application, polymer coatings embedded with various concentrations of CuI nanoparticles were tested for antibacterial efficacy against P. aeruginosa and S. aureus. Polyester-epoxy powder coatings were found to display superior uniformity, stability and antimicrobial properties against both organisms (>4.92 log 10 after six hours at

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%.

Ultrastable Photoelectrodes for Solar Water Splitting Based on Organic Metal Halide Perovskite Fabricated by Lift-Off Process.

PubMed

Nam, SeongSik; Mai, Cuc Thi Kim; Oh, Ilwhan

2018-05-02

Herein, we report an integrated photoelectrolysis of water employing organic metal halide (OMH) perovskite material. As generic OMH perovskite material and device architecture are highly susceptible to degradation by aqueous electrolytes, we have developed a versatile mold-cast and lift-off process to fabricate and assemble multipurpose metal encapsulation onto perovskite devices. With the metal encapsulation effectively protecting the perovskite cell and also functioning as electrocatalyst, the high-performance perovskite photoelectrodes exhibit high photovoltage and photocurrent that are effectively inherited from the original solid-state solar cell. More importantly, thus-fabricated perovskite photoelectrode demonstrates record-long unprecedented stability even at highly oxidizing potential in strong alkaline electrolyte. We expect that this versatile lift-off process can be adapted in a wide variety of photoelectrochemical devices to protect the material surfaces from corroding electrolyte and facilitate various electrochemical reactions.

Shift Happens. How Halide Ion Defects Influence Photoinduced Segregation in Mixed Halide Perovskites

DOE PAGES

Yoon, Seog Joon; Kuno, Masaru; Kamat, Prashant V.

2017-06-01

Minimizing photoinduced segregation in mixed halide lead perovskites is important for achieving stable photovoltaic performance. The shift in the absorption and the rate of formation of iodide- and bromide-rich regions following visible excitation of mixed halide lead perovskites is found to strongly depend on the halide ion concentration. Slower formation and recovery rates observed in halide-deficient films indicate the involvement of defect sites in influencing halide phase segregation. At higher halide concentrations (in stoichiometric excess), segregation effects become less prominent, as evidenced by faster recovery kinetics. These results suggest that light-induced compositional segregation can be minimized in mixed halide perovskitemore » films by using excess halide ions. In conclusion, the findings from this study further reflect the importance of halide ion post-treatment of perovskite films to improve their solar cell performance.« less

Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic-Inorganic Perovskites.

PubMed

Sutter-Fella, Carolin M; Ngo, Quynh P; Cefarin, Nicola; Gardner, Kira L; Tamura, Nobumichi; Stan, Camelia V; Drisdell, Walter S; Javey, Ali; Toma, Francesca M; Sharp, Ian D

2018-06-13

Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. Here, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2 ) 2 CsPb-halide (FACsPb-) and CH 3 NH 3 Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials. However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.

The role of halide ions on the electrochemical behaviour of iron in alkali solutions

NASA Astrophysics Data System (ADS)

Begum, S. Nathira; Muralidharan, V. S.; Basha, C. Ahmed

2008-02-01

Active dissolution and passivation of transition metals in alkali solutions is of technological importance in batteries. The performance of alkaline batteries is decided by the presence of halides as they influence passivation. Cyclic voltammetric studies were carried out on iron in different sodium hydroxide solutions in presence of halides. In alkali solutions iron formed hydroxo complexes and their polymers in the interfacial diffusion layer. With progress of time they formed a cation selective layer. The diffusion layer turned into bipolar ion selective layer consisted of halides, a selective inner sublayer to the metal side and cation selective outer layer to the solution side. At very high anodic potentials, dehydration and deprotonation led to the conversion of salt layer into an oxide.

Double-ended metal halide arc discharge lamp with electrically isolated containment shroud

NASA Technical Reports Server (NTRS)

Muzeroll, Martin M. (Inventor)

1994-01-01

A double-ended arc discharge lamp includes a sealed, light-transmissive outer jacket, a light-transmissive shroud mounted within the outer jacket and directly supported by the outer jacket, and an arc discharge tube mounted within the shroud. The arc tube is typically a metal halide arc discharge tube. In a preferred embodiment, the shroud includes an outwardly flared portion at each end. The outwardly flared portions space the shroud from the outer jacket and support the shroud within the outer jacket. The outwardly flared portions of the shroud can be affixed to the outer jacket by fusing. The outer jacket can be provided with inwardly extending dimples for locating the shroud with respect to the outer jacket. In another embodiment, the outer jacket includes reduced diameter portions near each end which are attached to the shroud.

Prediction of Intrinsic Ferromagnetic Ferroelectricity in a Transition-Metal Halide Monolayer

NASA Astrophysics Data System (ADS)

Huang, Chengxi; Du, Yongping; Wu, Haiping; Xiang, Hongjun; Deng, Kaiming; Kan, Erjun

2018-04-01

The realization of multiferroics in nanostructures, combined with a large electric dipole and ferromagnetic ordering, could lead to new applications, such as high-density multistate data storage. Although multiferroics have been broadly studied for decades, ferromagnetic ferroelectricity is rarely explored, especially in two-dimensional (2D) systems. Here we report the discovery of 2D ferromagnetic ferroelectricity in layered transition-metal halide systems. On the basis of first-principles calculations, we reveal that a charged CrBr3 monolayer exhibits in-plane multiferroicity, which is ensured by the combination of orbital and charge ordering as realized by the asymmetric Jahn-Teller distortions of octahedral Cr - Br6 units. As an example, we further show that (CrBr3)2Li is a ferromagnetic ferroelectric multiferroic. The explored phenomena and mechanism of multiferroics in this 2D system not only are useful for fundamental research in multiferroics but also enable a wide range of applications in nanodevices.

Polar Fluctuations in Metal Halide Perovskites Uncovered by Acoustic Phonon Anomalies

DOE PAGES

Guo, Peijun; Xia, Yi; Gong, Jue; ...

2017-09-28

Solution-processable metal-halide perovskites (MHPs) offer great promise for efficient light harvesting and emitting devices due to their long carrier lifetime and superior carrier transport characteristics. Ferroelectric effects, a hallmark of traditional oxide perovskites, was proposed to be a mechanism to suppress carrier recombination and enhance charge transport in MHPs, but the existence and influence of such polar order is still of considerable debate. Here we performed transient reflection measurements on single crystals of both inorganic and organic-inorganic (hybrid) MHPs over a range of temperatures, and demonstrate significant phonon softening in the cubic phases close to the cubic-to-tetragonal phase transition temperatures.more » Such phonon softening indicates the formation of polar domains, which grow in size upon cooling and can persist in the low-temperature tetragonal and orthorhombic phases. Our results link the extraordinary electronic properties of MHPs to the spontaneous polarizations which can contribute to more efficient charge separation and characteristics of an indirect bandgap.« less

Prediction of Intrinsic Ferromagnetic Ferroelectricity in a Transition-Metal Halide Monolayer.

PubMed

Huang, Chengxi; Du, Yongping; Wu, Haiping; Xiang, Hongjun; Deng, Kaiming; Kan, Erjun

2018-04-06

The realization of multiferroics in nanostructures, combined with a large electric dipole and ferromagnetic ordering, could lead to new applications, such as high-density multistate data storage. Although multiferroics have been broadly studied for decades, ferromagnetic ferroelectricity is rarely explored, especially in two-dimensional (2D) systems. Here we report the discovery of 2D ferromagnetic ferroelectricity in layered transition-metal halide systems. On the basis of first-principles calculations, we reveal that a charged CrBr_{3} monolayer exhibits in-plane multiferroicity, which is ensured by the combination of orbital and charge ordering as realized by the asymmetric Jahn-Teller distortions of octahedral Cr─Br_{6} units. As an example, we further show that (CrBr_{3})_{2}Li is a ferromagnetic ferroelectric multiferroic. The explored phenomena and mechanism of multiferroics in this 2D system not only are useful for fundamental research in multiferroics but also enable a wide range of applications in nanodevices.

2D halide perovskite-based van der Waals heterostructures: contact evaluation and performance modulation

NASA Astrophysics Data System (ADS)

Guo, Yaguang; Saidi, Wissam A.; Wang, Qian

2017-09-01

Halide perovskites and van der Waals (vdW) heterostructures are both of current interest owing to their novel properties and potential applications in nano-devices. Here, we show the great potential of 2D halide perovskite sheets (C4H9NH3)2PbX4 (X  =  Cl, Br and I) that were synthesized recently (Dou et al 2015 Science 349 1518-21) as the channel materials contacting with graphene and other 2D metallic sheets to form van der Waals heterostructures for field effect transistor (FET). Based on state-of-the-art theoretical simulations, we show that the intrinsic properties of the 2D halide perovskites are preserved in the heterojunction, which is different from the conventional contact with metal surfaces. The 2D halide perovskites form a p-type Schottky barrier (Φh) contact with graphene, where tunneling barrier exists, and a negative band bending occurs at the lateral interface. We demonstrate that the Schottky barrier can be turned from p-type to n-type by doping graphene with nitrogen atoms, and a low-Φh or an Ohmic contact can be realized by doping graphene with boron atoms or replacing graphene with other high-work-function 2D metallic sheets such as ZT-MoS2, ZT-MoSe2 and H-NbS2. This study not only predicts a 2D halide perovskite-based FETs, but also enhances the understanding of tuning Schottky barrier height in device applications.

Growth and yield characteristics of 'Waldmann's Green' leaf lettuce under different photon fluxes from metal halide or incandescent + fluorescent radiation

NASA Technical Reports Server (NTRS)

Knight, Sharon L.; Mitchell, Cary A.

1988-01-01

Growth of 'Waldmann's Green' leaf lettuce under metal halide radiation was compared with that under In = Fl at the same photosynthetic photon flux (920 micromol/s/sq m) to evaluate the influence of lamp type on growth. No differences in leaf dry weight, leaf area, relative growth rate or photosynthesis occurred after 8 days of exposure to these radiation treatments for 20 h/day.

Advancement on Lead-Free Organic-Inorganic Halide Perovskite Solar Cells: A Review.

PubMed

Sani, Faruk; Shafie, Suhaidi; Lim, Hong Ngee; Musa, Abubakar Ohinoyi

2018-06-14

Remarkable attention has been committed to the recently discovered cost effective and solution processable lead-free organic-inorganic halide perovskite solar cells. Recent studies have reported that, within five years, the reported efficiency has reached 9.0%, which makes them an extremely promising and fast developing candidate to compete with conventional lead-based perovskite solar cells. The major challenge associated with the conventional perovskite solar cells is the toxic nature of lead (Pb) used in the active layer of perovskite material. If lead continues to be used in fabricating solar cells, negative health impacts will result in the environment due to the toxicity of lead. Alternatively, lead free perovskite solar cells could give a safe way by substituting low-cost, abundant and non toxic material. This review focuses on formability of lead-free organic-inorganic halide perovskite, alternative metal cations candidates to replace lead (Pb), and possible substitutions of organic cations, as well as halide anions in the lead-free organic-inorganic halide perovskite architecture. Furthermore, the review gives highlights on the impact of organic cations, metal cations and inorganic anions on stability and the overall performance of lead free perovskite solar cells.

Adsorption of halogens on metal surfaces

NASA Astrophysics Data System (ADS)

Andryushechkin, B. V.; Pavlova, T. V.; Eltsov, K. N.

2018-06-01

This paper presents a review of the experimental and theoretical investigations of halogen interaction with metal surfaces. The emphasis was placed on the recent measurements performed with a scanning tunneling microscope in combination with density functional theory calculations. The surface structures formed on metal surface after halogen interaction are classified into three groups: chemisorbed monolayer, surface halide, bulk-like halide. Formation of monolayer structures is described in terms of surface phase transitions. Surface halide phases are considered to be intermediates between chemisorbed halogen and bulk halide. The modern theoretical approaches in studying the dynamics of metal halogenation reactions are also presented.

Universal scaling of potential energy functions describing intermolecular interactions. II. The halide-water and alkali metal-water interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Werhahn, Jasper C.; Akase, Dai; Xantheas, Sotiris S.

2014-08-14

The scaled versions of the newly introduced [S. S. Xantheas and J. C. Werhahn, J. Chem. Phys.141, 064117 (2014)] generalized forms of some popular potential energy functions (PEFs) describing intermolecular interactions – Mie, Lennard-Jones, Morse, and Buckingham exponential-6 – have been used to fit the ab initio relaxed approach paths and fixed approach paths for the halide-water, X -(H 2O), X = F, Cl, Br, I, and alkali metal-water, M +(H 2O), M = Li, Na, K, Rb, Cs, interactions. The generalized forms of those PEFs have an additional parameter with respect to the original forms and produce fits tomore » the ab initio data that are between one and two orders of magnitude better in the χ 2 than the original PEFs. They were found to describe both the long-range, minimum and repulsive wall of the respective potential energy surfaces quite accurately. Overall the 4-parameter extended Morse (eM) and generalized Buckingham exponential-6 (gBe-6) potentials were found to best fit the ab initio data for these two classes of ion-water interactions. Finally, the fitted values of the parameter of the (eM) and (gBe-6) PEFs that control the repulsive wall of the potential correlate remarkably well with the ionic radii of the halide and alkali metal ions.« less

Method for treating rare earth-transition metal scrap

DOEpatents

Schmidt, Frederick A.; Peterson, David T.; Wheelock, John T.; Jones, Lawrence L.

1992-12-29

Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a prefused, rare earth fluoride-bearing flux of CaF.sub.2, CaCl.sub.2 or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy.

Method for treating rare earth-transition metal scrap

DOEpatents

Schmidt, F.A.; Peterson, D.T.; Wheelock, J.T.; Jones, L.L.

1992-12-29

Rare earth-transition metal (e.g., iron) scrap (e.g., Nd-Fe-B scrap) is flux (slag) remelted to reduce tramp non-metallic impurities, such as oxygen and nitrogen, and metallic impurities, such as Li, Na, Al, etc., picked up by the scrap from previous fabrication operations. The tramp impurities are reduced to concentrations acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. The scrap is electroslag or inductoslag melted using a rare earth fluoride-bearing flux of CaF[sub 2], CaCl[sub 2] or mixtures thereof or the slag resulting from practice of the thermite reduction process to make a rare earth-iron alloy. 3 figs.

Rare-earth metal prices in the USA ca. 1960 to 1994

USGS Publications Warehouse

Hedrick, James B.

1997-01-01

Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass. CA, USA, in 1949, was significant because it led to the production of commercial quantities or rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

Rare-earth metal prices in the USA ca. 1960 to 1994

USGS Publications Warehouse

Hedrick, J.B.

1997-01-01

Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass, CA, USA, in 1949, was significant because it led to the production of commercial quantities of rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic–Inorganic Perovskites

DOE PAGES

Sutter-Fella, Carolin M.; Ngo, Quynh P.; Cefarin, Nicola; ...

2018-04-30

Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. In this paper, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2) 2CsPb-halide (FACsPb-) and CH 3NH 3Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials.more » However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Finally, because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.« less

Cation-Dependent Light-Induced Halide Demixing in Hybrid Organic–Inorganic Perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sutter-Fella, Carolin M.; Ngo, Quynh P.; Cefarin, Nicola

Mixed cation metal halide perovskites with increased power conversion efficiency, negligible hysteresis, and improved long-term stability under illumination, moisture, and thermal stressing have emerged as promising compounds for photovoltaic and optoelectronic applications. In this paper, we shed light on photoinduced halide demixing using in situ photoluminescence spectroscopy and in situ synchrotron X-ray diffraction (XRD) to directly compare the evolution of composition and phase changes in CH(NH 2) 2CsPb-halide (FACsPb-) and CH 3NH 3Pb-halide (MAPb-) perovskites upon illumination, thereby providing insights into why FACs-perovskites are less prone to halide demixing than MA-perovskites. We find that halide demixing occurs in both materials.more » However, the I-rich domains formed during demixing accumulate strain in FACsPb-perovskites but readily relax in MA-perovskites. The accumulated strain energy is expected to act as a stabilizing force against halide demixing and may explain the higher Br composition threshold for demixing to occur in FACsPb-halides. In addition, we find that while halide demixing leads to a quenching of the high-energy photoluminescence emission from MA-perovskites, the emission is enhanced from FACs-perovskites. This behavior points to a reduction of nonradiative recombination centers in FACs-perovskites arising from the demixing process and buildup of strain. FACsPb-halide perovskites exhibit excellent intrinsic material properties with photoluminescence quantum yields that are comparable to MA-perovskites. Finally, because improved stability is achieved without sacrificing electronic properties, these compositions are better candidates for photovoltaic applications, especially as wide bandgap absorbers in tandem cells.« less

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.

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.

Syntheses and structures of alkaline earth metal bis(diphenylamides).

PubMed

Gärtner, Martin; Fischer, Reinald; Langer, Jens; Görls, Helmar; Walther, Dirk; Westerhausen, Matthias

2007-06-11

Various preparative procedures are employed in order to synthesize alkaline earth metal bis(diphenylamides) such as (i) metalation of HNPh2 with the alkaline earth metal M, (ii) metalation of HNPh2 with MPh2, (iii) metathesis reaction of MI2 with KNPh2, (iv) metalation of HNPh2 with PhMI in THF, and (v) metathesis reaction of PhMI with KNPh2 followed by a dismutation reaction yielding MPh2 and M(NPh2)2. The magnesium compounds [(diox)MgPh2]infinity (1) and (thf)2Mg(NPh2)2 (2) show tetracoordinate metal atoms, whereas in (dme)2Ca(NPh2)2 (3), (thf)4Sr(NPh2)2 (4), and (thf)4Ba(NPh2)2 (5) the metals are 6-fold coordinated. Additional agostic interactions between an ipso-carbon of one of the phenyl groups of the amide ligand and the alkaline earth metal atom lead to unsymmetric coordination of the NPh2 anions with two strongly different M-N-C angles in 3-5.

Metal carboxylates with open architectures.

PubMed

Rao, C N R; Natarajan, Srinivasan; Vaidhyanathan, R

2004-03-12

The field of inorganic open-framework materials is dominated by aluminosilicates and phosphates. The metal carboxylates have emerged as an important family in the last few years. This family includes not only mono- and dicarboxylates of transition, rare-earth, and main-group metals, but also a variety of hybrid structures. Some of the carboxylates possess novel adsorption and magnetic properties. Dicarboxylates and related species provide an effective means of designing novel hybrid structures with porous and other properties. In some of these structures, the dicarboxylate acts as a linker between two inorganic units. Hybrid nanocomposites are also of particular note, for example, cadmium oxalate host lattices that can accommodate extended alkali-metal halide structures. This Review discusses the synthesis, structure, and properties of various types of open-framework metal carboxylates.

Ionic-Electronic Ambipolar Transport in Metal Halide Perovskites: Can Electronic Conductivity Limit Ionic Diffusion?

PubMed

Kerner, Ross A; Rand, Barry P

2018-01-04

Ambipolar transport describes the nonequilibrium, coupled motion of positively and negatively charged particles to ensure that internal electric fields remain small. It is commonly invoked in the semiconductor community where the motion of excess electrons and holes drift and diffuse together. However, the concept of ambipolar transport is not limited to semiconductor physics. Materials scientists working on ion conducting ceramics understand ambipolar transport dictates the coupled diffusion of ions and the rate is limited by the ion with the lowest diffusion coefficient. In this Perspective, we review a third application of ambipolar transport relevant to mixed ionic-electronic conducting materials for which the motion of ions is expected to be coupled to electronic carriers. In this unique situation, the ambipolar diffusion model has been successful at explaining the photoenhanced diffusion of metal ions in chalcogenide glasses and other properties of materials. Recent examples of photoenhanced phenomena in metal halide perovskites are discussed and indicate that mixed ionic-electronic ambipolar transport is similarly important for a deep understanding of these emerging materials.

Metal-Halide Perovskite Transistors for Printed Electronics: Challenges and Opportunities.

PubMed

Lin, Yen-Hung; Pattanasattayavong, Pichaya; Anthopoulos, Thomas D

2017-12-01

Following the unprecedented rise in photovoltaic power conversion efficiencies during the past five years, metal-halide perovskites (MHPs) have emerged as a new and highly promising class of solar-energy materials. Their extraordinary electrical and optical properties combined with the abundance of the raw materials, the simplicity of synthetic routes, and processing versatility make MHPs ideal for cost-efficient, large-volume manufacturing of a plethora of optoelectronic devices that span far beyond photovoltaics. Herein looks beyond current applications in the field of energy, to the area of large-area electronics using MHPs as the semiconductor material. A comprehensive overview of the relevant fundamental material properties of MHPs, including crystal structure, electronic states, and charge transport, is provided first. Thereafter, recent demonstrations of MHP-based thin-film transistors and their application in logic circuits, as well as bi-functional devices such as light-sensing and light-emitting transistors, are discussed. Finally, the challenges and opportunities in the area of MHPs-based electronics, with particular emphasis on manufacturing, stability, and health and environmental concerns, are highlighted. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Trivalent Rare-Earth-Metal Bis(trimethylsilyl)amide Halide Complexes by Targeted Oxidations.

PubMed

Bienfait, André M; Wolf, Benjamin M; Törnroos, Karl W; Anwander, Reiner

2018-05-07

In contrast to previously applied salt metathesis protocols the targeted rare-earth-metal compounds Ln[N(SiMe 3 ) 2 ] 2 (halogenido) were accessed by oxidation of Ln(II) silylamide precursors. Treatment of Sm[N(SiMe 3 ) 3 ] 2 (thf) 2 with 0.5 equiv of C 2 Cl 6 or 0.25 equiv of TeBr 4 in thf and crystallization thereof gave [Sm{N(SiMe 3 ) 2 } 2 (μ-X)(thf)] 2 (X = Cl, Br). A similar reaction/crystallization procedure performed with 0.5 equiv of 1,2-diiodoethane gave monomeric Sm[N(SiMe 3 ) 2 ] 2 I(thf) 2 . Switching to Yb[N(SiMe 3 ) 2 ] 2 (thf) 2 , the aforementioned oxidants generated monomeric five-coordinate complexes Yb[N(SiMe 3 ) 2 ] 2 X(thf) 2 (X = Cl, Br, I). The reaction of Eu[N(SiMe 3 ) 2 ] 2 (thf) 2 with 0.5 equiv of C 2 Cl 6 in thf yielded the separated ion pair [Eu{N(SiMe 3 ) 2 } 3 Cl][(thf) 5 Eu(μ-Cl) 2 Eu(thf) 5 ]. Performing the chlorination in n-hexane led to oxidation followed by rapid disproportionation into EuCl 3 (thf) x and Eu[N(SiMe 3 ) 2 ] 3 . The bromination reaction did not afford crystalline material, while the iodination gave crystals of divalent EuI 2 (thf) 5 . Use of trityl chloride (Ph 3 CCl) as the oxidant in thf accomplished the Eu(III) species [Eu{N(SiMe 3 ) 2 } 2 (μ-Cl)(thf)] 2 . In situ oxidation of putative [Tm{N(SiMe 3 ) 2 } 2 (thf) x ] using 0.5 equiv of C 2 Cl 6 in thf followed by crystallization from n-hexane led to the formation of a mixture of [Tm{N(SiMe 3 ) 2 } 2 (μ-Cl)(thf)] 2 and Tm[N(SiMe 3 ) 2 ] 3 . Switching the oxidant to 0.5 equiv of 1,2-diiodoethane and crystallizing from thf repeatedly afforded the bis-halogenated complex Tm[N(SiMe 3 ) 2 ]I 2 (thf) 3 .

Two-Dimensional Materials for Halide Perovskite-Based Optoelectronic Devices.

PubMed

Chen, Shan; Shi, Gaoquan

2017-06-01

Halide perovskites have high light absorption coefficients, long charge carrier diffusion lengths, intense photoluminescence, and slow rates of non-radiative charge recombination. Thus, they are attractive photoactive materials for developing high-performance optoelectronic devices. These devices are also cheap and easy to be fabricated. To realize the optimal performances of halide perovskite-based optoelectronic devices (HPODs), perovskite photoactive layers should work effectively with other functional materials such as electrodes, interfacial layers and encapsulating films. Conventional two-dimensional (2D) materials are promising candidates for this purpose because of their unique structures and/or interesting optoelectronic properties. Here, we comprehensively summarize the recent advancements in the applications of conventional 2D materials for halide perovskite-based photodetectors, solar cells and light-emitting diodes. The examples of these 2D materials are graphene and its derivatives, mono- and few-layer transition metal dichalcogenides (TMDs), graphdiyne and metal nanosheets, etc. The research related to 2D nanostructured perovskites and 2D Ruddlesden-Popper perovskites as efficient and stable photoactive layers is also outlined. The syntheses, functions and working mechanisms of relevant 2D materials are introduced, and the challenges to achieving practical applications of HPODs using 2D materials are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids.

PubMed

Carraher, Jack M; Pestovsky, Oleg; Bakac, Andreja

2012-05-21

Near-UV photolysis of aqueous solutions of propionic acid and aqueous Fe(3+) in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe(2+). The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize Fe(2+). The photochemistry in the presence of halide ions (X(-) = Cl(-), Br(-)) generates ethyl halides via halogen atom abstraction from FeX(n)(3-n) by ethyl radicals. Near-quantitative yields of C(2)H(5)X are obtained at ≥0.05 M X(-). Competition experiments with Co(NH(3))(5)Br(2+) provided kinetic data for the reaction of ethyl radicals with FeCl(2+) (k = (4.0 ± 0.5) × 10(6) M(-1) s(-1)) and with FeBr(2+) (k = (3.0 ± 0.5) × 10(7) M(-1) s(-1)). Photochemical decarboxylation of propionic acid in the presence of Cu(2+) generates ethylene and Cu(+). Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes Cu(+) to Cu(2+), and removes gaseous olefins to prevent accumulation of Cu(+)(olefin) complexes and depletion of Cu(2+). The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids.

Metal sulfide and rare-earth phosphate nanostructures and methods of making same

DOEpatents

Wong, Stanislaus; Zhang, Fen

2016-06-28

The present invention provides a method of producing a crystalline rare earth phosphate nanostructure. The method comprising: providing a rare earth metal precursor solution and providing a phosphate precursor solution; placing a porous membrane between the metal precursor solution and the phosphate precursor solution, wherein metal cations of the metal precursor solution and phosphate ions of the phosphate precursor solution react, thereby producing a crystalline rare earth metal phosphate nanostructure.

Maximizing and stabilizing luminescence from halide perovskites with potassium passivation

NASA Astrophysics Data System (ADS)

Abdi-Jalebi, Mojtaba; Andaji-Garmaroudi, Zahra; Cacovich, Stefania; Stavrakas, Camille; Philippe, Bertrand; Richter, Johannes M.; Alsari, Mejd; Booker, Edward P.; Hutter, Eline M.; Pearson, Andrew J.; Lilliu, Samuele; Savenije, Tom J.; Rensmo, Håkan; Divitini, Giorgio; Ducati, Caterina; Friend, Richard H.; Stranks, Samuel D.

2018-03-01

Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield—a quantity that must be maximized to obtain high efficiency—remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can

Maximizing and stabilizing luminescence from halide perovskites with potassium passivation.

PubMed

Abdi-Jalebi, Mojtaba; Andaji-Garmaroudi, Zahra; Cacovich, Stefania; Stavrakas, Camille; Philippe, Bertrand; Richter, Johannes M; Alsari, Mejd; Booker, Edward P; Hutter, Eline M; Pearson, Andrew J; Lilliu, Samuele; Savenije, Tom J; Rensmo, Håkan; Divitini, Giorgio; Ducati, Caterina; Friend, Richard H; Stranks, Samuel D

2018-03-21

Metal halide perovskites are of great interest for various high-performance optoelectronic applications. The ability to tune the perovskite bandgap continuously by modifying the chemical composition opens up applications for perovskites as coloured emitters, in building-integrated photovoltaics, and as components of tandem photovoltaics to increase the power conversion efficiency. Nevertheless, performance is limited by non-radiative losses, with luminescence yields in state-of-the-art perovskite solar cells still far from 100 per cent under standard solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps of approximately 1.7 to 1.9 electronvolts), photoinduced ion segregation leads to bandgap instabilities. Here we demonstrate substantial mitigation of both non-radiative losses and photoinduced ion migration in perovskite films and interfaces by decorating the surfaces and grain boundaries with passivating potassium halide layers. We demonstrate external photoluminescence quantum yields of 66 per cent, which translate to internal yields that exceed 95 per cent. The high luminescence yields are achieved while maintaining high mobilities of more than 40 square centimetres per volt per second, providing the elusive combination of both high luminescence and excellent charge transport. When interfaced with electrodes in a solar cell device stack, the external luminescence yield-a quantity that must be maximized to obtain high efficiency-remains as high as 15 per cent, indicating very clean interfaces. We also demonstrate the inhibition of transient photoinduced ion-migration processes across a wide range of mixed halide perovskite bandgaps in materials that exhibit bandgap instabilities when unpassivated. We validate these results in fully operating solar cells. Our work represents an important advance in the construction of tunable metal halide perovskite films and interfaces that can approach

Silicon halide-alkali metal flames as a source of solar grade silicon

NASA Technical Reports Server (NTRS)

Olsen, D. B.; Miller, W. J.

1979-01-01

The feasibility of using alkali metal-silicon halide diffusion flames to produce solar-grade silicon in large quantities and at low cost is demonstrated. Prior work shows that these flames are stable and that relatively high purity silicon can be produced using Na + SiCl4 flames. Silicon of similar purity is obtained from Na + SiF4 flames although yields are lower and product separation and collection are less thermochemically favored. Continuous separation of silicon from the byproduct alkali salt was demonstrated in a heated graphite reactor. The process was scaled up to reduce heat losses and to produce larger samples of silicon. Reagent delivery systems, scaled by a factor of 25, were built and operated at a production rate of 0.5 kg Si/h. Very rapid reactor heating rates are observed with wall temperatures reaching greater than 2000 K. Heat release parameters were measured using a cooled stainless steel reactor tube. A new reactor was designed.

Synthesis of Cesium Lead Halide Perovskite Nanocrystals in a Droplet-Based Microfluidic Platform: Fast Parametric Space Mapping.

PubMed

Lignos, Ioannis; Stavrakis, Stavros; Nedelcu, Georgian; Protesescu, Loredana; deMello, Andrew J; Kovalenko, Maksym V

2016-03-09

Prior to this work, fully inorganic nanocrystals of cesium lead halide perovskite (CsPbX3, X = Br, I, Cl and Cl/Br and Br/I mixed halide systems), exhibiting bright and tunable photoluminescence, have been synthesized using conventional batch (flask-based) reactions. Unfortunately, our understanding of the parameters governing the formation of these nanocrystals is still very limited due to extremely fast reaction kinetics and multiple variables involved in ion-metathesis-based synthesis of such multinary halide systems. Herein, we report the use of a droplet-based microfluidic platform for the synthesis of CsPbX3 nanocrystals. The combination of online photoluminescence and absorption measurements and the fast mixing of reagents within such a platform allows the rigorous and rapid mapping of the reaction parameters, including molar ratios of Cs, Pb, and halide precursors, reaction temperatures, and reaction times. This translates into enormous savings in reagent usage and screening times when compared to analogous batch synthetic approaches. The early-stage insight into the mechanism of nucleation of metal halide nanocrystals suggests similarities with multinary metal chalcogenide systems, albeit with much faster reaction kinetics in the case of halides. Furthermore, we show that microfluidics-optimized synthesis parameters are also directly transferrable to the conventional flask-based reaction.

The gas phase emitter effect of lanthanum within ceramic metal halide lamps and its dependence on the La vapor pressure and operating frequency

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruhrmann, C.; Hoebing, T.; Bergner, A.

2015-08-07

The gas phase emitter effect increases the lamp lifetime by lowering the work function and, with it, the temperature of the tungsten electrodes of metal halide lamps especially for lamps in ceramic vessels due to their high rare earth pressures. It is generated by a monolayer on the electrode surface of electropositive atoms of certain emitter elements, which are inserted into the lamp bulb by metal iodide salts. They are vaporized, dissociated, ionized, and deposited by an emitter ion current onto the electrode surface within the cathodic phase of lamp operation with a switched-dc or ac-current. The gas phase emittermore » effect of La and the influence of Na on the emitter effect of La are studied by spatially and phase-resolved pyrometric measurements of the electrode tip temperature, La atom, and ion densities by optical emission spectroscopy as well as optical broadband absorption spectroscopy and arc attachment images by short time photography. An addition of Na to the lamp filling increases the La vapor pressure within the lamp considerably, resulting in an improved gas phase emitter effect of La. Furthermore, the La vapor pressure is raised by a heating of the cold spot. In this way, conditions depending on the La vapor pressure and operating frequency are identified, at which the temperature of the electrodes becomes a minimum.« less

Thermophysical properties of liquid rare earth metals

NASA Astrophysics Data System (ADS)

Thakor, P. B.; Sonvane, Y. A.; Patel, H. P.; Jani, A. R.

2013-06-01

The thermodynamical properties like long wavelength limit S(0), iso-thermal compressibility (χT), thermal expansion coefficient (αV), thermal pressure coefficient (γV), specific heat at constant volume (CV) and specific heat at constant pressure (CP) are calculated for liquid rare earth metals. Our newly constructed parameter free model potential is used to describe the electron ion interaction due to Sarkar et al (S) local field correction function. Lastly, we conclude that our newly constructed model potential is capable to explain the thermophysical properties of liquid rare earth metals.

METHOD OF ALLOYING REACTIVE METALS WITH ALUMINUM OR BERYLLIUM

DOEpatents

Runnalls, O.J.C.

1957-10-15

A halide of one or more of the reactive metals, neptunium, cerium and americium, is mixed with aluminum or beryllium. The mass is heated at 700 to 1200 deg C, while maintaining a substantial vacuum of above 10/sup -3/ mm of mercury or better, until the halide of the reactive metal is reduced and the metal itself alloys with the reducing metal. The reaction proceeds efficiently due to the volatilization of the halides of the reducing metal, aluminum or beryllium.

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.

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 63.2465 - What requirements must I meet for process vents that emit hydrogen halide and halogen HAP or HAP...

Code of Federal Regulations, 2011 CFR

2011-07-01

... process vents that emit hydrogen halide and halogen HAP or HAP metals? 63.2465 Section 63.2465 Protection... Compliance Requirements § 63.2465 What requirements must I meet for process vents that emit hydrogen halide... section. (b) If any process vents within a process emit hydrogen halide and halogen HAP, you must...

Metal Based Synthetic Strategies and the Examination of Structure Determining Factors in Alkaline Earth Metal Compounds

NASA Astrophysics Data System (ADS)

Takahashi, Yuriko

Last decades have witnessed a large expansion of the organometallic heavier alkaline earth metal species. However, continued growth of this promising area of chemistry has been slowed by severe restrictions and limitations in viable synthetic methodologies leading to difficulties in preparing and characterizing the target compounds. There is clearly a need for the further development of synthetic methodologies and detailed structure function analysis that will promote the further advancement of organoalkaline earth metal chemistry in applications as diverse as materials chemistry and catalysis. This thesis work greatly extends the synthetic options currently available towards organoalkaline earth metal species by introducing redox transmetallation protolysis (RTP), a reaction based on the readily available Ph3Bi as a non-toxic transmetallation agent. Based on a straightforward one-pot procedure and work-up, Ph3Bi based RTP presents a powerful synthetic alternative for the facile preparation of a large variety of heavy alkaline earth metal compounds. The second part of the thesis explores the effect of secondary non covalent interactions on the coordination chemistry as well as thermal properties of a series of novel alkali, alkaline earth, rare earth as well as heterobimetallic alkali/alkaline earth fluoroalkoxides. These compounds showcase the significance of non-covalent M···F-C and agostic interactions on metal stabilization and structural features, providing critical input on ligand design for the design of advanced metal organic vapor deposition (MOCVD) precursor materials. This work also showcases the impact of M···F-C interactions over M---co-ligand coordination, a critical precursor design element as well.

Peroxidative oxidation of halides catalysed by myeloperoxidase. Effect of fluoride on halide oxidation.

PubMed

Zgliczyński, J M; Stelmaszyńska, T; Olszowska, E; Krawczyk, A; Kwasnowska, E; Wróbel, J T

1983-01-01

It was found that all halides can compete with cyanide for binding with myeloperoxidase. The lower is the pH, the higher is the affinity of halides. The apparent dissociation constants (Kd) of myeloperoxidase-cyanide complex were determined in the presence of F-, Cl-, Br- and I- in the pH range of 4 to 7. In slightly acidic pH (4 - 6) fluoride and chloride exhibit a higher affinity towards the enzyme than bromide and iodide. Taking into account competition between cyanide and halides for binding with myeloperoxidase the dissociation constants of halide-myeloperoxidase complexes were calculated. All halides except fluoride can be oxidized by H2O2 in the presence of myeloperoxidase. However, since fluoride can bind with myeloperoxidase, it can competitively inhibit the oxidation of other halides. Fluoride was a competitive inhibitor with respect to other halides as well as to H2O2. Inhibition constants (Ki) for fluoride as a competitive inhibitor with respect to H2O2 increased from iodide oxidation through bromide to chloride oxidation.

Destabilized and catalyzed borohydride for reversible hydrogen storage

DOEpatents

Mohtadi, Rana F [Northville, MI; Zidan, Ragaiy [Aiken, SC; Gray, Joshua [Aiken, SC; Stowe, Ashley C [Knoxville, TN; Sivasubramanian, Premkumar [Aiken, SC

2012-02-28

A process of forming a hydrogen storage material, including the steps of: providing a borohydride material of the formula: M(BH.sub.4).sub.x where M is an alkali metal or an alkaline earth metal and 1.ltoreq.x.ltoreq.2; providing an alanate material of the formula: M.sub.1(AlH.sub.4).sub.x where M.sub.1 is an alkali metal or an alkaline earth metal and 1.ltoreq.x.ltoreq.2; providing a halide material of the formula: M.sub.2Hal.sub.x where M.sub.2 is an alkali metal, an alkaline earth metal or transition metal and Hal is a halide and 1.ltoreq.x.ltoreq.4; combining the borohydride, alanate and halide materials such that 5 to 50 molar percent from the borohydride material is present forming a reaction product material having a lower hydrogen release temperature than the alanate material.

Positive electrode current collector for liquid metal cells

DOEpatents

Shimotake, Hiroshi; Bartholme, Louis G.

1984-01-01

A current collector for the positive electrode of an electrochemical cell with a positive electrode including a sulfide. The cell also has a negative electrode and a molten salt electrolyte including halides of a metal selected from the alkali metals and the alkaline earth metals in contact with both the positive and negative electrodes. The current collector has a base metal of copper, silver, gold, aluminum or alloys thereof with a coating thereon of iron, nickel, chromium or alloys thereof. The current collector when subjected to cell voltage forms a sulfur-containing compound on the surface thereby substantially protecting the current collector from further attack by sulfur ions during cell operation. Both electroless and electrolytic processes may be used to deposit coatings.

Origin of vertical orientation in two-dimensional metal halide perovskites and its effect on photovoltaic performance.

PubMed

Chen, Alexander Z; Shiu, Michelle; Ma, Jennifer H; Alpert, Matthew R; Zhang, Depei; Foley, Benjamin J; Smilgies, Detlef-M; Lee, Seung-Hun; Choi, Joshua J

2018-04-06

Thin films based on two-dimensional metal halide perovskites have achieved exceptional performance and stability in numerous optoelectronic device applications. Simple solution processing of the 2D perovskite provides opportunities for manufacturing devices at drastically lower cost compared to current commercial technologies. A key to high device performance is to align the 2D perovskite layers, during the solution processing, vertical to the electrodes to achieve efficient charge transport. However, it is yet to be understood how the counter-intuitive vertical orientations of 2D perovskite layers on substrates can be obtained. Here we report a formation mechanism of such vertically orientated 2D perovskite in which the nucleation and growth arise from the liquid-air interface. As a consequence, choice of substrates can be liberal from polymers to metal oxides depending on targeted application. We also demonstrate control over the degree of preferential orientation of the 2D perovskite layers and its drastic impact on device performance.

APPARATUS FOR HIGH PURITY METAL RECOVERY

DOEpatents

Magel, T.T.

1959-02-10

An apparatus is described for preparing high purity metal such as uranium, plutonium and the like from an impure mass of the same metal. The apparatus is arranged so that the impure metal is heated and swept by a stream of hydrogen gas bearing a halogen such as iodine. The volatiie metal halide formed is carried on to a hot filament where the metal halide is decomposed and the molten high purity metal is collected in a rceeiver below

APPARATUS FOR THE PRODUCTION OF LITHIUM METAL

DOEpatents

Baker, P.S.; Duncan, F.R.; Greene, H.B.

1961-08-22

Methods and apparatus for the production of high-purity lithium from lithium halides are described. The apparatus is provided for continuously contacting a molten lithium halide with molten barium, thereby forming lithium metal and a barium halide, establishing separate layers of these reaction products and unreacted barium and lithium halide, and continuously withdrawing lithium and barium halide from the reaction zone. (AEC)

First-principles Investigation of the Structure, Mobility and Optical Properties of Self-Trapped Excitons in Alkali Metal, Lanthanum and Barium Halide Scintillators

NASA Astrophysics Data System (ADS)

Bizarri, Gregory; Del Ben, Mauro; Bourret, Edith; Canning, Andrew

The performance of new and improved materials for gamma ray scintillator detectors is dependant on multiple factors such as quantum efficiency, energy transport etc. In halide scintillator materials the energy transport is often impacted by self-trapped exciton (STE) formation and mobility. We present first-principles calculations at the hybrid density functional theory level for the structure, mobility and optical properties of STEs and their associated lattice defects (VK centers) in two important families of scintillator materials, alkali metal and lanthanum halides (AX and LaX). AX and LaX have been extensively characterized by experiments and serve as benchmark systems to assess the accuracy of our theoretical procedure. We show that hydrid functionals accurately predict the different types of self-trapped excitons (on and off-center) found in AX and LX materials in agreement with EPR experiments. We then applied this approach to perform preliminary studies on classes of new scintillator materials including the barium mixed halides and compared with our new experimental results. These studies have the potential to benefit the development of improved scintillator materials tailored for specific applications. This work is supported by the U.S. Department of Energy/NNSA/DNN R&D and is carried out at Lawrence Berkeley National Laboratory under Contract No. AC02-05CH11231.

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

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.

Rare-Earth Metals and Their Applications in Aviation

DTIC Science & Technology

1984-08-01

metals are not as common as iron and steel which are visible everywhere, yet they are not unfamiliar to us. We often encounter them in everyday life...the flint of a lighter. It is an alloy of rare-earth metal and iron . It contains about 30% iron and the remainder is a composite rare-earth alloy...used to manufacture the detonators of bullets and shells as well as the pyrophoric alloys of firing devices. This type of alloy has a 49.5% content of

Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

DOE PAGES

Dou, Benjia; Wheeler, Lance M.; Christians, Jeffrey A.; ...

2018-03-14

Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporatesmore » into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.« less

Degradation of Highly Alloyed Metal Halide Perovskite Precursor Inks: Mechanism and Storage Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dou, Benjia; Wheeler, Lance M.; Christians, Jeffrey A.

Whereas the promise of metal halide perovskite (MHP) photovoltaics (PV) is that they can combine high efficiency with solution-processability, the chemistry occurring in precursor inks is largely unexplored. Herein, we investigate the degradation of MHP solutions based on the most widely used solvents, dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). For the MHP inks studied, which contain formamidinium (FA+), methylammonium (MA+), cesium (Cs+), lead (Pb2+), bromide (Br-), and iodide (I-), dramatic compositional changes are observed following storage of the inks in nitrogen in the dark. We show that hydrolysis of DMF in the precursor solution forms dimethylammonium formate, which subsequently incorporatesmore » into the MHP film to compromise the ability of Cs+ and MA+ to stabilize FA+-based MHP. The changes in solution chemistry lead to a modification of the perovskite film stoichiometry, band gap, and structure. The solid precursor salts are stable when ball-milled into a powder, allowing for the storage of large quantities of stoichiometric precursor materials.« less

Spectroscopic imaging of metal halide high-intensity discharge lamps

NASA Astrophysics Data System (ADS)

Bonvallet, Geoffrey A.

The body of this work consists of three main research projects. An optical- and near-ultraviolet-wavelength absorption study sought to determine absolute densities of ground and excited level Sc atoms, ground level Sc + ions, and ground level Na atoms in a commercial 250 W metal halide high intensity discharge lamp during operation. These measurements also allowed the determination of the arc temperature and absolute electron density as functions of radius. Through infrared emission spectroscopy, relative densities of sodium and scandium were determined as functions of radius. Using the absolute densities gained from the optical experiment, these relative densities were calibrated. In addition, direct observation of the infrared emission allowed us to characterize the infrared power losses of the lamp. When considered as a fraction of the overall power consumption, the near-infrared spectral power losses were not substantial enough to warrant thorough investigation of their reduction in these lamps. The third project was an attempt to develop a portable x-ray diagnostic experiment. Two-dimensional spatial maps of the lamps were analyzed to determine absolute elemental mercury densities and the arc temperature as a function of radius. Two methods were used to improve the calibration of the density measurements and to correct for the spread in x-ray energy: known solutions of mercury in nitric acid, and an arc lamp which was uniformly heated to evaporate the mercury content. Although many complexities arose in this experiment, its goal was successfully completed.

Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

PubMed

Meshram, Pratima; Pandey, B D; Mankhand, T R

2016-05-01

Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features. Copyright © 2015. Published by Elsevier Ltd.

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

2016-03-09

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.

Spermicidal activity of some halides.

PubMed

Narayan, J P; Singh, J N

1979-01-01

Though most of the metallic ions are spermicidal in action, the present investigation emphasises the spermicidal activity of anions. Among the inorganic compounds screened at 4 concentrations (0.01%, 0.1%, 1% and 5%) halides are mainly spermicidal, except NaCl, KCl & CsCl which are spermiostatic; sulphates and nitrates are mainly spermiostatic except ZnSO4 at 1% concentration and above; CuSO4, Al2 (SO4)3, Uo2(NO3)2.6H2O and AgNO3 at 5% concentration where they become spermicidal.

Analysis of molecular structure, spectroscopic properties (FT-IR, micro-Raman and UV-vis) and quantum chemical calculations of free and ligand 2-thiopheneglyoxylic acid in metal halides (Cd, Co, Cu, Ni and Zn).

PubMed

Gökce, Halil; Bahçeli, Semiha

2013-12-01

In this study, molecular geometries, experimental vibrational wavenumbers, electronic properties and quantum chemical calculations of 2-thiopheneglyoxylic acid molecule, (C6H4O3S), and its metal halides (Cd, Co, Cu, Ni and Zn) which are used as pharmacologic agents have been investigated experimentally by FT-IR, micro-Raman and UV-visible spectroscopies and elemental analysis. Meanwhile the vibrational calculations were verified by DFT/B3LYP method with 6-311++G(d,p) and LANL2DZ basis sets in the ground state, for free TPGA molecule and its metal halide complexes, respectively, for the first time. The calculated fundamental vibrational frequencies for the title compounds are in a good agreement with the experimental data. Copyright © 2013 Elsevier B.V. All rights reserved.

Radiative properties of ceramic metal-halide high intensity discharge lamps containing additives in argon plasma

NASA Astrophysics Data System (ADS)

Cressault, Yann; Teulet, Philippe; Zissis, Georges

2016-07-01

The lighting represents a consumption of about 19% of the world electricity production. We are thus searching new effective and environment-friendlier light sources. The ceramic metal-halide high intensity lamps (C-MHL) are one of the options for illuminating very high area. The new C-MHL lamps contain additives species that reduce mercury inside and lead to a richer spectrum in specific spectral intervals, a better colour temperature or colour rendering index. This work is particularly focused on the power radiated by these lamps, estimated using the net emission coefficient, and depending on several additives (calcium, sodium, tungsten, dysprosium, and thallium or strontium iodides). The results show the strong influence of the additives on the power radiated despite of their small quantity in the mixtures and the increase of visible radiation portion in presence of dysprosium.

Diode-Pumped Organo-Lead Halide Perovskite Lasing in a Metal-Clad Distributed Feedback Resonator.

PubMed

Jia, Yufei; Kerner, Ross A; Grede, Alex J; Brigeman, Alyssa N; Rand, Barry P; Giebink, Noel C

2016-07-13

Organic-inorganic lead halide perovskite semiconductors have recently reignited the prospect of a tunable, solution-processed diode laser, which has the potential to impact a wide range of optoelectronic applications. Here, we demonstrate a metal-clad, second-order distributed feedback methylammonium lead iodide perovskite laser that marks a significant step toward this goal. Optically pumping this device with an InGaN diode laser at low temperature, we achieve lasing above a threshold pump intensity of 5 kW/cm(2) for durations up to ∼25 ns at repetition rates exceeding 2 MHz. We show that the lasing duration is not limited by thermal runaway and propose instead that lasing ceases under continuous pumping due to a photoinduced structural change in the perovskite that reduces the gain on a submicrosecond time scale. Our results indicate that the architecture demonstrated here could provide the foundation for electrically pumped lasing with a threshold current density Jth < 5 kA/cm(2) under sub-20 ns pulsed drive.

Crystallographic phases in heavy rare earth metals under megabar pressures

NASA Astrophysics Data System (ADS)

Samudrala, G. K.; Vohra, Y. K.

2012-07-01

Experiments aimed at understanding the crystallographic phases of heavy rare earth metals were carried out in a diamond anvil cell at the Advanced Photon Source, Argonne National Laboratory. Heavy rare earth metals dysprosium (Dy), holmium (Ho), erbium (Er) and thulium (Tm) were compressed to multi-megabar pressures. The rare earth crystal sequence hcp→Sm-type→dhcp→distorted-fcc (dfcc) is observed in all four elements. Upon further compression, a structural transformation to a monoclinic C2/m phase has been observed. We summarize the results from these experiments and present Rietveld structural refinements on high pressure phases for the specific case of dysprosium.

Medical imaging scintillators from glass-ceramics using mixed rare-earth halides

NASA Astrophysics Data System (ADS)

Beckert, M. Brooke; Gallego, Sabrina; Ding, Yong; Elder, Eric; Nadler, Jason H.

2016-10-01

Recent years have seen greater interest in developing new luminescent materials to replace scintillator panels currently used in medical X-ray imaging systems. The primary areas targeted for improvement are cost and image resolution. Cost reduction is somewhat straightforward in that less expensive raw materials and processing methods will yield a less expensive product. The path to improving image resolution is more complex because it depends on several properties of the scintillator material including density, transparency, and composition, among others. The present study focused on improving image resolution using composite materials, known as glass-ceramics that contain nanoscale scintillating crystallites formed within a transparent host glass matrix. The small size of the particles and in-situ precipitation from the host glass are key to maintaining transparency of the composite scintillator, which ensures that a majority of the light produced from absorbed X-rays can actually be used to create an image of the patient. Because light output is the dominating property that determines the image resolution achievable with a given scintillator, it was used as the primary metric to evaluate performance of the glass-ceramics relative to current scintillators. Several glass compositions were formulated and then heat treated in a step known as "ceramization" to grow the scintillating nanocrystals, whose light output was measured in response to a 65 kV X-ray source. Performance was found to depend heavily on the thermal history of the glass and glass-ceramic, and so additional studies are required to more precisely determine optimal process temperatures. Of the compositions investigated, an alumino-borosilicate host glass containing 56mol% scintillating rare-earth halides (BaF2, GdF3, GdBr3, TbF3) produced the highest recorded light output at nearly 80% of the value recorded using a commercially-available GOS:Tb panel as a reference.

Silver-halide gelatin holograms

NASA Astrophysics Data System (ADS)

Chang, B. J.; Winick, K.

1980-05-01

The use of a silver-halide gelatin for volume phase holograms having a wide spectral response and lower exposure requirements than alternatives and using commercially available silver salts, is proposed. The main difference between the dichromated gelatin and silver-halide processes is the creation of a hologram latent image, which is given in the form of a hardness differential between exposed and unexposed regions in the silver halide hologram; the differential is in turn created by the reaction products of either tanning development or tanning bleach, which harden the gelatin with link-bonds between molecules.

Structural and Dynamical Properties of Alkaline Earth Metal Halides in Supercritical Water: Effect of Ion Size and Concentration.

PubMed

Keshri, Sonanki; Tembe, B L

2017-11-22

Constant temperature-constant pressure molecular dynamics simulations have been performed for aqueous alkaline earth metal chloride [M 2+ -Cl - (M = Mg, Ca, Sr, and Ba)] solutions over a wide range of concentrations (0.27-5.55 m) in supercritical (SC) and ambient conditions to investigate their structural and dynamical properties. A strong influence of the salt concentration is observed on the ion-ion pair correlation functions in both ambient and SC conditions. In SC conditions, significant clustering is observed in the 0.27 m solution, whereas the reverse situation is observed at room temperature and this is also supported by the residence times of the clusters. The concentration and ion size (cation size) seem to have opposite effects on the average number of hydrogen bonds. The simulation results show that the self-diffusion coefficients of water, cations, and the chloride ion increase with increasing temperature, whereas they decrease with increasing salt concentration. The cluster size distribution shows a strong density dependence in both ambient and SC conditions. In SC conditions, cluster sizes display a near-Gaussian distribution, whereas the distribution decays monotonically in ambient conditions.

Aluminum Pitting Corrosion in Halide Media: A Quantum Model and Empirical Evidence

NASA Astrophysics Data System (ADS)

Lashgari, Mohsen; Kianpour, Effat; Mohammadi, Esmaeil

2013-12-01

The phenomenon of localized damage of aluminum oxide surface in the presence of halide anions was scrutinized at an atomistic level, through the cluster approach and density functional theory. The phenomenon was also investigated empirically through Tafel polarization plots and scanning electron microscopy. A distinct behavior witnessed in the fluoride medium was justified through the hard-soft acid-base principle. The atomistic investigations revealed the greatest potency for chloride entrance into the metal oxide lattice and rationalized to the severity of damage. The interaction of halide anions with the oxide surface causing some displacements on the position of Al atoms provides a mechanistic insight of the phenomenon.

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

Making and Breaking of Lead Halide Perovskites

DOE PAGES

Manser, Joseph S.; Saidaminov, Makhsud I.; Christians, Jeffrey A.; ...

2016-01-20

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 rapidmore » 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

Theoretical study of the dipole moments of selected alkaline-earth halides

NASA Technical Reports Server (NTRS)

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.; Ahlrichs, R.

1986-01-01

Ab initio calculations at the self-consistent-field (SCF), singles-plus-doubles configuration-interaction (SDCI), and coupled-pair functional (CPF) level, are reported for the dipole moments and dipole derivatives of the X2Sigma(+) ground states of BeF, BeCl, MgF, MgCl, CaF, CaCl, and SrF. For comparison, analogous calculations are performed for the X1Sigma(+) state of KCl. The CPF results are found to be in remarkably better agreement with experiment than are the SCF and SDCI results. Apparently higher excitations are required to properly describe the radial extent along the bond axis of the remaining valence electron on the alkaline-earth metal.

Yb-doped large-mode-area laser fiber fabricated by halide-gas-phase-doping technique

NASA Astrophysics Data System (ADS)

Peng, Kun; Wang, Yuying; Ni, Li; Wang, Zhen; Gao, Cong; Zhan, Huan; Wang, Jianjun; Jing, Feng; Lin, Aoxiang

2015-06-01

In this manuscript, we designed a rare-earth-halide gas-phase-doping setup to fabricate a large-mode-area fiber for high power laser applications. YbCl3 and AlCl3 halides are evaporated, carried respectively and finally mixed with usual host gas material SiCl4 at the hot zone of MCVD system. Owing to the all-gas-phasing reaction process and environment, the home-made Yb-doped fiber preform has a homogeneous large core and modulated refractive index profile to keep high beam quality. The drawn fiber core has a small numerical aperture of 0.07 and high Yb concentration of 9500 ppm. By using a master oscillator power amplifier system, nearly kW-level (951 W) laser output power was obtained with a slope efficiency of 83.3% at 1063.8 nm, indicating the competition and potential of the halide-gas-phase-doping technique for high power laser fiber fabrication.

Inorganic rechargeable non-aqueous cell

DOEpatents

Bowden, William L.; Dey, Arabinda N.

1985-05-07

A totally inorganic non-aqueous rechargeable cell having an alkali or alkaline earth metal anode such as of lithium, a sulfur dioxide containing electrolyte and a discharging metal halide cathode, such as of CuCl.sub.2, CuBr.sub.2 and the like with said metal halide being substantially totally insoluble in SO.sub.2 and admixed with a conductive carbon material.

Hybrid Lead Halide Layered Perovskites with Silsesquioxane Interlayers.

PubMed

Kataoka, Sho; Kaburagi, Wako; Mochizuki, Hiroyuki; Kamimura, Yoshihiro; Sato, Kazuhiko; Endo, Akira

2018-01-01

Hybrid organic-lead halide perovskites exhibit remarkable properties as semiconductors and light absorbers. Here, we report the formation of silsesquioxane-lead halide hybrid layered perovskites. We prepared silsesquioxane with a cubic cage-like structure and fabricated hybrid silsesquioxane-lead halide layered perovskites in a self-assembled manner. It is demonstrated that the silsesquioxane maintain their cage-like structure between lead halide perovskite layers. The silsesquioxane-lead halide perovskites also show excitonic absorption and emission in the visible light region similar to typical lead halide layered perovskites.

Nanowires of metal (Cd, Cu) halide complexes with 8-hydroxyquinoline for photoelectrochemical and electrochemiluminescence sensing

NASA Astrophysics Data System (ADS)

Huang, Shan; Pang, Guangming; Li, Xiangkui; Li, Jianping; Pan, Hongcheng

2017-12-01

Metal-hydroxyquinoline-halogen (MqX, M = Cd, Cu; q = 8-hydroxyquinoline; X = Cl, Br, I) nanowires are synthesized via a sonochemical-assisted method. The elemental analysis (EA), inductively coupled plasma-optical emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS) support an M/q/X ratio of 1:1:1. The electron microscope images reveal a typical CdqX and CuqX nanowire diameter of 30-50 nm and a nanowire length of 400-600 nm. In addition, the synthesis of the MqX nanowires is only observed when there is an excess of halide ions (X/q molar ratio of 3 or greater). This halide deficiency results in the formation of micrometer-sized Mq2 sheets. We demonstrated the conversion of the MqX nanowires to Mq2 micro-sheets in an ultrasonic bath of 1 M 8-Hq ethanol solutions (50%, w/ w) at 50 °C for 2 h, but not vice versa. The MqX nanowires exhibited excellent properties for photoluminescence, electrochemiluminescence (ECL), and photoelectrochemistry (PEC). The CdqBr and CdqI nanowires were coated onto a glass carbon and a fluorine-doped tin oxide glass electrode to develop the above ECL and PEC methods for the detection of H2O2 and Cu2+, respectively. In the range of 2 to 14 μM, the ECL intensity of the CdqBr nanowires was inversely proportional to the concentration of H2O2 with a detection limit of 0.26 μM. For Cu2+ sensing, the photocurrent of the CdqI nanowires exhibited a linear response to Cu2+ over the range of 2 to 16 μM of which a detection limit of 0.2 μM was observed.

Asymmetric Catalysis with bis(hydroxyphenyl)diamides/rare-earth metal complexes.

PubMed

Kumagai, Naoya; Shibasaki, Masakatsu

2013-01-02

A series of asymmetric catalysts composed of conformationally flexible amide-based chiral ligands and rare-earth metals was developed for proton-transfer catalysis. These ligands derived from amino acids provide an intriguing chiral platform for the formation of asymmetric catalysts upon complexation with rare-earth metals. The scope of this arsenal of catalysts was further broadened by the development of heterobimetallic catalytic systems. The cooperative function of hydrogen bonding and metal coordination resulted in intriguing substrate specificity and stereocontrol, and the dynamic nature of the catalysts led to a switch of their function. Herein, we summarize our recent exploration of this class of catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rare earth-transition metal scrap treatment method

DOEpatents

Schmidt, Frederick A.; Peterson, David T.; Wheelock, John T.; Jones, Lawrence L.; Lincoln, Lanny P.

1992-02-11

Rare earth-transition metal (e.g. iron) scrap (e.g. Nd-Fe-B scrap) is melted to reduce the levels of tramp oxygen and nitrogen impurities therein. The tramp impurities are reduced in the melt by virtue of the reaction of the tramp impurities and the rare earth to form dross on the melt. The purified melt is separated from the dross for reuse. The oxygen and nitrogen of the melt are reduced to levels acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets.

Rare earth-transition metal scrap treatment method

DOEpatents

Schmidt, F.A.; Peterson, D.T.; Wheelock, J.T.; Jones, L.L.; Lincoln, L.P.

1992-02-11

Rare earth-transition metal (e.g. iron) scrap (e.g. Nd-Fe-B scrap) is melted to reduce the levels of tramp oxygen and nitrogen impurities therein. The tramp impurities are reduced in the melt by virtue of the reaction of the tramp impurities and the rare earth to form dross on the melt. The purified melt is separated from the dross for reuse. The oxygen and nitrogen of the melt are reduced to levels acceptable for reuse of the treated alloy in the manufacture of end-use articles, such as permanent magnets. 3 figs.

Alkali Metal/Salt Thermal-Energy-Storage Systems

NASA Technical Reports Server (NTRS)

Phillips, Wayne W.; Stearns, John W.

1987-01-01

Proposed thermal-energy-storage system based on mixture of alkali metal and one of its halide salts; metal and salt form slurry of two immiscible melts. Use of slurry expected to prevent incrustations of solidified salts on heat-transfer surfaces that occur where salts alone used. Since incrustations impede heat transfer, system performance improved. In system, charging heat-exchanger surface immersed in lower liquid, rich in halide-salt, phase-charge material. Discharging heat exchanger surface immersed in upper liquid, rich in alkali metal.

High Pressure Optical Studies of the Thallous Halides and of Charge-Transfer Complexes

NASA Astrophysics Data System (ADS)

Jurgensen, Charles Willard

High pressure was used to study the insulator -to-metal transition in sulfur and the thallous halides and to study the intermolecular interactions in charge -transfer complexes. The approach to the band overlap insulator -to-metal transition was studied in three thallous halides and sulfur by optical absorption measurements of the band gap as a function of pressure. The band gap of sulfur continuously decreases with pressure up to the insulator -to-metal transition which occurs between 450 and 485 kbars. The results on the thallous halides indicate that the indirect gap decreases more rapidly than the direct gap; the closing of the indirect gap is responsible for the observed insulator -to-metal transitions. High pressure electronic and vibrational spectroscopic measurements on the solid-state complexes of HMB-TCNE were used to study the intermolecular interactions of charge -transfer complexes. The vibrational frequency shifts indicate that the degree of charge transfer increases with pressure which is independently confirmed by an increase in the molar absorptivity of the electronic charge-transfer peak. Induction and dispersion forces contribute towards a red shift of the charge-transfer peak; however, charge-transfer resonance contributes toward a blue shift and this effect is dominant for the HMB-TCNE complexes. High pressure electronic spectra were used to study the effect of intermolecular interactions on the electronic states of TCNQ and its complexes. The red shifts with pressure of the electronic spectra of TCNQ and (TCNQ)(' -) in polymer media and of crystalline TCNQ can be understood in terms of Van der Waals interactions. None of the calculations which considered intradimer distance obtained the proper behavior for either the charge-transfer of the locally excited states of the complexes. The qualitative behavior of both states can be interpreted as the effect of increased mixing of the locally excited and charge transfer states.

Plasmonic characterization of photo-induced silver nanoparticles extracted from silver halide based TEM film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sudheer,, E-mail: sudheer@rrcat.gov.in; Tiwari, P.; Rai, V. N.

The plasmonic responses of silver nanoparticles extracted from silver halide based electron microscope film are investigated. Photo-reduction process is carried out to convert the silver halide grains into the metallic silver. The centrifuge technique is used for separating the silver nanoparticles from the residual solution. Morphological study performed by field emission scanning electron microscope (FESEM) shows that all the nanoparticles have an average diameter of ~120 nm with a high degree of mono dispersion in size. The localized surface plasmon resonance (LSPR) absorption peak at ~537 nm confirms the presence of large size silver nanoparticles.

Catalysts Based on Earth-Abundant Metals for Visible Light-Driven Water Oxidation Reaction.

PubMed

Lin, Junqi; Han, Qing; Ding, Yong

2018-06-04

Exploration of water oxidation catalyst (WOC) with excellent performance is the key for the overall water splitting reaction, which is a feasible strategy to convert solar energy to chemical energy. Although some compounds composed of noble metals, mainly Ru and Ir, have been reported to catalyze water oxidation with high efficiency, catalysts based on low-cost and earth-abundant transition metals are essential for realizing economical and large-scale light-driven water splitting. Various WOCs containing earth-abundant metals (mainly Mn, Fe, Co, Ni, Cu) have been utilized for visible light-driven water oxidation in recent years. In this Personal Account, we summarize our recent developments in WOCs based on earth-abundant transition metals including polyoxometalates (POMs), metal oxides or bimetal oxides, and metal complexes containing multidentate ligand scaffolds for visible light-driven water oxidation reaction. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photodynamic therapy using a novel irradiation source, LED lamp, is similarly effective to photodynamic therapy using diode laser or metal-halide lamp on DMBA- and TPA-induced mouse skin papillomas.

PubMed

Takahashi, Hidetoshi; Nakajima, Susumu; Ogasawara, Koji; Asano, Ryuji; Nakae, Yoshinori; Sakata, Isao; Iizuka, Hajime

2014-08-01

Photodynamic therapy (PDT) is useful for superficial skin tumors such as actinic keratosis and Bowen disease. Although PDT is non-surgical and easily-performed treatment modality, irradiation apparatus is large and expensive. Using 7, 12-dimethylbenz[a]anthracene (DMBA) and 12-ο-tetradecanoylphorbol-13-acetate (TPA)-induced mouse skin papilloma model, we compared the efficacy of TONS501- and ALA-PDT with a LED lamp, a diode laser lamp or a metal-halide lamp on the skin tumor regression. TONS501-PDT using 660 nm LED lamp showed anti-tumor effect at 1 day following the irradiation and the maximal anti-tumor effect was observed at 3 days following the irradiation. There was no significant difference in the anti-tumor effects among TONS501-PDT using LED, TONS501-PDT using diode laser, and 5-aminolevulinic acid hydrochloride (ALA)-PDT using metal-halide lamp. Potent anti-tumor effect on DMBA- and TPA-induced mouse skin papilloma was observed by TONS501-PDT using 660 nm LED, which might be more useful for clinical applications. © 2014 Japanese Dermatological Association.

Method for providing adhesion to a metal surface

DOEpatents

Harrah, L.A.; Allred, R.E.; Wilson, K.V. Jr.

1992-02-18

A process for treating metal surfaces to obtain improved susceptibility to bonding with adhesive compositions is disclosed. A metal surface is oxidized with a halogen to form a monolayer of halide ions on the surface. The halide ions are then exchanged with azide ions to form an azide monolayer on the metal surface. Upon contact of the treated surface with an adhesive composition, the azide layer may be thermally or photochemically decomposed to form active nitrene species, which react to bond the adhesive composition to the metal surface.

Method for providing adhesion to a metal surface

DOEpatents

Harrah, Larry A.; Allred, Ronald E.; Wilson, Jr., Kennard V.

1992-01-01

A process for treating metal surfaces to obtain improved susceptibility to bonding with adhesive compositions is disclosed. A metal surface is oxidized with a halogen to form a monolayer of halide ions on the surface. The halide ions are then exchanged with azide ions to form an azide monolayer on the metal surface. Upon contact of the treated surface with an adhesive composition, the azide layer may be thermally or photochemically decomposed to form active nitrene species, which react to bond the adhesive composition to the metal surface.

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 12 2011-07-01 2009-07-01 true Emission Limits for Hydrogen Halide and... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions or...

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 12 2010-07-01 2010-07-01 true Emission Limits for Hydrogen Halide and... to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP... following table that applies to your process vents that contain hydrogen halide and halogen HAP emissions or...

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.

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 13 2013-07-01 2012-07-01 true Emission Limits for Hydrogen Halide and..., Table 3 Table 3 to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP Emissions... limit in the following table that applies to your process vents that contain hydrogen halide and halogen...

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 13 2014-07-01 2014-07-01 false Emission Limits for Hydrogen Halide.... FFFF, Table 3 Table 3 to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP... limit in the following table that applies to your process vents that contain hydrogen halide and halogen...

40 CFR Table 3 to Subpart Ffff of... - Emission Limits for Hydrogen Halide and Halogen HAP Emissions or HAP Metals Emissions From...

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 13 2012-07-01 2012-07-01 false Emission Limits for Hydrogen Halide.... FFFF, Table 3 Table 3 to Subpart FFFF of Part 63—Emission Limits for Hydrogen Halide and Halogen HAP... limit in the following table that applies to your process vents that contain hydrogen halide and halogen...

Process for preparing higher oxides of the alkali and alkaline earth metals

NASA Technical Reports Server (NTRS)

Sadhukhan, P.; Bell, A. (Inventor)

1978-01-01

High purity inorganic higher oxides of the alkali and alkaline earth metals are prepared by subjecting the hydroxide of the alkali and alkaline earth metal to a radio frequency discharge sustained in oxygen. The process is particulary adaptable to the production of high purity potassium superoxide by subjecting potassium hydroxide to glow discharge sustained in oxygen under the pressure of about 0.75 to 1.00 torr.

Changes in Carbon Isotope Composition of Methyl Halides Resulting from Biological and Chemical Degradation

NASA Astrophysics Data System (ADS)

Baesman, S. M.; Miller, L. G.; Oremland, R. S.

2003-12-01

Methyl bromide (MeBr), methyl chloride (MeCl) and methyl iodide (MeI) are reactive trace gases that are produced and released to the atmosphere at the Earths surface. These methyl halides have the potential to influence ozone levels in the stratosphere. Current estimates of the relative contributions of natural and anthropogenic sources of these methyl halides are the subject of considerable debate. In addition, there is uncertainty in the magnitude of some of the largest sinks for these compounds. Hence, the atmospheric budgets of MeBr, MeCl and MeI, while uncertain at present, may be better constrained using stable isotope ratio (13C/12C) mass balances of sources and sinks. Our work has focused on characterizing the effects upon δ 13C values of methyl halides released after reactions which discriminate in favor of 12C during removal processes. Previously, we determined very large fractionations of carbon isotopes by pure cultures of soil bacteria. Further, we have documented large fractionations (kinetic isotope effects or KIEs) of methyl halides in live soils. In the case of MeBr and MeI, substantial fractionation also occurred in heat-killed soil, suggesting that chemical degradation resulted in a shift in the stable isotopic composition. At elevated concentrations, for instance during agricultural soil fumigations, the δ 13C value of MeBr or MeI released from soil can be determined by flux measurements or soil profiles. However, more information is needed regarding the processes responsible for isotope fractionation to be able to extrapolate to areas where the concentration is low or direct measurement is not otherwise possible. We report here on measurements of the fractionation of carbon isotopes in methyl halides during degradation by chemical processes that are likely to occur in soil or seawater. These processes include aqueous hydrolysis and halide exchange and the methylation of organic matter using humic acid as the model methyl acceptor. Results are

Improving the Stability of Metal Halide Perovskite Materials and Light-Emitting Diodes.

PubMed

Cho, Himchan; Kim, Young-Hoon; Wolf, Christoph; Lee, Hyeon-Dong; Lee, Tae-Woo

2018-01-25

Metal halide perovskites (MHPs) have numerous advantages as light emitters such as high photoluminescence quantum efficiency with a direct bandgap, very narrow emission linewidth, high charge-carrier mobility, low energetic disorder, solution processability, simple color tuning, and low material cost. Based on these advantages, MHPs have recently shown unprecedented radical progress (maximum current efficiency from 0.3 to 42.9 cd A -1 ) in the field of light-emitting diodes. However, perovskite light-emitting diodes (PeLEDs) suffer from intrinsic instability of MHP materials and instability arising from the operation of the PeLEDs. Recently, many researchers have devoted efforts to overcome these instabilities. Here, the origins of the instability in PeLEDs are reviewed by categorizing it into two types: instability of (i) the MHP materials and (ii) the constituent layers and interfaces in PeLED devices. Then, the strategies to improve the stability of MHP materials and PeLEDs are critically reviewed, such as A-site cation engineering, Ruddlesden-Popper phase, suppression of ion migration with additives and blocking layers, fabrication of uniform bulk polycrystalline MHP layers, and fabrication of stable MHP nanoparticles. Based on this review of recent advances, future research directions and an outlook of PeLEDs for display applications are suggested. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shallow halogen vacancies in halide optoelectronic materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Hongliang; Du, Mao -Hua

2014-11-05

Halogen vacancies (V H) are usually deep color centers (F centers) in halides and can act as major electron traps or recombination centers. The deep V H contributes to the typically poor carrier transport properties in halides. However, several halides have recently emerged as excellent optoelectronic materials, e.g., CH 3NH 3PbI 3 and TlBr. Both CH 3NH 3PbI 3 and TlBr have been found to have shallow V H, in contrast to commonly seen deep V H in halides. In this paper, several halide optoelectronic materials, i.e., CH 3NH 3PbI 3, CH 3NH 3SnI 3 (photovoltaic materials), TlBr, and CsPbBrmore » 3, (gamma-ray detection materials) are studied to understand the material chemistry and structure that determine whether V H is a shallow or deep defect in a halide material. It is found that crystal structure and chemistry of ns 2 ions both play important roles in creating shallow V H in halides such as CH 3NH 3PbI 3, CH 3NH 3SnI 3, and TlBr. The key to identifying halides with shallow V H is to find the right crystal structures and compounds that suppress cation orbital hybridization at V H, 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 V H. Furthermore, the results of this paper provide insight and guidance to identifying halides with shallow V H as good electronic and optoelectronic materials.« less

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.

Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Chenkun; Worku, Michael; Neu, Jennifer

Here, we report the synthesis and characterization of (Ph 4P) 2SbCl 5, a novel ionically bonded organic metal halide hybrid with a zero-dimensional (0D) structure at the molecular level. By cocrystallization of tetraphenylphosphonium (Ph 4P +) and antimony (Sb 3+) chloride salts, (Ph 4P) 2SbCl 5 bulk single crystals can be prepared in high yield, which exhibit a highly efficient broadband red emission peaked at 648 nm with a photoluminescence quantum efficiency (PLQE) of around 87%. Density functional theory (DFT) calculations reveal the origin of emission as phosphorescence from the excitons localized at SbCl 5 2– with strong excited-state structuralmore » distortion. Interestingly, (Ph 4P) 2SbCl 5 bulk crystals with a PLQE of around 100% can be prepared via a rapid crystal growth process within minutes, followed by a spontaneous structural transformation. It was found that the rapid growth process yielded a yellow emitting kinetically favored metastable product containing solvent molecules, which turned into the red emitting thermodynamically stable product slowly at room temperature or quickly upon thermal treatment.« less

Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency

DOE PAGES

Zhou, Chenkun; Worku, Michael; Neu, Jennifer; ...

2018-03-12

Here, we report the synthesis and characterization of (Ph 4P) 2SbCl 5, a novel ionically bonded organic metal halide hybrid with a zero-dimensional (0D) structure at the molecular level. By cocrystallization of tetraphenylphosphonium (Ph 4P +) and antimony (Sb 3+) chloride salts, (Ph 4P) 2SbCl 5 bulk single crystals can be prepared in high yield, which exhibit a highly efficient broadband red emission peaked at 648 nm with a photoluminescence quantum efficiency (PLQE) of around 87%. Density functional theory (DFT) calculations reveal the origin of emission as phosphorescence from the excitons localized at SbCl 5 2– with strong excited-state structuralmore » distortion. Interestingly, (Ph 4P) 2SbCl 5 bulk crystals with a PLQE of around 100% can be prepared via a rapid crystal growth process within minutes, followed by a spontaneous structural transformation. It was found that the rapid growth process yielded a yellow emitting kinetically favored metastable product containing solvent molecules, which turned into the red emitting thermodynamically stable product slowly at room temperature or quickly upon thermal treatment.« less

Revealing the ultrafast charge carrier dynamics in organo metal halide perovskite solar cell materials using time resolved THz spectroscopy

NASA Astrophysics Data System (ADS)

Ponseca, C. S., Jr.; Sundström, V.

2016-03-01

Ultrafast charge carrier dynamics in organo metal halide perovskite has been probed using time resolved terahertz (THz) spectroscopy (TRTS). Current literature on its early time characteristics is unanimous: sub-ps charge carrier generation, highly mobile charges and very slow recombination rationalizing the exceptionally high power conversion efficiency for a solution processed solar cell material. Electron injection from MAPbI3 to nanoparticles (NP) of TiO2 is found to be sub-ps while Al2O3 NPs do not alter charge dynamics. Charge transfer to organic electrodes, Spiro-OMeTAD and PCBM, is sub-ps and few hundreds of ps respectively, which is influenced by the alignment of energy bands. It is surmised that minimizing defects/trap states is key in optimizing charge carrier extraction from these materials.

When VSEPR Fails: Experimental and Theoretical Investigations of the Behavior of Alkaline-Earth-Metal Acetylides

PubMed Central

Guino-o, Marites A.; Alexander, Jacob S.; McKee, Michael L.; Hope, Håkon; Englich, Ulrich B.

2014-01-01

The synthesis, structural, and spectral characterization as well as a theoretical study of a family of alkaline-earth-metal acetylides provides insights into synthetic access and the structural and bonding characteristics of this group of highly reactive compounds. Based on our earlier communication that reported unusual geometry for a family of triphenylsilyl-substituted alkaline-earth-metal acetylides, we herein present our studies on an expanded family of target derivatives, providing experimental and theoretical data to offer new insights into the intensively debated theme of structural chemistry in heavy alkaline-earth-metal chemistry. PMID:19844925

Application of Freeze-Dried Powders of Genetically Engineered Microbial Strains as Adsorbents for Rare Earth Metal Ions.

PubMed

Moriwaki, Hiroshi; Masuda, Reiko; Yamazaki, Yuki; Horiuchi, Kaoru; Miyashita, Mari; Kasahara, Jun; Tanaka, Tatsuhito; Yamamoto, Hiroki

2016-10-12

The adsorption behaviors of the rare earth metal ions onto freeze-dried powders of genetically engineered microbial strains were compared. Cell powders obtained from four kinds of strains, Bacillus subtilis 168 wild type (WT), lipoteichoic acid-defective (ΔLTA), wall teichoic acid-defective (ΔWTA), and cell wall hydrolases-defective (EFKYOJLp) strains, were used as an adsorbent of the rare earth metal ions at pH 3. The adsorption ability of the rare earth metal ions was in the order of EFKYOJLp > WT > ΔLTA > ΔWTA. The order was the same as the order of the phosphorus quantity of the strains. This result indicates that the main adsorption sites for the ions are the phosphate groups and the teichoic acids, LTA and WTA, that contribute to the adsorption of the rare earth metal ions onto the cell walls. The contribution of WTA was clearly greater than that of LTA. Each microbial powder was added to a solution containing 16 kinds of rare earth metal ions, and the removals (%) of each rare earth metal ion were obtained. The scandium ion showed the highest removal (%), while that of the lanthanum ion was the lowest for all the microbial powders. Differences in the distribution coefficients between the kinds of lanthanide ions by the EFKYOJLp and ΔWTA powders were greater than those of the other strains. Therefore, the EFKYOJLp and ΔWTA powders could be applicable for the selective extraction of the lanthanide ions. The ΔLTA powder coagulated by mixing with a rare earth metal ion, although no sedimentation of the WT or ΔWTA powder with a rare earth metal ion was observed under the same conditions. The EFKYOJLp powder was also coagulated, but its flocculating activity was lower than that of ΔLTA. The ΔLTA and EFKYOJLp powders have a long shape compared to those of the WT or ΔWTA strain. The shapes of the cells will play an important role in the sedimentation of the microbial powders with rare earth metal ions. As the results, three kinds of the genetically

Trends in Syntheses, Structures, and Properties for Three Series of Ammine Rare-Earth Metal Borohydrides, M(BH4)3·nNH3 (M = Y, Gd, and Dy).

PubMed

Jepsen, Lars H; Ley, Morten B; Černý, Radovan; Lee, Young-Su; Cho, Young Whan; Ravnsbæk, Dorthe; Besenbacher, Flemming; Skibsted, Jørgen; Jensen, Torben R

2015-08-03

Fourteen solvent- and halide-free ammine rare-earth metal borohydrides M(BH4)3·nNH3, M = Y, Gd, Dy, n = 7, 6, 5, 4, 2, and 1, have been synthesized by a new approach, and their structures as well as chemical and physical properties are characterized. Extensive series of coordination complexes with systematic variation in the number of ligands are presented, as prepared by combined mechanochemistry, solvent-based methods, solid-gas reactions, and thermal treatment. This new synthesis approach may have a significant impact within inorganic coordination chemistry. Halide-free metal borohydrides have been synthesized by solvent-based metathesis reactions of LiBH4 and MCl3 (3:1), followed by reactions of M(BH4)3 with an excess of NH3 gas, yielding M(BH4)3·7NH3 (M = Y, Gd, and Dy). Crystal structure models for M(BH4)3·nNH3 are derived from a combination of powder X-ray diffraction (PXD), (11)B magic-angle spinning NMR, and density functional theory (DFT) calculations. The structures vary from two-dimensional layers (n = 1), one-dimensional chains (n = 2), molecular compounds (n = 4 and 5), to contain complex ions (n = 6 and 7). NH3 coordinates to the metal in all compounds, while BH4(-) has a flexible coordination, i.e., either as a terminal or bridging ligand or as a counterion. M(BH4)3·7NH3 releases ammonia stepwise by thermal treatment producing M(BH4)3·nNH3 (6, 5, and 4), whereas hydrogen is released for n ≤ 4. Detailed analysis of the dihydrogen bonds reveals new insight about the hydrogen elimination mechanism, which contradicts current hypotheses. Overall, the present work provides new general knowledge toward rational materials design and preparation along with limitations of PXD and DFT for analysis of structures with a significant degree of dynamics in the structures.

Environmental Defects And Economic Impact On Global Market Of Rare Earth Metals

NASA Astrophysics Data System (ADS)

Charalampides, G.; Vatalis, K.; Karayannis, V.; Baklavaridis, A.

2016-11-01

Rare earth elements include the 14 lanthanides as well as lanthanium and often yttrium. Actually, most of them are not very rare and occur widely dispersed in a variety of rocks. Rare earth metals are vital to some of the world's faster growing industries: catalysts, Nd-magnets, ceramics, glass, metallurgy, battery alloys, electronics and phosphors. Worldwide, the main countries for distribution of rare earths deposits include China, USA, Russia, Brasil, India, Australia, Greenland and Malaysia. The mining and processing of rare earth metals usually result in significant environmental defects. Many deposits are associated with high concentrations of radioactive elements such as uranium and thorium, which requires separate treatment and disposal. The accumulation of rare earth elements in soils has occurred due to pollution caused by the exploitation of rare earth resources and the wide use of rare earths as fertilizers in agriculture. This accumulation has a toxic effect on the soil microfauna community. However, there are large differences in market prices due to the degree of purity determined by the specifications in the applications. The main focus of this article is to overview Rare Earth Metals’ overall impact on global economy and their environmental defects on soils during processing techniques and as they are used as fertilizers.

Mixed-Halide Perovskites with Stabilized Bandgaps.

PubMed

Xiao, Zhengguo; Zhao, Lianfeng; Tran, Nhu L; Lin, Yunhui Lisa; Silver, Scott H; Kerner, Ross A; Yao, Nan; Kahn, Antoine; Scholes, Gregory D; Rand, Barry P

2017-11-08

One merit of organic-inorganic hybrid perovskites is their tunable bandgap by adjusting the halide stoichiometry, an aspect critical to their application in tandem solar cells, wavelength-tunable light emitting diodes (LEDs), and lasers. However, the phase separation of mixed-halide perovskites caused by light or applied bias results in undesirable recombination at iodide-rich domains, meaning open-circuit voltage (V OC ) pinning in solar cells and infrared emission in LEDs. Here, we report an approach to suppress halide redistribution by self-assembled long-chain organic ammonium capping layers at nanometer-sized grain surfaces. Using the stable mixed-halide perovskite films, we are able to fabricate efficient and wavelength-tunable perovskite LEDs from infrared to green with high external quantum efficiencies of up to 5%, as well as linearly tuned V OC from 1.05 to 1.45 V in solar cells.

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.

Transition from metal-ligand bonding to halogen bonding involving a metal as halogen acceptor a study of Cu, Ag, Au, Pt, and Hg complexes

NASA Astrophysics Data System (ADS)

Oliveira, Vytor; Cremer, Dieter

2017-08-01

Utilizing all-electron Dirac-exact relativistic calculations with the Normalized Elimination of the Small Component (NESC) method and the local vibrational mode approach, the transition from metal-halide to metal halogen bonding is determined for Au-complexes interacting with halogen-donors. The local stretching force constants of the metal-halogen interactions reveal a smooth transition from weak non-covalent halogen bonding to non-classical 3-center-4-electron bonding and finally covalent metal-halide bonding. The strongest halogen bonds are found for dialkylaurates interacting with Cl2 or FCl. Differing trends in the intrinsic halogen-metal bond strength, the binding energy, and the electrostatic potential are explained.

A study of the convective flow as a function of external parameters in a high-pressure metal halide discharge lamp (HgDyI3)

NASA Astrophysics Data System (ADS)

Hajji, S.; HadjSalah, S.; Benhalima, A.; Charrada, K.; Zissis, G.

2016-06-01

This paper deals with the modelling of the convection processes in metal-halide lamp discharges (HgDyI3). For this, we realized a 3D model, a steady, direct current powered and time-depending model for the solution of conservation equations relative to mass, momentum, and energy. After validation, this model was applied to the study of the effect of some parameters that have appeared on major transport phenomena of mass and energy in studying the lamp. Indeed, the electric current, the atomic ratio (Hg/Dy), and the effect of the convective transport have been studied.

Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

PubMed

Yin, Jun; Hu, Ying; Yoon, Juyoung

2015-07-21

All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems.

Two-Dimensional Halide Perovskites: Tuning Electronic Activities of Defects

DOE PAGES

Liu, Yuanyue; Xiao, Hai; Goddard, William A.

2016-04-21

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 MX 2) 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 gapmore » states. Here, we show that this difference originates from the enhanced ionic bonding in these perovskites compared with MX 2. 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.« less

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

PubMed Central

Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

2016-01-01

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manna, Kuntal; Ji, Pengfei; Lin, Zekai

2016-08-30

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturatedmore » metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.« less

Broadband enhancement of photoluminance from colloidal metal halide perovskite nanocrystals on plasmonic nanostructured surfaces.

PubMed

Zhang, Si; Liang, Yuzhang; Jing, Qiang; Lu, Zhenda; Lu, Yanqing; Xu, Ting

2017-11-07

Metal halide perovskite nanocrystals (NCs) as a new kind of promising optoelectronic material have attracted wide attention due to their high photoluminescence (PL) quantum yield, narrow emission linewidth and wideband color tunability. Since the PL intensity always has a direct influence on the performance of optoelectronic devices, it is of vital importance to improve the perovskite NCs' fluorescence emission efficiency. Here, we synthesize three inorganic perovskite NCs and experimentally demonstrate a broadband fluorescence enhancement of perovskite NCs by exploiting plasmonic nanostructured surface consisting of nanogrooves array. The strong near-field optical localization associated with surface plasmon polariton-coupled emission effect generated by the nanogrooves array can significantly boost the absorption of perovskite NCs and tailor the fluorescence emissions. As a result, the PL intensities of perovskite NCs are broadband enhanced with a maximum factor higher than 8-fold achieved in experimental demonstration. Moreover, the high efficiency PL of perovskite NCs embedded in the polymer matrix layer on the top of plasmonic nanostructured surface can be maintained for more than three weeks. These results imply that plasmonic nanostructured surface is a good candidate to stably broadband enhance the PL intensity of perovskite NCs and further promote their potentials in the application of visible-light-emitting devices.

Highly stable noble-metal nanoparticles in tetraalkylphosphonium ionic liquids for in situ catalysis.

PubMed

Banerjee, Abhinandan; Theron, Robin; Scott, Robert W J

2012-01-09

Gold and palladium nanoparticles were prepared by lithium borohydride reduction of the metal salt precursors in tetraalkylphosphonium halide ionic liquids in the absence of any organic solvents or external nanoparticle stabilizers. These colloidal suspensions remained stable and showed no nanoparticle agglomeration over many months. A combination of electrostatic interactions between the coordinatively unsaturated metal nanoparticle surface and the ionic-liquid anions, bolstered by steric protection offered by the bulky alkylated phosphonium cations, is likely to be the reason behind such stabilization. The halide anion strongly absorbs to the nanoparticle surface, leading to exceptional nanoparticle stability in halide ionic liquids; other tetraalkylphosphonium ionic liquids with non-coordinating anions, such as tosylate and hexafluorophosphate, show considerably lower affinities towards the stabilization of nanoparticles. Palladium nanoparticles stabilized in the tetraalkylphosphonium halide ionic liquid were stable, efficient, and recyclable catalysts for a variety of hydrogenation reactions at ambient pressures with sustained activity. Aerial oxidation of the metal nanoparticles occurred over time and was readily reversed by re-reduction of oxidized metal salts. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

PubMed

Chen, Kun; Tüysüz, Harun

2015-11-09

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composition-Graded Cesium Lead Halide Perovskite Nanowires with Tunable Dual-Color Lasing Performance.

PubMed

Huang, Ling; Gao, Qinggang; Sun, Ling-Dong; Dong, Hao; Shi, Shuo; Cai, Tong; Liao, Qing; Yan, Chun-Hua

2018-05-21

Cesium lead halide (CsPbX 3 ) perovskite has emerged as a promising low-threshold multicolor laser material; however, realizing wavelength-tunable lasing output from a single CsPbX 3 nanostructure is still constrained by integrating different composition. Here, the direct synthesis of composition-graded CsPbBr x I 3- x nanowires (NWs) is reported through vapor-phase epitaxial growth on mica. The graded composition along the NW, with an increased Br/I from the center to the ends, comes from desynchronized deposition of cesium lead halides and temperature-controlled anion-exchange reaction. The graded composition results in varied bandgaps along the NW, which induce a blueshifted emission from the center to the ends. As an efficient gain media, the nanowire exerts position-dependent lasing performance, with a different color at the ends and center respectively above the threshold. Meanwhile, dual-color lasing with a wavelength separation of 35 nm is activated simultaneously at a site with an intermediate composition. This position-dependent dual-color lasing from a single nanowire makes these metal halide perovskites promising for applications in nanoscale optical devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

PubMed

Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

2013-06-15

The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system. Copyright © 2013 Elsevier B.V. All rights reserved.

Transport, Optical, and Magnetic Properties of the Conducting Halide Perovskite CH 3NH 3SnI 3

NASA Astrophysics Data System (ADS)

Mitzi, D. B.; Feild, C. A.; Schlesinger, Z.; Laibowitz, R. B.

1995-01-01

A low-temperature ( T ≤ 100°C) solution technique is described for the preparation of polycrystalline and single crystal samples of the conducting halide perovskite, CH 3NH 3SnI 3. Transport, Hall effect, magnetic, and optical properties are examined over the temperature range 1.8-300 K, confirming that this unusual conducting halide perovskite is a low carrier density p-type metal with a Hall hole density, 1/ RHe ≃ 2 × 10 19 cm -3. The resistivity of pressed pellet samples decreases with decreasing temperature with resistivity ratio ρ(300 K)/ρ(2 K) ≃ 3 and room temperature resistivity ρ(300 K) ≃ 7 mΩ-cm. A free-carrier infrared reflectivity spectrum with a plasma edge observed at approximately 1600 cm -1 further attests to the metallic nature of this compound and suggests a small optical effective mass, m* ≃ 0.2.

First-principles study on interlayer state in alkali and alkaline earth metal atoms intercalated bilayer graphene

NASA Astrophysics Data System (ADS)

Kaneko, Tomoaki; Saito, Riichiro

2017-11-01

Energetics and electronic structures of alkali metal (Li, Na, K, Rb, and Cs) and alkaline earth metal (Be, Mg, Ca, Sr, and Ba) atoms intercalated bilayer graphene are systematically investigated using first-principles calculations based on density functional theory. Formation of alkali and alkaline earth metal atoms intercalated bilayer graphene is exothermic except for Be and Mg. The interlayer state between two graphene layers is occupied for K, Rb, Cs, Ca, Sr, and Ba. We find that the energetic position of the interlayer states between bilayer graphene monotonically shifts downward with increasing of interlayer distance. The interlayer distances of more than 4.5 Å and 4.0 Å, respectively, are necessary for the occupation of the interlayer state in bilayer graphene for alkali and alkaline earth metal atoms, which is almost independent of the intercalant metal species. We discuss the relevance to occurrence of superconductivity for the metal intercalated bilayer graphene in terms of the occupation of the interlayer state and the phonon frequency of metal ions.

Molten metal containment vessel with rare earth oxysulfide protective coating thereon and method of making same

DOEpatents

Krikorian, Oscar H.; Curtis, Paul G.

1992-01-01

An improved molten metal containment vessel is disclosed in which wetting of the vessel's inner wall surfaces by molten metal is inhibited by coating at least the inner surfaces of the containment vessel with one or more rare earth oxysulfide or rare earth sulfide compounds to inhibit wetting and or adherence by the molten metal to the surfaces of the containment vessel.

Low frequency vibrational spectra and the nature of metal-oxygen bond of alkaline earth metal acetylacetonates

NASA Astrophysics Data System (ADS)

Fakheri, Hamideh; Tayyari, Sayyed Faramarz; Heravi, Mohammad Momen; Morsali, Ali

2017-12-01

Theoretical quantum chemistry calculations were used to assign the observed vibrational band frequencies of Be, Mg, Ca, Sr, and Ba acetylacetonates complexes. Density functional theory (DFT) calculations have been carried out at the B3LYP level, using LanL2DZ, def2SVP, and mixed, GenECP, (def2SVP for metal ions and 6-311++G** for all other atoms) basis sets. The B3LYP level, with mixed basis sets, was utilized for calculations of vibrational frequencies, IR intensity, and Raman activity. Analysis of the vibrational spectra indicates that there are several bands which could almost be assigned mainly to the metal-oxygen vibrations. The strongest Raman band in this region could be used as a measure of the stability of the complex. The effects of central metal on the bond orders and charge distributions in alkaline earth metal acetylacetonates were studied by the Natural Bond Orbital (NBO) method for fully optimized compounds. Optimization were performed at the B3LYP/6-311++G** level for the lighter alkaline earth metal complexes (Be, Mg, and Ca acetylacetonates) while the B3LYP level, using LanL2DZ (extrabasis, d and f on oxygen and metal atoms), def2SVP and mixed (def2SVP on metal ions and 6-311++G** for all other atoms) basis sets for all understudy complexes. Calculations indicate that the covalence nature of metal-oxygen bonds considerably decreases from Be to Ba complexes. The nature of metal-oxygen bond was further studied by using Atoms In Molecules (AIM) analysis. The topological parameters, Wiberg bond orders, natural charges of O and metal ions, and also some vibrational band frequencies were correlated with the stability constants of understudy complexes.

High Pressure Phase Transformations in Heavy Rare Earth Metals and Connections to Actinide Crystal Structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vohra, Yogesh K.; Sangala, Bagvanth Reddy; Stemshorn, Andrew K.

2008-07-01

High-pressure studies have been performed on heavy rare earth metals Terbium (Tb) to 155 GPa and Holmium (Ho) to 134 GPa in a diamond anvil cell at room temperature. The following crystal structure sequence was observed in both metals hcp {yields} Sm-type {yields} dhcp {yields} distorted fcc (hR-24) {yields} monoclinic (C2/m) with increasing pressure. The last transformation to a low symmetry monoclinic phase is accompanied by a volume collapse of 5 % for Tb at 51 GPa and a volume collapse of 3 % for Ho at 103 GPa. This volume collapse under high pressure is reminiscent of f-shell delocalizationmore » in light rare earth metal Cerium (Ce), Praseodymium (Pr), and heavy actinide metals Americium (Am) and Curium (Cm). The orthorhombic Pnma phase that has been reported in Am and Cm after f-shell delocalization is not observed in heavy rare earth metals under high pressures. (authors)« less

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

PubMed

Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I; Krieg, Franziska; Caputo, Riccarda; Hendon, Christopher H; Yang, Ruo Xi; Walsh, Aron; Kovalenko, Maksym V

2015-06-10

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.

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Synthesis and spectral studies of platinum metal complexes of benzoin thiosemicarbazone

NASA Astrophysics Data System (ADS)

Offiong, Offiong E.

1994-11-01

The platinum metal chelates of benzoin thiosemicarbazone obtained with Ru(III), Rh(III), Ir(III), Pd(II) and Pt(II) were prepared from their corresponding halide salts. The complexes were characterized by elemental analysis, conductance measurement, IR, Raman, 1H-NMR, 13C-NMR and UV-visible spectra studies. Various ligand field parameters and nephelauxetic parameters were also calculated. The mode of bonding and the geometry of the ligand environment around the metal ion have been discussed in the light of the available data obtained. Complexes of Ru(III), Rh(III) and Ir(III) are six-coordinate octahedral, while Pd(II) and Pt(II) halide complexes are four-coordinated with halides bridging.

The Impact of Atmosphere on the Local Luminescence Properties of Metal Halide Perovskite Grains.

PubMed

Brenes, Roberto; Eames, Christopher; Bulović, Vladimir; Islam, M Saiful; Stranks, Samuel D

2018-04-01

Metal halide perovskites are exceptional candidates for inexpensive yet high-performing optoelectronic devices. Nevertheless, polycrystalline perovskite films are still limited by nonradiative losses due to charge carrier trap states that can be affected by illumination. Here, in situ microphotoluminescence measurements are used to elucidate the impact of light-soaking individual methylammonium lead iodide grains in high-quality polycrystalline films while immersing them with different atmospheric environments. It is shown that emission from each grain depends sensitively on both the environment and the nature of the specific grain, i.e., whether it shows good (bright grain) or poor (dark grain) luminescence properties. It is found that the dark grains show substantial rises in emission, while the bright grain emission is steady when illuminated in the presence of oxygen and/or water molecules. The results are explained using density functional theory calculations, which reveal strong adsorption energies of the molecules to the perovskite surfaces. It is also found that oxygen molecules bind particularly strongly to surface iodide vacancies which, in the presence of photoexcited electrons, lead to efficient passivation of the carrier trap states that arise from these vacancies. The work reveals a unique insight into the nature of nonradiative decay and the impact of atmospheric passivation on the microscale properties of perovskite films. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polaronic Charge Carrier-Lattice Interactions in Lead Halide Perovskites.

PubMed

Wolf, Christoph; Cho, Himchan; Kim, Young-Hoon; Lee, Tae-Woo

2017-10-09

Almost ten years after the renaissance of the popular perovskite-type semiconductors based on lead salts with the general formula AMX 3 (A=organic or inorganic cation; M=divalent metal; X=halide), many facets of photophysics continue to puzzle researchers. In this Minireview, light is shed on the low mobilities of charge carriers in lead halide perovskites with special focus on the lattice properties at non-zero temperature. The polar and soft lattice leads to pronounced electron-phonon coupling, limiting carrier mobility and retarding recombination. We propose that the proper picture of excited charge carriers at temperature ranges that are relevant for device operations is that of a polaron, with Fröhlich coupling constants between 1<α<3. Under the aspect of light-emitting diode application, APbX 3 perovskite show moderate second order (bimolecular) recombination rates and high third-order (Auger) rate constants. It has become apparent that this is a direct consequence of the anisotropic polar A-site cation in organic-inorganic hybrid perovskites and might be alleviated by replacing the organic moiety with an isotropic cation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rare-earth metal oxide doped transparent mesoporous silica plates under non-aqueous condition as a potential UV sensor.

PubMed

Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik

2013-11-01

Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.

X-ray Scintillation in Lead Halide Perovskite Crystals

PubMed Central

Birowosuto, M. D.; Cortecchia, D.; Drozdowski, W.; Brylew, K.; Lachmanski, W.; Bruno, A.; Soci, C.

2016-01-01

Current technologies for X-ray detection rely on scintillation from expensive inorganic crystals grown at high-temperature, which so far has hindered the development of large-area scintillator arrays. Thanks to the presence of heavy atoms, solution-grown hybrid lead halide perovskite single crystals exhibit short X-ray absorption length and excellent detection efficiency. Here we compare X-ray scintillator characteristics of three-dimensional (3D) MAPbI3 and MAPbBr3 and two-dimensional (2D) (EDBE)PbCl4 hybrid perovskite crystals. X-ray excited thermoluminescence measurements indicate the absence of deep traps and a very small density of shallow trap states, which lessens after-glow effects. All perovskite single crystals exhibit high X-ray excited luminescence yields of >120,000 photons/MeV at low temperature. Although thermal quenching is significant at room temperature, the large exciton binding energy of 2D (EDBE)PbCl4 significantly reduces thermal effects compared to 3D perovskites, and moderate light yield of 9,000 photons/MeV can be achieved even at room temperature. This highlights the potential of 2D metal halide perovskites for large-area and low-cost scintillator devices for medical, security and scientific applications. PMID:27849019

Adsorption Behavior of Rare Earth Metal Cations in the Interlayer Space of γ-ZrP.

PubMed

Takei, Takahiro; Iidzuka, Kiyoaki; Miura, Akira; Yanagida, Sayaka; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2016-10-04

Adsorption competencies of rare earth metal cations in γ-zirconium phosphate were examined by ICP, synchrotron X-ray diffraction (SXRD), and ab initio simulation. The adsorption amounts are around 0.06-0.10 per zirconium phosphate. From the SXRD patterns of the adsorbed samples, the basal spacing estimated by c sin β increased linearly with an increasing ionic radius of rare earth metal cation, though a and b lattice constants show no change. These SXRD patterns can be classified into four groups that have different super lattices. The four superlattices have multiplicities of x131, x241, and x221 for the xabc axis, and the location of the rare earth metal cation in the original unit cell changes depending on the superlattice cell. In the x131 superlattice, Yb and Er occupied the site near the zirconium phosphate layer, though La and Ce in the x221 superlattice remained in the center position between the phosphate sheet. For the ab initio simulation of γ-ZrP with the typical rare earth metal cations (Tb, Eu, Dy, and La), the results of simulation show a similar tendency of the position estimated by SXRD refinements.

High pressure phase transitions in the rare earth metal erbium to 151 GPa.

PubMed

Samudrala, Gopi K; Thomas, Sarah A; Montgomery, Jeffrey M; Vohra, Yogesh K

2011-08-10

High pressure x-ray diffraction studies have been performed on the heavy rare earth metal erbium (Er) in a diamond anvil cell at room temperature to a pressure of 151 GPa and Er has been compressed to 40% of its initial volume. The rare earth crystal structure sequence hcp → Sm type → dhcp → distorted fcc (hcp: hexagonal close packed; fcc: face centered cubic; dhcp: double hcp) is observed in Er below 58 GPa. We have carried out Rietveld refinement of crystal structures in the pressure range between 58 GPa and 151 GPa. We have examined various crystal structures that have been proposed for the distorted fcc (dfcc) phase and the post-dfcc phase in rare earth metals. We find that the hexagonal hR 24 structure is the best fit between 58 and 118 GPa. Above 118 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.9%. We have also established a clear trend for the pressure at which a post-dfcc phase is formed in rare earth metals and show that there is a monotonic increase in this pressure with the filling of 4f shell.

High pressure phase transitions in the rare earth metal erbium to 151 GPa

NASA Astrophysics Data System (ADS)

Samudrala, Gopi K.; Thomas, Sarah A.; Montgomery, Jeffrey M.; Vohra, Yogesh K.

2011-08-01

High pressure x-ray diffraction studies have been performed on the heavy rare earth metal erbium (Er) in a diamond anvil cell at room temperature to a pressure of 151 GPa and Er has been compressed to 40% of its initial volume. The rare earth crystal structure sequence {hcp} \\to {Sm}~ {type} \\to {dhcp} \\to {distorted} fcc (hcp: hexagonal close packed; fcc: face centered cubic; dhcp: double hcp) is observed in Er below 58 GPa. We have carried out Rietveld refinement of crystal structures in the pressure range between 58 GPa and 151 GPa. We have examined various crystal structures that have been proposed for the distorted fcc (dfcc) phase and the post-dfcc phase in rare earth metals. We find that the hexagonal hR 24 structure is the best fit between 58 and 118 GPa. Above 118 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.9%. We have also established a clear trend for the pressure at which a post-dfcc phase is formed in rare earth metals and show that there is a monotonic increase in this pressure with the filling of 4f shell.

Investigation of surface halide modification of nitrile butadiene rubber

NASA Astrophysics Data System (ADS)

Sukhareva, K. V.; Mikhailov, I. A.; Andriasyan, Yu O.; Mastalygina, E. E.; Popov, A. A.

2017-12-01

The investigation is devoted to the novel technology of surface halide modification of rubber samples based on nitrile butadiene rubber (NBR). 1,1,2-trifluoro-1,2,2-trichlorethane was used as halide modifier. The developed technology is characterized by production stages reduction to one by means of treating the rubber compound with a halide modifier. The surface halide modification of compounds based on nitrile butadiene rubber (NBR) was determined to result in increase of resistance to thermal oxidation and aggressive media. The conducted research revealed the influence of modification time on chemical resistance and physical-mechanical properties of rubbers under investigation.

Pore-Environment Engineering with Multiple Metal Sites in Rare-Earth Porphyrinic Metal-Organic Frameworks.

PubMed

Zhang, Liangliang; Yuan, Shuai; Feng, Liang; Guo, Bingbing; Qin, Jun-Sheng; Xu, Ben; Lollar, Christina; Sun, Daofeng; Zhou, Hong-Cai

2018-04-23

Multi-component metal-organic frameworks (MOFs) with precisely controlled pore environments are highly desired owing to their potential applications in gas adsorption, separation, cooperative catalysis, and biomimetics. A series of multi-component MOFs, namely PCN-900(RE), were constructed from a combination of tetratopic porphyrinic linkers, linear linkers, and rare-earth hexanuclear clusters (RE 6 ) under the guidance of thermodynamics. These MOFs exhibit high surface areas (up to 2523 cm 2  g -1 ) and unlimited tunability by modification of metal nodes and/or linker components. Post-synthetic exchange of linear linkers and metalation of two organic linkers were realized, allowing the incorporation of a wide range of functional moieties. Two different metal sites were sequentially placed on the linear linker and the tetratopic porphyrinic linker, respectively, giving rise to an ideal platform for heterogeneous catalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Myeloperoxidase-Halide-Hydrogen Peroxide Antibacterial System

PubMed Central

Klebanoff, Seymour J.

1968-01-01

An antibacterial effect of myeloperoxidase, a halide, such as iodide, bromide, or chloride ion, and H2O2 on Escherichia coli or Lactobacillus acidophilus is described. When L. acidophilus was employed, the addition of H2O2 was not required; however, the protective effect of catalase suggested that, in this instance, H2O2 was generated by the organisms. The antibacterial effect was largely prevented by preheating the myeloperoxidase at 80 C or greater for 10 min or by the addition of a number of inhibitors; it was most active at the most acid pH employed (5.0). Lactoperoxidase was considerably less effective than was myeloperoxidase when chloride was the halide employed. Myeloperoxidase, at high concentrations, exerted an antibacterial effect on L. acidophilus in the absence of added halide, which also was temperature- and catalase-sensitive. Peroxidase was extracted from intact guinea pig leukocytes by weak acid, and the extract with peroxidase activity had antibacterial properties which were similar, in many respects, to those of the purified preparation of myeloperoxidase. Under appropriate conditions, the antibacterial effect was increased by halides and by H2O2 and was decreased by catalase, as well as by cyanide, azide, Tapazole, and thiosulfate. This suggests that, under the conditions employed, the antibacterial properties of a weak acid extract of guinea pig leukocytes is due, in part, to its peroxidase content, particularly if a halide is present in the reaction mixture. A heat-stable antibacterial agent or agents also appear to be present in the extract. PMID:4970226

Pentadienyl chemistry of the heavy alkaline-earth metals revisited.

PubMed

Reiners, Matthias; Fecker, Ann Christin; Freytag, Matthias; Jones, Peter G; Walter, Marc D

2014-05-14

Open-metallocenes of the heavy alkaline-earth metals [(η(5)-Pdl')2M(thf)n] (M = Ca (1), Sr (2), n = 1; M = Ba (3), n = 2; Pdl' = 2,4-tBu2C5H5) are readily prepared by salt-metathesis between MI2 and KPdl' and characterized by NMR spectroscopy and X-ray diffraction studies.

Hybrid lead halide perovskites for light energy conversion: Excited state properties and photovoltaic applications

NASA Astrophysics Data System (ADS)

Manser, Joseph S.

The burgeoning class of metal halide perovskites constitutes a paradigm shift in the study and application of solution-processed semiconductors. Advancements in thin film processing and our understanding of the underlying structural, photophysical, and electronic properties of these materials over the past five years have led to development of perovskite solar cells with power conversion efficiencies that rival much more mature first and second-generation commercial technologies. It seems only a matter of time before the real-world impact of these compounds is put to the test. Like oxide perovskites, metal halide perovskites have ABX3 stoichiometry, where typically A is a monovalent cation, B a bivalent post-transition metal, and X a halide anion. Characterizing the behavior of photogenerated charges in metal halide perovskites is integral for understanding the operating principles and fundamental limitations of perovskite optoelectronics. The majority of studies outlined in this dissertation involve fundamental study of the prototypical organic-inorganic compound methylammonium lead iodide (CH3NH3PbI 3). Time-resolved pump-probe spectroscopy serves as a principle tool in these investigations. Excitation of a semiconductor can lead to formation of a number different excited state species and electronic complexes. Through analysis of excited state decay kinetics and optical nonlinearities in perovskite thin films, we identify spontaneous formation of a large fraction of free electrons and holes, whose presence is requisite for efficient photovoltaic operation. Following photogeneration of charge carriers in a semiconductor absorber, these species must travel large distances across the thickness of the material to realize large external quantum efficiencies and efficient carrier extraction. Using a powerful technique known as transient absorption microscopy, we directly image long-range carrier diffusion in a CH3NH3PbI 3 thin film. Charges are unambiguously shown to

Computational Studies of Thermodynamics and Kinetics of Metal Oxides in Li-Ion Batteries and Earth's Lower Mantle Materials

NASA Astrophysics Data System (ADS)

Xu, Shenzhen

Metal oxide materials are ubiquitous in nature and in our daily lives. For example, the Earth's mantle layer that makes up about 80% of our Earth's volume is composed of metal oxide materials, the cathode materials in the lithium-ion batteries that provide power for most of our mobile electronic devices are composed of metal oxides, the chemical components of the passivation layers on many kinds of metal materials that protect the metal from further corrosion are metal oxides. This thesis is composed of two major topics about the metal oxide materials in nature. The first topic is about our computational study of the iron chemistry in the Earth's lower mantle metal oxide materials, i.e. the bridgmanite (Fe-bearing MgSiO3 where iron is the substitution impurity element) and the ferropericlase (Fe-bearing MgO where iron is the substitution impurity element). The second topic is about our multiscale modeling works for understanding the nanoscale kinetic and thermodynamic properties of the metal oxide cathode interfaces in Li-ion batteries, including the intrinsic cathode interfaces (intergrowth of multiple types of cathode materials, compositional gradient cathode materials, etc.), the cathode/coating interface systems and the cathode/electrolyte interface systems. This thesis uses models based on density functional theory quantum mechanical calculations to explore the underlying physics behind several types of metal oxide materials existing in the interior of the Earth or used in the applications of lithium-ion batteries. The exploration of this physics can help us better understand the geochemical and seismic properties of our Earth and inspire us to engineer the next generation of electrochemical technologies.

Effect of rare earth metal on the spin-orbit torque in magnetic heterostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ueda, Kohei; Pai, Chi-Feng; Tan, Aik Jun

2016-06-06

We report the effect of the rare earth metal Gd on current-induced spin-orbit torques (SOTs) in perpendicularly magnetized Pt/Co/Gd heterostructures, characterized using harmonic measurements and spin-torque ferromagnetic resonance (ST-FMR). By varying the Gd metal layer thickness from 0 nm to 8 nm, harmonic measurements reveal a significant enhancement of the effective fields generated from the Slonczewski-like and field-like torques. ST-FMR measurements confirm an enhanced effective spin Hall angle and show a corresponding increase in the magnetic damping constant with increasing Gd thickness. These results suggest that Gd plays an active role in generating SOTs in these heterostructures. Our finding may lead tomore » spin-orbitronics device application such as non-volatile magnetic random access memory, based on rare earth metals.« less

40 CFR 721.530 - Substituted aliphatic acid halide (generic name).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted aliphatic acid halide... Specific Chemical Substances § 721.530 Substituted aliphatic acid halide (generic name). (a) Chemical... acid halide (PMN P-84-491) is subject to reporting under this section for the significant new uses...

40 CFR 721.530 - Substituted aliphatic acid halide (generic name).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Substituted aliphatic acid halide... Specific Chemical Substances § 721.530 Substituted aliphatic acid halide (generic name). (a) Chemical... acid halide (PMN P-84-491) is subject to reporting under this section for the significant new uses...

Theoretical Study of pKa Values for Trivalent Rare-Earth Metal Cations in Aqueous Solution.

PubMed

Yu, Donghai; Du, Ruobing; Xiao, Ji-Chang; Xu, Shengming; Rong, Chunying; Liu, Shubin

2018-01-18

Molecular acidity of trivalent rare-earth metal cations in aqueous solution is an important factor dedicated to the efficiency of their extraction and separation processes. In this work, the aqueous acidity of these metal ions has been quantitatively investigated using a few theoretical approaches. Our computational results expressed in terms of pK a values agree well with the tetrad effect of trivalent rare-earth ions extensively reported in the extraction and separation of these elements. Strong linear relationships have been observed between the acidity and quantum electronic descriptors such as the molecular electrostatic potential on the acidic nucleus and the sum of the valence natural atomic orbitals energies of the dissociating proton. Making use of the predicted pK a values, we have also predicted the major ionic forms of these species in the aqueous environment with different pH values, which can be employed to rationalize the behavior difference of different rare-earth metal cations during the extraction process. Our present results should provide needed insights not only for the qualitatively understanding about the extraction and separation between yttrium and lanthanide elements but also for the prediction of novel and more efficient rare-earth metal extractants in the future.

Theoretical study of the alkaline-earth metal superoxides BeO2 through SrO2

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Sodupe, Mariona; Langhoff, Stephen R.

1992-01-01

Three competing bonding mechanisms have been identified for the alkaline-earth metal superoxides: these result in a change in the optimal structure and ground state as the alkaline-earth metal becomes heavier. For example, BeO2 has a linear 3Sigma(-)g ground-state structure, whereas both CaO2 and SrO2 have C(2v)1A1 structures. For MgO2, the theoretical calculations are less definitive, as the 3A2 C(2v) structure is computed to lie only about 3 kcal/mol above the 3Sigma(-)g linear structure. The bond dissociation energies for the alkaline-earth metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional or coupled-cluster singles and doubles level with a perturbational estimate of the triple excitations.

Alkaline earth metal doped tin oxide as a novel oxygen storage material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Qiang, E-mail: dong@tagen.tohoku.ac.jp; Yin, Shu; Yoshida, Mizuki

2015-09-15

Alkaline earth metal doped tin oxide (SnO{sub 2}) hollow nanospheres with a diameter of 50 nm have been synthesized successfully via a facial solvothermal route in a very simple system composed of only ethanol, acetic acid, SnCl{sub 4}·5H{sub 2}O and A(NO{sub 3}){sub 2}·xH{sub 2}O (A = Mg, Ca, Sr, Ba). The synthesized undoped SnO{sub 2} and A-doped SnO{sub 2} hollow nanospheres were characterized by the oxygen storage capacity (OSC), X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique. The OSC values of all samples were measured using thermogravimetric-differential thermal analysis. The incorporation of alkaline earth metal ion into tinmore » oxide greatly enhanced the thermal stability and OSC. Especially, Ba-doped SnO{sub 2} hollow nanospheres calcined at 1000 °C for 20 h with a BET surface area of 61 m{sup 2} g{sup −1} exhibited the considerably high OSC of 457 μmol-O g{sup −1} and good thermal stability. Alkaline earth metal doped tin oxide has the potential to be a novel oxygen storage material.« less

Exploration geochemical technique for the determination of preconcentrated organometallic halides by ICP-AES

USGS Publications Warehouse

Motooka, J.M.

1988-01-01

An atomic absorption extraction technique which is widely used in geochemical exploration for the determination of Ag, As, Au, Bi, Cd, Cu, Mo, Pb, Sb, and Zn has been modified and adapted to a simultaneous inductively coupled plasma-atomic emission instrument. the experimental and operating parameters are described for the preconcentration of the metals into their organometallic halides and for the determination of the metals. Lower limits of determination are equal to or improved over those for flame atomic absorption (except Au) and ICP results are very similar to the accepted AA values, with precision for the ICP data in excess of that necessary for exploration purposes.

Blending Non-Group-3 Transition Metal and Rare-Earth Metal into a C80 Fullerene Cage with D5h Symmetry.

PubMed

Wei, Tao; Jin, Fei; Guan, Runnan; Huang, Jing; Chen, Muqing; Li, Qunxiang; Yang, Shangfeng

2018-02-11

Rare-earth metals have been mostly entrapped into fullerene cages to form endohedral clusterfullerenes, whereas non-Group-3 transition metals that can form clusterfullerenes are limited to titanium (Ti) and vanadium (V), and both are exclusively entrapped within an I h -C 80 cage. Non-Group-3 transition-metal-containing endohedral fullerenes based on a C 80 cage with D 5h symmetry, V x Sc 3-x N@D 5h -C 80 (x=1, 2), have now been synthesized, which exhibit two variable cluster compositions. The molecular structure of VSc 2 N@D 5h -C 80 was unambiguously determined by X-ray crystallography. According to a comparative study with the reported Ti- and V-containing clusterfullerenes based on a I h -C 80 cage and the analogous D 5h -C 80 -based metal nitride clusterfullerenes containing rare-earth metals only, the decisive role of the non-Group-3 transition metal on the formation of the corresponding D 5h -C 80 -based clusterfullerenes is unraveled. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

High-pressure metallization of FeO and implications for the earth's core

NASA Technical Reports Server (NTRS)

Knittle, Elise; Jeanloz, Raymond

1986-01-01

The phase diagram of FeO has been experimentally determined to pressures of 155 GPa and temperatures of 4000 K using shock-wave and diamond-cell techniques. A metallic phase of FeO is observed at pressures greater than 70 GPa and temperatures exceeding 1000 K. The metallization of FeO at high pressures implies that oxygen can be present as the light alloying element of the earth's outer core, in accord with the geochemical predictions of Ringwood (1977 and 1979). The high pressures necessary for this metallization suggest that the core has acquired its composition well after the initial stages of the earth's accretion. Direct experimental observations at elevated pressures and temperatures indicate that core-forming alloy can react chemically with oxides such as those forming the mantle. The core and mantle may never have reached complete chemical equilibrium, however. If this is the case, the core-mantle boundary is likely to be a zone of active chemical reactions.

Spectral Changes in Metal Halide and High-Pressure Sodium Lamps Equipped with Electronic Dimming

NASA Technical Reports Server (NTRS)

Bubenheim, David L.; Sargis, Raman; Wilson, David

1995-01-01

Electronic dimming of high-intensity discharge lamps offers control of Photosynthetic Photon Flux (PPF) but is often characterized as causing significant spectral changes. Growth chambers with 400-W Metal Halide (MH) and High-Pressure Sodium (HPS) lamps were equipped with a dimmer system using Silicon-Controlled Rectifiers (SCR) as high-speed switches. Phase control operation turned the line power off for some period of the alternating current cycle. At full power, the electrical input to HPS and MH lamps was 480 W (root mean squared) and could be decreased to 267 W and 428 W, respectively, before the arc was extinguished. Concomitant with this decrease in input power, PPF decreased by 60% in HPS and 50% in MH. The HPS lamp has characteristic spectral peaks at 589 and 595 nm. As power to the HPS lamps was decreased, the 589-nm peak remained constant while the 595-nm peak decreased, equaling the 589-nm peak at 345-W input, and 589-nm peak was almost absent at 270-W input. The MH lamp has a broader spectral output but also has a peak at 589 nm and another smaller peak at 545 nm. As input power approached 428 W, the 589-nm peak shifted to 570 nm. While the spectrum changed as input power was decreased in the MH and HPS lamps, the phytochrome equilibrium ratio (P(sub ft):P(sub tot)) remains unchanged for both lamp types.

Development of processes for the production of solar grade silicon from halides and alkali metals, phase 1 and phase 2

NASA Technical Reports Server (NTRS)

Dickson, C. R.; Gould, R. K.; Felder, W.

1981-01-01

High temperature reactions of silicon halides with alkali metals for the production of solar grade silicon are described. Product separation and collection processes were evaluated, measure heat release parameters for scaling purposes and effects of reactants and/or products on materials of reactor construction were determined, and preliminary engineering and economic analysis of a scaled up process were made. The feasibility of the basic process to make and collect silicon was demonstrated. The jet impaction/separation process was demonstrated to be a purification process. The rate at which gas phase species from silicon particle precursors, the time required for silane decomposition to produce particles, and the competing rate of growth of silicon seed particles injected into a decomposing silane environment were determined. The extent of silane decomposition as a function of residence time, temperature, and pressure was measured by infrared absorption spectroscopy. A simplistic model is presented to explain the growth of silicon in a decomposing silane enviroment.

Positron Annihilation in Insulating Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Asoka-Kumar, P; Sterne, PA

2002-10-18

We describe positron results from a wide range of insulating materials. We have completed positron experiments on a range of zeolite-y samples, KDP crystals, alkali halides and laser damaged SiO{sub 2}. Present theoretical understanding of positron behavior in insulators is incomplete and our combined theoretical and experimental approach is aimed at developing a predictive understanding of positrons and positronium annihilation characteristics in insulators. Results from alkali halides and alkaline-earth halides show that positrons annihilate with only the halide ions, with no apparent contribution from the alkali or alkaline-earth cations. This contradicts the results of our existing theory for metals, whichmore » predicts roughly equal annihilation contributions from cation and anion. We also present result obtained using Munich positron microprobe on laser damaged SiO{sub 2} samples.« less

PREPARATION OF PLUTONIUM

DOEpatents

Kolodney, M.

1959-07-01

Methods are presented for the electro-deposition of plutonium from fused mixtures of plutonium halides and halides of the alkali metals and alkaline earth metals. Th salts, preferably chlorides and with the plutonium prefer ably in the trivalent state, are placed in a refractory crucible such as tantalum or molybdenam and heated in a non-oxidizing atmosphere to 600 to 850 deg C, the higher temperatatures being used to obtain massive plutonium and the lower for the powder form. Electrodes of graphite or non reactive refractory metals are used, the crucible serving the cathode in one apparatus described in the patent.

Method of coating graphite tubes with refractory metal carbides

DOEpatents

Wohlberg, C.

1973-12-11

A method of coating graphite tubes with a refractory metal carbide is described. An alkali halide is reacted with a metallic oxide, the metallic portion being selected from the IVth or Vth group of the Periodic Table, the resulting salt reacting in turn with the carbon to give the desired refractory metal carbide coating. (Official Gazette)

Experimentally determined Si isotope fractionation between silicate and Fe metal and implications for Earth's core formation

NASA Astrophysics Data System (ADS)

Shahar, Anat; Ziegler, Karen; Young, Edward D.; Ricolleau, Angele; Schauble, Edwin A.; Fei, Yingwei

2009-10-01

Stable isotope fractionation amongst phases comprising terrestrial planets and asteroids can be used to elucidate planet-forming processes. To date, the composition of the Earth's core remains largely unknown though cosmochemical and geophysical evidence indicates that elements lighter than iron and nickel must reside there. Silicon is often cited as a light element that could explain the seismic properties of the core. The amount of silicon in the core, if any, can be deduced from the difference in 30Si/ 28Si between meteorites and terrestrial rocks if the Si isotope fractionation between silicate and Fe-rich metal is known. Recent studies (e.g., [Georg R.B., Halliday A.N., Schauble E.A., Reynolds B.C., 2007. Silicon in the Earth's core. Nature 447 (31), 1102-1106.]; [Fitoussi, C., Bourdon, B., Kleine, T., Oberli, F., Reynolds, B. C., 2009. Si isotope systematics of meteorites and terrestrial peridotites: implications for Mg/Si fractionation in the solar nebula and for Si in the Earth's core. Earth Planet. Sci. Lett. 287, 77-85.]) showing (sometimes subtle) differences between 30Si/ 28Si in meteorites and terrestrial rocks suggest that Si missing from terrestrial rocks might be in the core. However, any conclusion based on Earth-meteorite comparisons depends on the veracity of the 30Si/ 28Si fractionation factor between silicates and metals at appropriate conditions. Here we present the first direct experimental evidence that silicon isotopes are not distributed uniformly between iron metal and rock when equilibrated at high temperatures. High-precision measurements of the silicon isotope ratios in iron-silicon alloy and silicate equilibrated at 1 GPa and 1800 °C show that Si in silicate has higher 30Si/ 28Si than Si in metal, by at least 2.0‰. These findings provide an experimental foundation for using isotope ratios of silicon as indicators of terrestrial planet formation processes. They imply that if Si isotope equilibrium existed during segregation of Earth

Composite nanoparticles containing rare earth metal and methods of preparation thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kandapallil, Binil Itty Ipe; Krishnan, Lakshmi; Johnson, Francis

The present invention is directed to composite nanoparticles comprising a metal, a rare earth element, and, optionally, a complexing ligand. The invention is also directed to composite nanoparticles having a core-shell structure and to processes for preparation of composite nanoparticles of the invention.

Entropy in halide perovskites

NASA Astrophysics Data System (ADS)

Katan, Claudine; Mohite, Aditya D.; Even, Jacky

2018-05-01

Claudine Katan, Aditya D. Mohite and Jacky Even discuss the possible impact of various entropy contributions (stochastic structural fluctuations, anharmonicity and lattice softness) on the optoelectronic properties of halide perovskite materials and devices.

Perspective: Theory and simulation of hybrid halide perovskites

PubMed Central

Jung, Young-Kwang

2017-01-01

Organic-inorganic halide perovskites present a number of challenges for first-principles atomistic materials modeling. Such “plastic crystals” feature dynamic processes across multiple length and time scales. These include the following: (i) transport of slow ions and fast electrons; (ii) highly anharmonic lattice dynamics with short phonon lifetimes; (iii) local symmetry breaking of the average crystallographic space group; (iv) strong relativistic (spin-orbit coupling) effects on the electronic band structure; and (v) thermodynamic metastability and rapid chemical breakdown. These issues, which affect the operation of solar cells, are outlined in this perspective. We also discuss general guidelines for performing quantitative and predictive simulations of these materials, which are relevant to metal-organic frameworks and other hybrid semiconducting, dielectric and ferroelectric compounds. PMID:29166078

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.

A Victim of Halide Ion Segregation. How Light Soaking Affects Solar Cell Performance of Mixed Halide Lead Perovskites

DOE PAGES

Samu, Gergely F.; Janaky, Csaba; Kamat, Prashant V.

2017-07-24

Photoinduced segregation in mixed halide perovskites has a direct influence on decreasing the solar cell efficiency as segregated I-rich domains serve as charge recombination centers. Here, the changes in the external quantum efficiency mirror the spectral loss in the absorption; however, the time scale of the IPCE recovery in the dark is slower than the absorption recovery, showing the intricate nature of the photoinduced halide segregation and charge collection in solar cell devices.

Metallic rare-earth silicide nanowires on silicon surfaces.

PubMed

Dähne, Mario; Wanke, Martina

2013-01-09

The formation, atomic structure, and electronic properties of self-assembled rare-earth silicide nanowires on silicon surfaces were studied by scanning tunneling microscopy and angle-resolved photoelectron spectroscopy. Metallic dysprosium and erbium silicide nanowires were observed on both the Si(001) and Si(557) surfaces. It was found that they consist of hexagonal rare-earth disilicides for both surface orientations. On Si(001), the nanowires are characterized by a one-dimensional band structure, while the electronic dispersion is two-dimensional for the nanowires formed on Si(557). This behavior is explained by the different orientations of the hexagonal c axis of the silicide leading to different conditions for the carrier confinement. By considering this carrier confinement it is demonstrated how the one-dimensional band structure of the nanowires on Si(001) can be derived from the two-dimensional one of the silicide monolayer on Si(111).

Epitaxial growth of CoO films on semiconductor and metal substrates by constructing a complex heterostructure

NASA Astrophysics Data System (ADS)

Entani, S.; Kiguchi, M.; Saiki, K.; Koma, A.

2003-01-01

Epitaxial growth of CoO films was studied using reflection high-energy electron diffraction (RHEED), electron energy loss spectroscopy (EELS), ultraviolet photoelectron spectroscopy (UPS) and Auger electron spectroscopy (AES). The RHEED results indicated that an epitaxial CoO film grew on semiconductor and metal substrates (CoO (0 0 1)∥GaAs (0 0 1), Cu (0 0 1), Ag (0 0 1) and [1 0 0]CoO∥[1 0 0] substrates) by constructing a complex heterostructure with two alkali halide buffer layers. The AES, EELS and UPS results showed that the grown CoO film had almost the same electronic structure as bulk CoO. We could show that use of alkali halide buffer layers was a good way to grow metal oxide films on semiconductor and metal substrates in an O 2 atmosphere. The alkali halide layers not only works as glue to connect very dissimilar materials but also prevents oxidation of metal and semiconductor substrates.

Spectral Changes in Metal Halide and High-pressure Sodium Lamps Equipped with Electronic Dimming

NASA Technical Reports Server (NTRS)

Bubenheim, David L.; Sargis, Raman; Wilson, David

1995-01-01

Electronic dimming of high-intensity discharge lamps offers control of photosynthetic photon flux (PPF) but is often characterized as causing significant spectral changes. Growth chambers with 400-W metal halide (MH) and high-pressure sodium (HPS) lamps were equipped with a dimmer system using silicon-controlled rectifiers (SCR) as high-speed switches. Phase control operation turned the line power off for some period of the alternating current cycle. At full power, the electrical input to HPS and MH lamps was 480 W (root mean squared) and could be decreased to 267 W and 428 W, respectively, before the arc was extinguished. Concomitant with this decrease in input power, PPF decreased by 60% in HPS and 50% in MH. The HPS lamp has characteristic spectral peaks at 589 and 595 nm. As power to the HPS lamps was decreased, the 589-nm peak remained constant while the 595-nm peak decreased, equaling the 589-nm peak at 345-W input, and the 589-nm peak was almost absent at 270-W input. The MH lamp has a broader spectral output but also has a peak at 589 nm and another smaller peak at 545 nm. As input power to the MH lamps decreased, the peak at 589 diminished to equal the 545-nm peak. As input power approached 428 W, the 589-nm peak shifted to 570 nm. While the spectrum changed as input power was decreased in the MH and HPS lamps, the phytochrome equilibrium ratio (P(sub fr):P(sub tot)) remains unchanged for both lamp types.

Rare earth element recycling from waste nickel-metal hydride batteries.

PubMed

Yang, Xiuli; Zhang, Junwei; Fang, Xihui

2014-08-30

With an increase in number of waste nickel-metal hydride batteries, and because of the importance of rare earth elements, the recycling of rare earth elements is becoming increasingly important. In this paper, we investigate the effects of temperature, hydrochloric acid concentration, and leaching time to optimize leaching conditions and determine leach kinetics. The results indicate that an increase in temperature, hydrochloric acid concentration, and leaching time enhance the leaching rate of rare earth elements. A maximum rare earth elements recovery of 95.16% was achieved at optimal leaching conditions of 70°C, solid/liquid ratio of 1:10, 20% hydrochloric acid concentration, -74μm particle size, and 100min leaching time. The experimental data were best fitted by a chemical reaction-controlled model. The activation energy was 43.98kJ/mol and the reaction order for hydrochloric acid concentration was 0.64. The kinetic equation for the leaching process was found to be: 1-(1-x)(1/3)=A/ρr0[HCl](0.64)exp-439,8008.314Tt. After leaching and filtration, by adding saturated oxalic solution to the filtrate, rare earth element oxalates were obtained. After removing impurities by adding ammonia, filtering, washing with dilute hydrochloric acid, and calcining at 810°C, a final product of 99% pure rare earth oxides was obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

A review of bacterial methyl halide degradation: biochemistry, genetics and molecular ecology

USGS Publications Warehouse

McDonald, I.R.; Warner, K.L.; McAnulla, C.; Woodall, C.A.; Oremland, R.S.; Murrell, J.C.

2002-01-01

Methyl halide-degrading bacteria are a diverse group of organisms that are found in both terrestrial and marine environments. They potentially play an important role in mitigating ozone depletion resulting from methyl chloride and methyl bromide emissions. The first step in the pathway(s) of methyl halide degradation involves a methyltransferase and, recently, the presence of this pathway has been studied in a number of bacteria. This paper reviews the biochemistry and genetics of methyl halide utilization in the aerobic bacteria Methylobacterium chloromethanicum CM4T, Hyphomicrobium chloromethanicum CM2T, Aminobacter strain IMB-1 and Aminobacter strain CC495. These bacteria are able to use methyl halides as a sole source of carbon and energy, are all members of the α-Proteobacteria and were isolated from a variety of polluted and pristine terrestrial environments. An understanding of the genetics of these bacteria identified a unique gene (cmuA) involved in the degradation of methyl halides, which codes for a protein (CmuA) with unique methyltransferase and corrinoid functions. This unique functional gene, cmuA, is being used to develop molecular ecology techniques to examine the diversity and distribution of methyl halide-utilizing bacteria in the environment and hopefully to understand their role in methyl halide degradation in different environments. These techniques will also enable the detection of potentially novel methyl halide-degrading bacteria.

High-pressure phase transitions in rare earth metal thulium to 195 GPa.

PubMed

Montgomery, Jeffrey M; Samudrala, Gopi K; Tsoi, Georgiy M; Vohra, Yogesh K

2011-04-20

We have performed image plate x-ray diffraction studies on a heavy rare earth metal, thulium (Tm), in a diamond anvil cell to a pressure of 195 GPa and volume compression V/V₀ = 0.38 at room temperature. The rare earth crystal structure sequence, hcp →Sm-type→ dhcp →fcc → distorted fcc, is observed in Tm below 70 GPa with the exception of a pure fcc phase. The focus of our study is on the ultrahigh-pressure phase transition and Rietveld refinement of crystal structures in the pressure range between 70 and 195 GPa. The hexagonal hR-24 phase is seen to describe the distorted fcc phase between 70 and 124 GPa. Above 124 ± 4 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of -1.5%. The equation of state data shows rapid stiffening above the phase transition at 124 GPa and is indicative of participation of f-electrons in bonding. We compare the behavior of Tm to other heavy rare-earths and heavy actinide metals under extreme conditions of pressure.

High-pressure phase transitions in rare earth metal thulium to 195 GPa

NASA Astrophysics Data System (ADS)

Montgomery, Jeffrey M.; Samudrala, Gopi K.; Tsoi, Georgiy M.; Vohra, Yogesh K.

2011-04-01

We have performed image plate x-ray diffraction studies on a heavy rare earth metal, thulium (Tm), in a diamond anvil cell to a pressure of 195 GPa and volume compression V/Vo = 0.38 at room temperature. The rare earth crystal structure sequence, {hcp}\\to {Sm {-}type} \\to {dhcp} \\to {fcc} \\to distorted fcc, is observed in Tm below 70 GPa with the exception of a pure fcc phase. The focus of our study is on the ultrahigh-pressure phase transition and Rietveld refinement of crystal structures in the pressure range between 70 and 195 GPa. The hexagonal hR- 24 phase is seen to describe the distorted fcc phase between 70 and 124 GPa. Above 124 ± 4 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.5%. The equation of state data shows rapid stiffening above the phase transition at 124 GPa and is indicative of participation of f-electrons in bonding. We compare the behavior of Tm to other heavy rare-earths and heavy actinide metals under extreme conditions of pressure.

Dynamical Correlation In Some Liquid Alkaline Earth Metals Near Melting

NASA Astrophysics Data System (ADS)

Thakore, B. Y.; Suthar, P. H.; Khambholja, S. G.; Gajjar, P. N.; Jani, A. R.

2010-12-01

The study of dynamical variables: velocity autocorrelation function (VACF) and power spectrum of liquid alkaline earth metals (Ca, Sr, and Ba) have been presented based on the static harmonic well approximation. The effective interatomic potential for liquid metals is computed using our well recognized model potential with the exchange correlation functions due to Hartree, Taylor, Ichimaru and Utsumi, Farid et al. and Sarkar et al. It is observed that the VACF computed using Sarkar et al. gives the good agreement with available molecular dynamics simulation (MD) results [Phys Rev. B 62, 14818 (2000)]. The shoulder of the power spectrum depends upon the type of local field correlation function used.

Separation of rare earths from transition metals by liquid-liquid extraction from a molten salt hydrate to an ionic liquid phase.

PubMed

Rout, Alok; Binnemans, Koen

2014-02-28

The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mixtures of rare earths in the hydrated melt. The influence of different extraction parameters was investigated: the initial metal loading in the feed phase, percentage of water in the feed solution, equilibration time, and the type of hydrated melt. The extraction of rare earths from Ca(NO3)2·4H2O was compared with extraction from CaCl2·4H2O by [A336][Cl] (Aliquat 336). The nitrate system was found to be the better one. The extraction and separation of rare earths from the transition metals nickel, cobalt and zinc were also investigated. Remarkably high separation factors of rare-earth ions over transition metal ions were observed for extraction from Ca(NO3)2·4H2O by the [A336][NO3] extracting phase. Furthermore, rare-earth ions could be separated efficiently from transition metal ions, even in melts with very high concentrations of transition metal ions. Rare-earth oxides could be directly dissolved in the Ca(NO3)2·4H2O phase in the presence of small amounts of Al(NO3)3·9H2O or concentrated nitric acid. The efficiency of extraction after dissolving the rare-earth oxides in the hydrated nitrate melt was identical to extraction from solutions with rare-earth nitrates dissolved in the molten phase. The stripping of the rare-earth ions from the loaded ionic liquid phase and the reuse of the recycled ionic liquid were also investigated in detail.

Thermodynamic Considerations of Direct Oxygen Removal from Titanium by Utilizing the Deoxidation Capability of Rare Earth Metals

NASA Astrophysics Data System (ADS)

Okabe, Toru H.; Zheng, Chenyi; Taninouchi, Yu-ki

2018-06-01

Oxygen removal from metallic Ti is extremely difficult and, currently, there is no commercial process for effectively deoxidizing Ti or its alloys. The oxygen concentration in Ti scraps is normally higher than that in virgin metals such as in Ti sponges produced by the Kroll process. When scraps are remelted with virgin metals for producing primary ingots of Ti or its alloys, the amount of scrap that can be used is limited owing to the accumulation of oxygen impurities. Future demands of an increase in Ti production and of mitigating environmental impacts require that the amount of scrap recycled as a feed material of Ti ingots should also increase. Therefore, it is important to develop methods for removing oxygen directly from Ti scraps. In this study, we evaluated the deoxidation limit for β-Ti using Y or light rare earth metals (La, Ce, Pr, or Nd) as a deoxidant. Thermodynamic considerations suggest that extra-low-oxygen Ti, with an oxygen concentration of 100 mass ppm or less can be obtained using a molten salt equilibrating with rare earth metals. The results presented herein also indicate that methods based on molten salt electrolysis for producing rare earth metals can be utilized for effectively and directly deoxidizing Ti scraps.

Resonance Raman and excitation energy dependent charge transfer mechanism in halide-substituted hybrid perovskite solar cells.

PubMed

Park, Byung-wook; Jain, Sagar M; Zhang, Xiaoliang; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

2015-02-24

Organo-metal halide perovskites (OMHPs) are materials with attractive properties for optoelectronics. They made a recent introduction in the photovoltaics world by methylammonium (MA) lead triiodide and show remarkably improved charge separation capabilities when chloride and bromide are added. Here we show how halide substitution in OMHPs with the nominal composition CH3NH3PbI2X, where X is I, Br, or Cl, influences the morphology, charge quantum yield, and local interaction with the organic MA cation. X-ray diffraction and photoluminescence data demonstrate that halide substitution affects the local structure in the OMHPs with separate MAPbI3 and MAPbCl3 phases. Raman spectroscopies as well as theoretical vibration calculations reveal that this at the same time delocalizes the charge to the MA cation, which can liberate the vibrational movement of the MA cation, leading to a more adaptive organic phase. The resonance Raman effect together with quantum chemical calculations is utilized to analyze the change in charge transfer mechanism upon electronic excitation and gives important clues for the mechanism of the much improved photovoltage and photocurrent also seen in the solar cell performance for the materials when chloride compounds are included in the preparation.

Volatile Gas Production by Methyl Halide Transferase: An In Situ Reporter Of Microbial Gene Expression In Soil.

PubMed

Cheng, Hsiao-Ying; Masiello, Caroline A; Bennett, George N; Silberg, Jonathan J

2016-08-16

Traditional visual reporters of gene expression have only very limited use in soils because their outputs are challenging to detect through the soil matrix. This severely restricts our ability to study time-dependent microbial gene expression in one of the Earth's largest, most complex habitats. Here we describe an approach to report on dynamic gene expression within a microbial population in a soil under natural water levels (at and below water holding capacity) via production of methyl halides using a methyl halide transferase. As a proof-of-concept application, we couple the expression of this gas reporter to the conjugative transfer of a bacterial plasmid in a soil matrix and show that gas released from the matrix displays a strong correlation with the number of transconjugant bacteria that formed. Gas reporting of gene expression will make possible dynamic studies of natural and engineered microbes within many hard-to-image environmental matrices (soils, sediments, sludge, and biomass) at sample scales exceeding those used for traditional visual reporting.

Lithium-aluminum-magnesium electrode composition

DOEpatents

Melendres, Carlos A.; Siegel, Stanley

1978-01-01

A negative electrode composition is presented for use in a secondary, high-temperature electrochemical cell. The cell also includes a molten salt electrolyte of alkali metal halides or alkaline earth metal halides and a positive electrode including a chalcogen or a metal chalcogenide as the active electrode material. The negative electrode composition includes up to 50 atom percent lithium as the active electrode constituent and a magnesium-aluminum alloy as a structural matrix. Various binary and ternary intermetallic phases of lithium, magnesium, and aluminum are formed but the electrode composition in both its charged and discharged state remains substantially free of the alpha lithium-aluminum phase and exhibits good structural integrity.

Voltage Control of Rare-Earth Magnetic Moments at the Magnetic-Insulator-Metal Interface

NASA Astrophysics Data System (ADS)

Leon, Alejandro O.; Cahaya, Adam B.; Bauer, Gerrit E. W.

2018-01-01

The large spin-orbit interaction in the lanthanides implies a strong coupling between their internal charge and spin degrees of freedom. We formulate the coupling between the voltage and the local magnetic moments of rare-earth atoms with a partially filled 4 f shell at the interface between an insulator and a metal. The rare-earth-mediated torques allow the power-efficient control of spintronic devices by electric-field-induced ferromagnetic resonance and magnetization switching.

Preferential Eu Site Occupation and Its Consequences in the Ternary Luminescent Halides AB 2 I 5 : Eu 2 + ( A = Li – Cs ; B = Sr , Ba)

DOE PAGES

Fang, C.  M.; Biswas, Koushik

2015-07-22

Several rare-earth-doped, heavy-metal halides have recently been identified as potential next-generation luminescent materials with high efficiency at low cost. AB 2I 5:Eu 2+ (A=Li–Cs; B=Sr, Ba) is one such family of halides. Its members, such as CsBa 2I 5:Eu 2+ and KSr 2I 5:Eu 2+, are currently being investigated as high-performance scintillators with improved sensitivity, light yield, and energy resolution less than 3% at 662 keV. Within the AB 2I 5 family, our first-principles-based calculations reveal two remarkably different trends in Eu site occupation. The substitutional Eu ions occupy both eightfold-coordinated B1(VIII) and the sevenfold-coordinated B2(VII) sites in the Sr-containingmore » compounds. However, in the Ba-containing crystals, Eu ions strongly prefer the B2(VII)sites. This random versus preferential distribution of Eu affects their electronic properties. The calculations also suggest that in the Ba-containing compounds one can expect the formation of Eu-rich domains. These results provide atomistic insight into recent experimental observations about the concentration and temperature effects in Eu-doped CsBa 2I 5. We discuss the implications of our results with respect to luminescent properties and applications. We also hypothesize Sr, Ba-mixed quaternary iodides ABa VIIISr VIII 5:Eu as scintillators having enhanced homogeneity and electronic properties.« less

Method of enhancing the wettability of boron nitride for use as an electrochemical cell separator

DOEpatents

McCoy, L.R.

1981-01-23

A felt or other fabric of boron nitride suitable for use as an interelectrode separator within an electrochemical cell is wetted with a solution containing a thermally decomposable organic salt of an alkaline earth metal. An aqueous solution of magnesium acetate is the preferred solution for this purpose. After wetting the boron nitride, the solution is dried by heating at a sufficiently low temperature to prevent rapid boiling and the creation of voids within the separator. The dried material is then calcined at an elevated temperature in excess of 400/sup 0/C to provide a coating of an oxide of magnesium on the surface of the boron nitride fibers. A fabric or felt of boron nitride treated in this manner is easily wetted by molten electrolytic salts, such as the alkali metal halides or alkaline earth metal halides, that are used in high temperature, secondary electrochemical cells.

Method of enhancing the wettability of boron nitride for use as an electrochemical cell separator

DOEpatents

McCoy, Lowell R.

1982-01-01

A felt or other fabric of boron nitride suitable for use as an interelecte separator within an electrochemical cell is wetted with a solution containing a thermally decomposable organic salt of an alkaline earth metal. An aqueous solution of magnesium acetate is the preferred solution for this purpose. After wetting the boron nitride, the solution is dried by heating at a sufficiently low temperature to prevent rapid boiling and the creation of voids within the separator. The dried material is then calcined at an elevated temperature in excess of 400.degree. C. to provide a coating of an oxide of magnesium on the surface of the boron nitride fibers. A fabric or felt of boron nitride treated in this manner is easily wetted by molten electrolytic salts, such as the alkali metal halides or alkaline earth metal halides, that are used in high temperature, secondary electrochemical cells.

Self-Organized Superlattice and Phase Coexistence inside Thin Film Organometal Halide Perovskite.

PubMed

Kim, Tae Woong; Uchida, Satoshi; Matsushita, Tomonori; Cojocaru, Ludmila; Jono, Ryota; Kimura, Kohei; Matsubara, Daiki; Shirai, Manabu; Ito, Katsuji; Matsumoto, Hiroaki; Kondo, Takashi; Segawa, Hiroshi

2018-02-01

Organometal halide perovskites have attracted widespread attention as the most favorable prospective material for photovoltaic technology because of their high photoinduced charge separation and carrier transport performance. However, the microstructural aspects within the organometal halide perovskite are still unknown, even though it belongs to a crystal system. Here direct observation of the microstructure of the thin film organometal halide perovskite using transmission electron microscopy is reported. Unlike previous reports claiming each phase of the organometal halide perovskite solely exists at a given temperature range, it is identified that the tetragonal and cubic phases coexist at room temperature, and it is confirmed that superlattices composed of a mixture of tetragonal and cubic phases are self-organized without a compositional change. The organometal halide perovskite self-adjusts the configuration of phases and automatically organizes a buffer layer at boundaries by introducing a superlattice. This report shows the fundamental crystallographic information for the organometal halide perovskite and demonstrates new possibilities as promising materials for various applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of halide ions on the photodegradation of ibuprofen in aqueous environments.

PubMed

Li, Fuhua; Kong, Qingqing; Chen, Ping; Chen, Min; Liu, Guoguang; Lv, Wenying; Yao, Kun

2017-01-01

Typically contained within ambient surface waters and certain industrial wastewaters, are plentiful halide ions, which possess varying degrees of photosensitivity. The effects of halide ions on the photodegradation of ibuprofen (IBP) were investigated under UV irradiation using a 500 W mercury lamp as a light source. Studies of the mechanism of halide ions were inclusive of both their light shielding effects and quenching experiments. The results indicated that chloride ion has a slight inhibition against IBP photodegradation under neutral condition, and significant inhibition is observed with bromide ions and iodide ions. In addition to the observed increased rate of IBP photodegradation in conjunction with elevated pH in solution, the inhibitory effect of halide ions was different. When the pH value of the IBP solution was 5, chloride ions were seen to facilitate the photodegradation of IBP. Halide ions can inhibit IBP photodegradation by means of a light attenuation effect. All of the halide ions significantly facilitated the generation of 1 O 2 . Copyright © 2016 Elsevier Ltd. All rights reserved.

Metallaphotoredox-catalysed sp3-sp3 cross-coupling of carboxylic acids with alkyl halides

NASA Astrophysics Data System (ADS)

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

2016-08-01

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 sp3-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 sp2-hybridized species, the development of methods for sp3-sp3 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 sp3-sp3 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 sp3-sp3 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 sp3-sp3 bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. This metallaphotoredox protocol is suitable for

Adsorption of alkali and alkaline earth metal atoms and dimers on monolayer germanium carbide

NASA Astrophysics Data System (ADS)

Gökçe, Aytaç Gürhan; Ersan, Fatih

2017-01-01

First-principles plane wave calculations have been performed to study the adsorption of alkali and alkaline earth metals on monolayer germanium carbide (GeC). We found that the favourable adsorption sites on GeC sheet for single alkali and alkaline earth adatoms are generally different from graphene or germanene. Among them, Mg, Na and their dimers have weakly bounded to GeC due to their closed valence electron shells, so they may have high mobility on GeC. Two different levels of adatom coverage (? and ?) have been investigated and we concluded that different electronic structures and magnetic moments for both coverages owing to alkali and alkaline earth atoms have long range electrostatic interactions. Lithium atom prefers to adsorbed on hollow site similar to other group-IV monolayers and the adsorption results in metallisation of GeC instead of semiconducting behaviour. Na and K adsorption can induce 1 ? total magnetic moment on GeC structures and they have shown semiconductor property which may have potential use in spintronic devices. We also showed that alkali or alkaline earth metal atoms can form dimer on GeC sheet. Calculated adsorption energies suggest that clustering of alkali and alkaline earth atoms is energetically favourable. All dimer adsorbed GeC systems have nonmagnetic semiconductor property with varying band gaps from 0.391 to 1.311 eV which are very suitable values for various device applications.

Effects of halides on plasmid-mediated silver resistance in Escherichia coli.

PubMed

Gupta, A; Maynes, M; Silver, S

1998-12-01

Silver resistance of sensitive Escherichia coli J53 and resistance plasmid-containing J53(pMG101) was affected by halides in the growth medium. The effects of halides on Ag+ resistance were measured with AgNO3 and silver sulfadiazine, both on agar and in liquid. Low concentrations of chloride made the differences in MICs between sensitive and resistant strains larger. High concentrations of halides increased the sensitivities of both strains to Ag+.

Cu-In Halide Perovskite Solar Absorbers.

PubMed

Zhao, Xin-Gang; Yang, Dongwen; Sun, Yuanhui; Li, Tianshu; Zhang, Lijun; Yu, Liping; Zunger, Alex

2017-05-17

The long-term chemical instability and the presence of toxic Pb in otherwise stellar solar absorber APbX 3 made of organic molecules on the A site and halogens for X have hindered their large-scale commercialization. Previously explored ways to achieve Pb-free halide perovskites involved replacing Pb 2+ with other similar M 2+ cations in ns 2 electron configuration, e.g., Sn 2+ or by Bi 3+ (plus Ag + ), but unfortunately this showed either poor stability (M = Sn) or weakly absorbing oversized indirect gaps (M = Bi), prompting concerns that perhaps stability and good optoelectronic properties might be contraindicated. Herein, we exploit the electronic structure underpinning of classic Cu[In,Ga]Se 2 (CIGS) chalcopyrite solar absorbers to design Pb-free halide perovskites by transmuting 2Pb to the pair [B IB + C III ] such as [Cu + Ga] or [Ag + In] and combinations thereof. The resulting group of double perovskites with formula A 2 BCX 6 (A = K, Rb, Cs; B = Cu, Ag; C = Ga, In; X = Cl, Br, I) benefits from the ionic, yet narrow-gap character of halide perovskites, and at the same time borrows the advantage of the strong Cu(d)/Se(p) → Ga/In(s/p) valence-to-conduction-band absorption spectra known from CIGS. This constitutes a new group of CuIn-based Halide Perovskite (CIHP). Our first-principles calculations guided by such design principles indicate that the CIHPs class has members with clear thermodynamic stability, showing direct band gaps, and manifesting a wide-range of tunable gap values (from zero to about 2.5 eV) and combination of light electron and heavy-light hole effective masses. Materials screening of candidate CIHPs then identifies the best-of-class Rb 2 [CuIn]Cl 6 , Rb 2 [AgIn]Br 6 , and Cs 2 [AgIn]Br 6 , having direct band gaps of 1.36, 1.46, and 1.50 eV, and theoretical spectroscopic limited maximal efficiency comparable to chalcopyrites and CH 3 NH 3 PbI 3 . Our finding offers a new routine for designing new-type Pb-free halide perovskite solar

Determination of Thermodynamic Properties of Alkaline Earth-liquid Metal Alloys Using the Electromotive Force Technique

PubMed Central

Nigl, Thomas P.; Smith, Nathan D.; Lichtenstein, Timothy; Gesualdi, Jarrod; Kumar, Kuldeep; Kim, Hojong

2017-01-01

A novel electrochemical cell based on a CaF2 solid-state electrolyte has been developed to measure the electromotive force (emf) of binary alkaline earth-liquid metal alloys as functions of both composition and temperature in order to acquire thermodynamic data. The cell consists of a chemically stable solid-state CaF2-AF2 electrolyte (where A is the alkaline-earth element such as Ca, Sr, or Ba), with binary A-B alloy (where B is the liquid metal such as Bi or Sb) working electrodes, and a pure A metal reference electrode. Emf data are collected over a temperature range of 723 K to 1,123 K in 25 K increments for multiple alloy compositions per experiment and the results are analyzed to yield activity values, phase transition temperatures, and partial molar entropies/enthalpies for each composition. PMID:29155770

Metal-metal bonds in f-element chemistry.

PubMed

Liddle, Stephen T; Mills, David P

2009-08-07

The molecular chemistry of the f-elements is traditionally dominated by the use of carbon-, nitrogen-, oxygen-, or halide-ligands. However, the use of metal-based fragments as ligands is underdeveloped, which contrasts to the fields of d- and p-block metal-metal complexes that have developed extensively over the last fifty years. This perspective outlines the development of compounds, which possess polarised covalent or donor-acceptor f-element-metal bonds. For this review, the f-element is defined as (i) a group 3 or lanthanide metal: scandium, yttrium, lanthanum to lutetium, or (ii) an actinide metal: thorium, or uranium, and the metal is defined as a d-block transition metal, or a group 13 (aluminium or gallium), a group 14 (silicon, germanium, or tin), or a group 15 (antimony, or bismuth) metal. Silicon, germanium, and antimony are traditionally classified as metalloids but they are included for completeness. This review focuses mainly on complexes that have been structurally authenticated by single-crystal X-ray diffraction studies and we highlight novel aspects of their syntheses, properties, and reactivities.

Ground-state properties of rare-earth metals: an evaluation of density-functional theory.

PubMed

Söderlind, Per; Turchi, P E A; Landa, A; Lordi, V

2014-10-15

The rare-earth metals have important technological applications due to their magnetic properties, but are scarce and expensive. Development of high-performance magnetic materials with less rare-earth content is desired, but theoretical modeling is hampered by complexities of the rare earths electronic structure. The existence of correlated (atomic-like) 4f electrons in the vicinity of the valence band makes any first-principles theory challenging. Here, we apply and evaluate the efficacy of density-functional theory for the series of lanthanides (rare earths), investigating the influence of the electron exchange and correlation functional, spin-orbit interaction, and orbital polarization. As a reference, the results are compared with those of the so-called 'standard model' of the lanthanides in which electrons are constrained to occupy 4f core states with no hybridization with the valence electrons. Some comparisons are also made with models designed for strong electron correlations. Our results suggest that spin-orbit coupling and orbital polarization are important, particularly for the magnitude of the magnetic moments, and that calculated equilibrium volumes, bulk moduli, and magnetic moments show correct trends overall. However, the precision of the calculated properties is not at the level of that found for simpler metals in the Periodic Table of Elements, and the electronic structures do not accurately reproduce x-ray photoemission spectra.

The Electronic Structure and Optical Properties of Anatase TiO₂ with Rare Earth Metal Dopants from First-Principles Calculations.

PubMed

Xie, Kefeng; Jia, Qiangqiang; Wang, Yizhe; Zhang, Wenxue; Xu, Jingcheng

2018-01-24

The electronic and optical properties of the rare earth metal atom-doped anatase TiO₂ have been investigated systematically via density functional theory calculations. The results show that TiO₂ doped by Ce or Pr is the optimal choice because of its small band gap and strong optical absorption. Rare earth metal atom doping induces several impurity states that tune the location of valence and conduction bands and an obvious lattice distortion that should reduce the probability of electron-hole recombination. This effect of band change originates from the 4 f electrons of the rare earth metal atoms, which leads to an improved visible light absorption. This finding indicates that the electronic structure of anatase TiO₂ is tuned by the introduction of impurity atoms.

Miscellaneous Lasing Actions in Organo-Lead Halide Perovskite Films.

PubMed

Duan, Zonghui; Wang, Shuai; Yi, Ningbo; Gu, Zhiyuan; Gao, Yisheng; Song, Qinghai; Xiao, Shumin

2017-06-21

Lasing actions in organo-lead halide perovskite films have been heavily studied in the past few years. However, due to the disordered nature of synthesized perovskite films, the lasing actions are usually understood as random lasers that are formed by multiple scattering. Herein, we demonstrate the miscellaneous lasing actions in organo-lead halide perovskite films. In addition to the random lasers, we show that a single or a few perovskite microparticles can generate laser emissions with their internal resonances instead of multiple scattering among them. We experimentally observed and numerically confirmed whispering gallery (WG)-like microlasers in polygon shaped and other deformed microparticles. Meanwhile, owing to the nature of total internal reflection and the novel shape of the nanoparticle, the size of the perovskite WG laser can be significantly decreased to a few hundred nanometers. Thus, wavelength-scale lead halide perovskite lasers were realized for the first time. All of these laser behaviors are complementary to typical random lasers in perovskite film and will help the understanding of lasing actions in complex lead halide perovskite systems.

Switchable S = 1/2 and J = 1/2 Rashba bands in ferroelectric halide perovskites

PubMed Central

Kim, Minsung; Im, Jino; Freeman, Arthur J.; Ihm, Jisoon; Jin, Hosub

2014-01-01

The Rashba effect is spin degeneracy lift originated from spin–orbit coupling under inversion symmetry breaking and has been intensively studied for spintronics applications. However, easily implementable methods and corresponding materials for directional controls of Rashba splitting are still lacking. Here, we propose organic–inorganic hybrid metal halide perovskites as 3D Rashba systems driven by bulk ferroelectricity. In these materials, it is shown that the helical direction of the angular momentum texture in the Rashba band can be controlled by external electric fields via ferroelectric switching. Our tight-binding analysis and first-principles calculations indicate that and Rashba bands directly coupled to ferroelectric polarization emerge at the valence and conduction band edges, respectively. The coexistence of two contrasting Rashba bands having different compositions of the spin and orbital angular momentum is a distinctive feature of these materials. With recent experimental evidence for the ferroelectric response, the halide perovskites will be, to our knowledge, the first practical realization of the ferroelectric-coupled Rashba effect, suggesting novel applications to spintronic devices. PMID:24785294

Thermodynamic Investigation of the Reduction-Distillation Process for Rare Earth Metals Production

NASA Astrophysics Data System (ADS)

Judge, W. D.; Azimi, G.

2017-10-01

Owing to their high vapor pressure, the four rare earth metals samarium, europium, thulium, and ytterbium are produced by reduction-distillation whereby their oxides are reduced with metallic lanthanum in vacuo, and the produced metal is subsequently vaporized off. Here, we performed a thorough thermodynamic investigation to establish a fundamental understanding of the reduction-distillation process. Thermodynamic functions including vapor pressures, Gibbs free energies, and enthalpies of reaction were calculated and compared with available experimental data. Furthermore, the kinetics of the process was explored and theoretical evaporation rates were calculated from thermodynamic data. The thermodynamic model developed in this work can help optimize processing conditions to maximize the yield and improve the overall process.

Distribution behavior of uranium, neptunium, rare-earth elements ( Y, La, Ce, Nd, Sm, Eu, Gd) and alkaline-earth metals (Sr,Ba) between molten LiClKCI eutectic salt and liquid cadmium or bismuth

NASA Astrophysics Data System (ADS)

Kurata, M.; Sakamura, Y.; Hijikata, T.; Kinoshita, K.

1995-12-01

Distribution coefficients of uranium neptunium, eight rare-earth elements (Y, La, Ce, Pr, Nd, Sm, Eu and Gd) and two alkaline-earth metals (Sr and Ba) between molten LiCl-KCI eutectic salt and either liquid cadmium or bismuth were measured at 773 K. Separation factors of trivalent rare-earth elements to uranium or neptunium in the LiCl-KCl/Bi system were by one or two orders of magnitude larger than those in the LiCl-KCl/Cd system. On the contrary, the separation factors of alkaline-earth metals and divalent rare-earth elements to trivalent rare-earth elements were by one or two orders of magnitude smaller in the LiCl-KCl/Bi system.

Effects of Halides on Plasmid-Mediated Silver Resistance in Escherichia coli

PubMed Central

Gupta, Amit; Maynes, Maria; Silver, Simon

1998-01-01

Silver resistance of sensitive Escherichia coli J53 and resistance plasmid-containing J53(pMG101) was affected by halides in the growth medium. The effects of halides on Ag+ resistance were measured with AgNO3 and silver sulfadiazine, both on agar and in liquid. Low concentrations of chloride made the differences in MICs between sensitive and resistant strains larger. High concentrations of halides increased the sensitivities of both strains to Ag+. PMID:9835606

Strong Turbulence in Alkali Halide Negative Ion Plasmas

NASA Astrophysics Data System (ADS)

Sheehan, Daniel

1999-11-01

Negative ion plasmas (NIPs) are charge-neutral plasmas in which the negative charge is dominated by negative ions rather than electrons. They are found in laser discharges, combustion products, semiconductor manufacturing processes, stellar atmospheres, pulsar magnetospheres, and the Earth's ionosphere, both naturally and man-made. They often display signatures of strong turbulence^1. Development of a novel, compact, unmagnetized alkali halide (MX) NIP source will be discussed, it incorporating a ohmically-heated incandescent (2500K) tantulum solenoid (3cm dia, 15 cm long) with heat shields. The solenoid ionizes the MX vapor and confines contaminant electrons, allowing a very dry (electron-free) source. Plasma densities of 10^10 cm-3 and positive to negative ion mass ratios of 1 <= fracm_+m- <= 20 are achievable. The source will allow tests of strong turbulence theory^2. 1 Sheehan, D.P., et al., Phys. Fluids B5, 1593 (1993). 2 Tsytovich, V. and Wharton, C.W., Comm. Plasma Phys. Cont. Fusion 4, 91 (1978).

Cu-catalyzed Suzuki-Miyaura reactions of primary and secondary benzyl halides with arylboronates.

PubMed

Sun, Yan-Yan; Yi, Jun; Lu, Xi; Zhang, Zhen-Qi; Xiao, Bin; Fu, Yao

2014-09-28

A copper-catalyzed Suzuki-Miyaura coupling of benzyl halides with arylboronates is described. Varieties of primary benzyl halides as well as more challenging secondary benzyl halides with β hydrogens or steric hindrance could be successfully converted into the corresponding products. Thus it provides access to diarylmethanes, diarylethanes and triarylmethanes.

Electrochemical Doping of Halide Perovskites with Ion Intercalation.

PubMed

Jiang, Qinglong; Chen, Mingming; Li, Junqiang; Wang, Mingchao; Zeng, Xiaoqiao; Besara, Tiglet; Lu, Jun; Xin, Yan; Shan, Xin; Pan, Bicai; Wang, Changchun; Lin, Shangchao; Siegrist, Theo; Xiao, Qiangfeng; Yu, Zhibin

2017-01-24

Halide perovskites have recently been investigated for various solution-processed optoelectronic devices. The majority of studies have focused on using intrinsic halide perovskites, and the intentional incoporation of dopants has not been well explored. In this work, we discovered that small alkali ions, including lithium and sodium ions, could be electrochemically intercalated into a variety of halide and pseudohalide perovskites. The ion intercalation caused a lattice expansion of the perovskite crystals and resulted in an n-type doping of the perovskites. Such electrochemical doping improved the conductivity and changed the color of the perovskites, leading to an electrochromism with more than 40% reduction of transmittance in the 450-850 nm wavelength range. The doped perovskites exhibited improved electron injection efficiency into the pristine perovskite crystals, resulting in bright light-emitting diodes with a low turn-on voltage.

New technology of extracting the amount of rare earth metals from the red mud

NASA Astrophysics Data System (ADS)

Martoyan, G. A.; Karamyan, G. G.; Vardan, G. A.

2016-01-01

The paper outlined the environmental and economic problems associated with red mud - the waste generated in processing of bauxite ore for aluminum production. The chemical analysis of red mud has identified a number of useful elements including rare earth metals. The electromembrane technology of red mud processing with extraction of valuable elements is described. A possible scheme of separation of these metals through electrolysis is also given.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, J.W.; Wender, I.; Palekar, V.M.

1995-01-31

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

DOEpatents

Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

1995-01-01

The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

Neutron Diffraction Studies of Some Rare Earth-Transition Metal Deuterides.

DTIC Science & Technology

1986-05-01

RD-A168 M NEUTRON DIFFRACTION STUDIES OF SONE RARE EARTH-TRANSITION METAL DEUTERIDES(U) MISSOURI UNIV-ROLLR MATERIALS RESEARCH CENTER N J JAMES MY 86...REPORT William J. James OTtO -il May 1986 ZLECTEJU U. S. Army Research Office DAAG29-83-K-01 59 ".;’ Graduate Center for Materials Research ...9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT, PROJECT. TASK AREA & WORK UNIT NUMBERS 2* Graduate Center for Materials Research

FT-IR, micro-Raman and UV-vis spectroscopic and quantum chemical investigations of free 2,2'-dithiodipyridine and its metal (Co, Cu and Zn) halide complexes.

PubMed

Gökce, Halil; Bahçeli, Semiha

2013-10-01

In this study the elemental analysis results, molecular geometries, vibrational and electronic absorption spectra of free 2,2'-dithiodipyridine(C10H8N2S2), (or DTDP) (with synonym, 2,2'-dipyridyl disulfide) and M(C10H8N2S2)Cl2 (M=Co, Cu and Zn) complexes have been reported. Vibrational wavenumbers of free DTDP and its metal halide complexes have been calculated by using DFT/B3LYP calculation method with 6-31++G(d,p) and Lanl2DZ basis sets, respectively, in the ground state, for the first time. The calculated fundamental vibrational frequencies are in a good agreement with experimental data. The HOMO, LUMO and MEP analyses of all compounds are performed by DFT method. Copyright © 2013. Published by Elsevier B.V.

In Situ Preparation of Metal Halide Perovskite Nanocrystal Thin Films for Improved Light-Emitting Devices.

PubMed

Zhao, Lianfeng; Yeh, Yao-Wen; Tran, Nhu L; Wu, Fan; Xiao, Zhengguo; Kerner, Ross A; Lin, YunHui L; Scholes, Gregory D; Yao, Nan; Rand, Barry P

2017-04-25

Hybrid organic-inorganic halide perovskite semiconductors are attractive candidates for optoelectronic applications, such as photovoltaics, light-emitting diodes, and lasers. Perovskite nanocrystals are of particular interest, where electrons and holes can be confined spatially, promoting radiative recombination. However, nanocrystalline films based on traditional colloidal nanocrystal synthesis strategies suffer from the use of long insulating ligands, low colloidal nanocrystal concentration, and significant aggregation during film formation. Here, we demonstrate a facile method for preparing perovskite nanocrystal films in situ and that the electroluminescence of light-emitting devices can be enhanced up to 40-fold through this nanocrystal film formation strategy. Briefly, the method involves the use of bulky organoammonium halides as additives to confine crystal growth of perovskites during film formation, achieving CH 3 NH 3 PbI 3 and CH 3 NH 3 PbBr 3 perovskite nanocrystals with an average crystal size of 5.4 ± 0.8 nm and 6.4 ± 1.3 nm, respectively, as confirmed through transmission electron microscopy measurements. Additive-confined perovskite nanocrystals show significantly improved photoluminescence quantum yield and decay lifetime. Finally, we demonstrate highly efficient CH 3 NH 3 PbI 3 red/near-infrared LEDs and CH 3 NH 3 PbBr 3 green LEDs based on this strategy, achieving an external quantum efficiency of 7.9% and 7.0%, respectively, which represent a 40-fold and 23-fold improvement over control devices fabricated without the additives.

Characterization of metal binding sites onto biochar using rare earth elements as a fingerprint.

PubMed

Pourret, Olivier; Houben, David

2018-02-01

The ability of biochar to immobilize metals relies on the amount of functional groups at its surface but the contribution of each functional groups (e.g. carboxylic, phenolic) to metal bonding is poorly known. Using a new approach based on previous works on rare earth element (REE) interactions with humic substances, we aim at elucidating the relative contribution of these binding sites to metal sorption under various conditions (i.e. pH and ionic strengths, IS). Using batch experiments, REE sorption onto biochar was analyzed from pH 3 to 9 and IS 10 -1 mol/L to 10 -3 mol/L. Rare earth element patterns show a Middle REE (MREE) downward concavity at acidic pH and low ionic strength. These patterns are in good agreement with existing datasets quantifying REE binding with humic substances. Indeed, the MREE downward concavity displayed by REE-biochar complexation pattern compares well with REE patterns with various organic compounds. This similarity in the REE complexation pattern shapes suggests that carboxylic groups are the main binding sites of REE in biochar. Overall, our results indicate that the strength of the metal bonding with biochar increases when pH and IS increase, suggesting that biochar is more efficient for long-term metal immobilization at near neutral pH and high ionic strength.

Oxidation behavior of Cr(III) during thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides.

PubMed

Mao, Linqiang; Gao, Bingying; Deng, Ning; Liu, Lu; Cui, Hao

2016-02-01

The oxidation behavior of Cr(III) during the thermal treatment of chromium hydroxide in the presence of alkali and alkaline earth metal chlorides (NaCl, KCl, MgCl2, and CaCl2) was investigated. The amounts of Cr(III) oxidized at various temperatures and heating times were determined, and the Cr-containing species in the residues were characterized. During the transformation of chromium hydroxide to Cr2O3 at 300 °C approximately 5% of the Cr(III) was oxidized to form intermediate compounds containing Cr(VI) (i.e., CrO3), but these intermediates were reduced to Cr2O3 when the temperature was above 400 °C. Alkali and alkaline earth metals significantly promoted the oxidation of Cr(III) during the thermal drying process. Two pathways were involved in the influences the alkali and alkaline earth metals had on the formation of Cr(VI). In pathway I, the alkali and alkaline earth metals were found to act as electron transfer agents and to interfere with the dehydration process, causing more intermediate Cr(VI)-containing compounds (which were identified as being CrO3 and Cr5O12) to be formed. The reduction of intermediate compounds to Cr2O3 was also found to be hindered in pathway I. In pathway II, the alkali and alkaline earth metals were found to contribute to the oxidation of Cr(III) to form chromates. The results showed that the presence of alkali and alkaline earth metals significantly increases the degree to which Cr(III) is oxidized during the thermal drying of chromium-containing sludge. Copyright © 2015 Elsevier Ltd. All rights reserved.

High-temperature corrosion of metals in the salt and metallic melts containing rare earths

NASA Astrophysics Data System (ADS)

Karpov, V. V.; Abramov, A. V.; Zhilyakov, A. Yu.; Belikov, S. V.; Volkovich, V. A.; Polovov, I. B.; Rebrin, O. I.

2016-09-01

A complex of independent methods was employed to study the corrosion resistance of molybdenum, zirconium, tantalum and tungsten in chloride, chloride-fluoride and fluoride-oxide melts based on LiCl, CaCl2, NaCl- KCl, LiF, and containing rare earths. Tests were conducted for 30 h at 750-1050 °C. The metals showed excellent corrosion resistance in fused chlorides (the corrosion rates were below 0.0005 g/(m2 h). Despite the presence of chemically active fluoride ions in the chloride-fluoride melts, the metals studied also showed very low corrosion rates, except molybdenum, for which the rate of corrosion was 0,8 g/(m2 h). The corrosion resistance of tantalum was considerably reduced in the fluoride-oxide melts; the corrosion rate was over 1 g/(m2 h) corresponding to the 8-th grade of stability and placing tantalum to the group of "low stability" materials.

Local polar fluctuations in lead halide perovskite crystals

DOE PAGES

Yaffe, Omer; Guo, Yinsheng; Tan, Liang Z.; ...

2017-03-28

Hybrid lead-halide perovskites have emerged as an excellent class of photovoltaic materials. Recent reports suggest that the organic molecular cation is responsible for local polar fluctuations that inhibit carrier recombination. We combine low-frequency Raman scattering with first-principles molecular dynamics (MD) to study the fundamental nature of these local polar fluctuations. Our observations of a strong central peak in the cubic phase of both hybrid (CH 3NH 3PbBr 3) and all-inorganic (CsPbBr 3) lead-halide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. Furthermore, MD simulations indicatemore » that head-to-head Cs motion coupled to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr 3.« less

Lanthanide-halide based humidity indicators

DOEpatents

Beitz, James V [Hinsdale, IL; Williams, Clayton W [Chicago, IL

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.

Unraveling halide hydration: A high dilution approach.

PubMed

Migliorati, Valentina; Sessa, Francesco; Aquilanti, Giuliana; D'Angelo, Paola

2014-07-28

The hydration properties of halide aqua ions have been investigated combining classical Molecular Dynamics (MD) with Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Three halide-water interaction potentials recently developed [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)], along with three plausible choices for the value of the absolute hydration free energy of the proton (ΔG [minus sign in circle symbol]hyd[H+]), have been checked for their capability to properly describe the structural properties of halide aqueous solutions, by comparing the MD structural results with EXAFS experimental data. A very good agreement between theory and experiment has been obtained with one parameter set, namely LE, thus strengthening preliminary evidences for a ΔG [minus sign in circle symbol]hyd[H] value of -1100 kJ mol(-1) [M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144104 (2011)]. The Cl(-), Br(-), and I(-) ions have been found to form an unstructured and disordered first hydration shell in aqueous solution, with a broad distribution of instantaneous coordination numbers. Conversely, the F(-) ion shows more ordered and defined first solvation shell, with only two statistically relevant coordination geometries (six and sevenfold complexes). Our thorough investigation on the effect of halide ions on the microscopic structure of water highlights that the perturbation induced by the Cl(-), Br(-), and I(-) ions does not extend beyond the ion first hydration shell, and the structure of water in the F(-) second shell is also substantially unaffected by the ion.

A mini-review on rare earth metal-doped TiO2 for photocatalytic remediation of wastewater.

PubMed

Saqib, Najm Us; Adnan, Rohana; Shah, Irfan

2016-08-01

Titanium dioxide (TiO2) has been considered a useful material for the treatment of wastewater due to its non-toxic character, chemical stability and excellent electrical and optical properties which contribute in its wide range of applications, particularly in environmental remediation technology. However, the wide band gap of TiO2 photocatalyst (anatase phase, 3.20 eV) limits its photocatalytic activity to the ultraviolet region of light. Besides that, the electron-hole pair recombination has been found to reduce the efficiency of the photocatalyst. To overcome these problems, tailoring of TiO2 surface with rare earth metals to improve its surface, optical and photocatalytic properties has been investigated by many researchers. The surface modifications with rare earth metals proved to enhance the efficiency of TiO2 photocatalyts by way of reducing the band gap by shifting the working wavelength to the visible region and inhibiting the anatase-to-rutile phase transformations. This review paper summarises the attempts on modification of TiO2 using rare earth metals describing their effect on the photocatalytic activities of the modified TiO2 photocatalyst.

Dual Functionalization of White Phosphorus: Formation, Characterization, and Reactivity of Rare-Earth-Metal Cyclo-P3 Complexes.

PubMed

Du, Shanshan; Yin, Jianhao; Chi, Yue; Xu, Ling; Zhang, Wen-Xiong

2017-12-11

The [3+1] fragmentation reaction of rare-earth metallacyclopentadienes 1 a-c with 0.5 equivalents of P 4 affords a series of rare-earth metal cyclo-P 3 complexes 2 a-c and a phospholyl anion 3. 2 a-c demonstrate an unusual η 3 coordination mode with one P-P bond featuring partial π-bonding character. 2 a-c are the first cyclo-P 3 complexes of rare-earth metals, and also the first organo-substituted polyphosphides in the category of Group 3 and f-block elements. Rare-earth metallacyclopentadienes play a dual role in the combination of aromatization and Diels-Alder reaction. Compounds 2 a-c can coordinate to one or two [W(CO) 5 ] units, yielding 4 a-c or 5 c, respectively. Furthermore, oxidation of 2 a with p-benzoquinone produces its corresponding phospholyllithium and regenerated P 4 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An easy access to nanocrystalline alkaline earth metal fluorides - just by shaking

NASA Astrophysics Data System (ADS)

Dreger, M.; Scholz, G.; Kemnitz, E.

2012-04-01

High energy ball milling as fast, direct and solvent free method allows an easy access to nanocrystalline alkaline earth metal fluorides MF2 (M: Mg, Ca, Sr, Ba). Comparable metal sources (acetates, carbonates, hydroxides, alkoxides) were used for the reaction with NH4F as fluorinating agent. Even very simple manual shaking experiments between NH4F and the corresponding hydroxides in the stoichiometric ratio (M:F = 1:2, M: Ca, Sr, Ba) give phase pure fluorides. Moreover, comparable classical thermal reactions in closed crucibles at higher temperatures provide phase pure crystalline fluorides in nearly all cases as well.

Conducting tin halides with a layered organic-based perovskite structure

NASA Astrophysics Data System (ADS)

Mitzi, D. B.; Feild, C. A.; Harrison, W. T. A.; Guloy, A. M.

1994-06-01

THE discovery1 of high-temperature superconductivity in layered copper oxide perovskites has generated considerable fundamental and technological interest in this class of materials. Only a few other examples of conducting layered perovskites are known; these are also oxides such as (La1-xSrx)n+1 MnnO3n+1 (ref. 2), Lan+1NinO3n+1 (ref. 3) and Ban+1PbnO3n+1 (ref. 4), all of which exhibit a trend from semiconducting to metallic behaviour with increasing number of perovskite layers (n). We report here the synthesis of a family of organic-based layered halide perovskites, (C4H9NH3)2(CH3NH3)n-1Snnl3n+1 which show a similar transition from semiconducting to metallic behaviour with increasing n. The incorporation of an organic modulation layer between the conducting tin iodide sheets potentially provides greater flexibility for tuning the electrical properties of the perovskite sheets, and we suggest that such an approach will prove valuable for exploring the range of transport properties possible with layered perovskites.

Oxygen-induced defects at the lead halide perovskite/graphene oxide interfaces

DOE PAGES

Acik, Muge; Park, In Kee; Koritala, Rachel E.; ...

2017-12-21

Here, graphene oxide or its reduced derivative (GO/RGO) replace metal oxides in perovskite photovoltaics to achieve energy band alignment for minimization of the energy barriers at the film interfaces allowing efficient charge transport, and eliminate stability issues. However, the power conversion efficiencies fall in a wide range (~0.6–18%). Therefore, the perovskite growth and nucleation on GO/RGO require fundamental understanding to improve device function for controlled fabrication, which remain a major challenge. We analyze the surface morphology and crystallization of the lead halide perovskites (MAPbX 3) at 20–300 °C on GO using X-ray diffraction and photoelectron spectroscopy. To determine defect mechanismsmore » and their composition, we perform in situ transmission infrared and micro Raman spectroscopy, and the cross-sectional scanning microscopy that captures interfacial imperfections with the oxygen defects. We demonstrate the oxygen-induced defects at the MAPbX 3/GO interfaces that initiate at room temperature, and occur through the nucleophilic substitution reactions. Unexpectedly, structural defects nucleate in GO forming chemically reduced GO, and modify the surface morphology that yield a poor perovskite growth. Our theoretical studies also reveal that energetically favorable, exothermic reactions between the halides of the perovskite precursors and the oxygen groups of GO generate acidic reaction by-products ( i.e. HX), that confirm the formation of oxygen-induced defects.« less

Oxygen-induced defects at the lead halide perovskite/graphene oxide interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Acik, Muge; Park, In Kee; Koritala, Rachel E.

Here, graphene oxide or its reduced derivative (GO/RGO) replace metal oxides in perovskite photovoltaics to achieve energy band alignment for minimization of the energy barriers at the film interfaces allowing efficient charge transport, and eliminate stability issues. However, the power conversion efficiencies fall in a wide range (~0.6–18%). Therefore, the perovskite growth and nucleation on GO/RGO require fundamental understanding to improve device function for controlled fabrication, which remain a major challenge. We analyze the surface morphology and crystallization of the lead halide perovskites (MAPbX 3) at 20–300 °C on GO using X-ray diffraction and photoelectron spectroscopy. To determine defect mechanismsmore » and their composition, we perform in situ transmission infrared and micro Raman spectroscopy, and the cross-sectional scanning microscopy that captures interfacial imperfections with the oxygen defects. We demonstrate the oxygen-induced defects at the MAPbX 3/GO interfaces that initiate at room temperature, and occur through the nucleophilic substitution reactions. Unexpectedly, structural defects nucleate in GO forming chemically reduced GO, and modify the surface morphology that yield a poor perovskite growth. Our theoretical studies also reveal that energetically favorable, exothermic reactions between the halides of the perovskite precursors and the oxygen groups of GO generate acidic reaction by-products ( i.e. HX), that confirm the formation of oxygen-induced defects.« less

Observation of Quantum Confinement in Monodisperse Methylammonium Lead Halide Perovskite Nanocrystals Embedded in Mesoporous Silica.

PubMed

Malgras, Victor; Tominaka, Satoshi; Ryan, James W; Henzie, Joel; Takei, Toshiaki; Ohara, Koji; Yamauchi, Yusuke

2016-10-13

Hybrid organic-inorganic metal halide perovskites have fascinating electronic properties and have already been implemented in various devices. Although the behavior of bulk metal halide perovskites has been widely studied, the properties of perovskite nanocrystals are less well-understood because synthesizing them is still very challenging, in part because of stability. Here we demonstrate a simple and versatile method to grow monodisperse CH 3 NH 3 PbBr x I x-3 perovskite nanocrystals inside mesoporous silica templates. The size of the nanocrystal is governed by the pore size of the templates (3.3, 3.7, 4.2, 6.2, and 7.1 nm). In-depth structural analysis shows that the nanocrystals maintain the perovskite crystal structure, but it is slightly distorted. Quantum confinement was observed by tuning the size of the particles via the template. This approach provides an additional route to tune the optical bandgap of the nanocrystal. The level of quantum confinement was modeled taking into account the dimensions of the rod-shaped nanocrystals and their close packing inside the channels of the template. Photoluminescence measurements on CH 3 NH 3 PbBr clearly show a shift from green to blue as the pore size is decreased. Synthesizing perovskite nanostructures in templates improves their stability and enables tunable electronic properties via quantum confinement. These structures may be useful as reference materials for comparison with other perovskites, or as functional materials in all solid-state light-emitting diodes.

White-Light Emission from Layered Halide Perovskites.

PubMed

Smith, Matthew D; Karunadasa, Hemamala I

2018-03-20

With nearly 20% of global electricity consumed by lighting, more efficient illumination sources can enable massive energy savings. However, effectively creating the high-quality white light required for indoor illumination remains a challenge. To accurately represent color, the illumination source must provide photons with all the energies visible to our eye. Such a broad emission is difficult to achieve from a single material. In commercial white-light sources, one or more light-emitting diodes, coated by one or more phosphors, yield a combined emission that appears white. However, combining emitters leads to changes in the emission color over time due to the unequal degradation rates of the emitters and efficiency losses due to overlapping absorption and emission energies of the different components. A single material that emits broadband white light (a continuous emission spanning 400-700 nm) would obviate these problems. In 2014, we described broadband white-light emission upon near-UV excitation from three new layered perovskites. To date, nine white-light-emitting perovskites have been reported by us and others, making this a burgeoning field of study. This Account outlines our work on understanding how a bulk material, with no obvious emissive sites, can emit every color of the visible spectrum. Although the initial discoveries were fortuitous, our understanding of the emission mechanism and identification of structural parameters that correlate with the broad emission have now positioned us to design white-light emitters. Layered hybrid halide perovskites feature anionic layers of corner-sharing metal-halide octahedra partitioned by organic cations. The narrow, room-temperature photoluminescence of lead-halide perovskites has been studied for several decades, and attributed to the radiative recombination of free excitons (excited electron-hole pairs). We proposed that the broad white emission we observed primarily stems from exciton self-trapping. Here, the

Effects of pH on frog gustatory responses to chloride salts of alkali-metal and alkali-earth-metal.

PubMed

Kumai, T; Nomura, H

1980-01-01

The pH effects on frog gustatory responses to alkali-metal and alkali-earth-metal chloride salts were examined using single fungi-form papilla preparations. Responses to 0.1-0.5 M NaCl were clearly dependent upon the pH of the stimulating solutions. The responses increased as the pH decreased from 6.5 to 4.5 and were almost completely suppressed at pH's above 6.5. There was no significant difference in the pH dependency of the response among alkali-metal chlorides. HCl solutions elicited only a poor response under conditions in which the water response was suppressed by the simultaneous presence of a low NaCl concentration. Responses to alkali-earth-metal chlorides varied in their pH dependency. Response to CaCl2 was slightly affected by pH changes from 4.5 to 9.0, response to SrCl2 was considerably suppressed in the alkaline region, and responses to BaCl2 and MgCl2 were strongly suppressed at pH's above 6.5. BeCl2 solutions showed less marked stimulating effects over the pH range tested. The differences in pH dependency described above suggest the existence of two kinds of receptor sites, one being pH-insensitive sites responsible for the calcium response and the other pH-sensitive sites responsible for the sodium response. A cross-adaptation test appeared to support this possibility. Assuming that the pH effect mentioned is related to changes in the state of ionization of the receptor molecule, the pKa of the ionizable group responsible for the sodium response was determined to be approximately 5.5.

Cation Dynamics Governed Thermal Properties of Lead Halide Perovskite Nanowires.

PubMed

Wang, Yuxi; Lin, Renxing; Zhu, Pengchen; Zheng, Qinghui; Wang, Qianjin; Li, Deyu; Zhu, Jia

2018-05-09

Metal halide perovskite (MHP) nanowires such as hybrid organic-inorganic CH 3 NH 3 PbX 3 (X = Cl, Br, I) have drawn significant attention as promising building blocks for high-performance solar cells, light-emitting devices, and semiconductor lasers. However, the physics of thermal transport in MHP nanowires is still elusive even though it is highly relevant to the device thermal stability and optoelectronic performance. Through combined experimental measurements and theoretical analyses, here we disclose the underlying mechanisms governing thermal transport in three different kinds of lead halide perovskite nanowires (CH 3 NH 3 PbI 3 , CH 3 NH 3 PbBr 3 and CsPbBr 3 ). It is shown that the thermal conductivity of CH 3 NH 3 PbBr 3 nanowires is significantly suppressed as compared to that of CsPbBr 3 nanowires, which is attributed to the cation dynamic disorder. Furthermore, we observed different temperature-dependent thermal conductivities of hybrid perovskites CH 3 NH 3 PbBr 3 and CH 3 NH 3 PbI 3 , which can be attributed to accelerated cation dynamics in CH 3 NH 3 PbBr 3 at low temperature and the combined effects of lower phonon group velocity and higher Umklapp scattering rate in CH 3 NH 3 PbI 3 at high temperature. These data and understanding should shed light on the design of high-performance MHP based thermal and optoelectronic devices.

The Electronic Structure and Optical Properties of Anatase TiO2 with Rare Earth Metal Dopants from First-Principles Calculations

PubMed Central

Xie, Kefeng; Jia, Qiangqiang; Wang, Yizhe; Zhang, Wenxue; Xu, Jingcheng

2018-01-01

The electronic and optical properties of the rare earth metal atom-doped anatase TiO2 have been investigated systematically via density functional theory calculations. The results show that TiO2 doped by Ce or Pr is the optimal choice because of its small band gap and strong optical absorption. Rare earth metal atom doping induces several impurity states that tune the location of valence and conduction bands and an obvious lattice distortion that should reduce the probability of electron–hole recombination. This effect of band change originates from the 4f electrons of the rare earth metal atoms, which leads to an improved visible light absorption. This finding indicates that the electronic structure of anatase TiO2 is tuned by the introduction of impurity atoms. PMID:29364161

Exhaustive thin-layer cyclic voltammetry for absolute multianalyte halide detection.

PubMed

Cuartero, Maria; Crespo, Gastón A; Ghahraman Afshar, Majid; Bakker, Eric

2014-11-18

Water analysis is one of the greatest challenges in the field of environmental analysis. In particular, seawater analysis is often difficult because a large amount of NaCl may mask the determination of other ions, i.e., nutrients, halides, and carbonate species. We demonstrate here the use of thin-layer samples controlled by cyclic voltammetry to analyze water samples for chloride, bromide, and iodide. The fabrication of a microfluidic electrochemical cell based on a Ag/AgX wire (working electrode) inserted into a tubular Nafion membrane is described, which confines the sample solution layer to less than 15 μm. By increasing the applied potential, halide ions present in the thin-layer sample (X(-)) are electrodeposited on the working electrode as AgX, while their respective counterions are transported across the perm-selective membrane to an outer solution. Thin-layer cyclic voltammetry allows us to obtain separated peaks in mixed samples of these three halides, finding a linear relationship between the halide concentration and the corresponding peak area from about 10(-5) to 0.1 M for bromide and iodide and from 10(-4) to 0.6 M for chloride. This technique was successfully applied for the halide analysis in tap, mineral, and river water as well as seawater. The proposed methodology is absolute and potentially calibration-free, as evidenced by an observed 2.5% RSD cell to cell reproducibility and independence from the operating temperature.

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.

Formation of an integrated holding company to produce rare-earth metal articles

NASA Astrophysics Data System (ADS)

Bogdanov, S. V.; Grishaev, S. I.

2013-12-01

The possibility of formation of a Russian holding company for the production of rare-earth metal articles under conditions of its increasing demand on the world market is considered. It is reasonable to ensure stable business operation on the market under conditions of state-private partnership after the fraction of soled products is determined and supported by the competitive advantages of Russian products.

New silver-halide-sensitized gelatin material: the influence of bleaches on holograms

NASA Astrophysics Data System (ADS)

Zhang, Weiping; Pang, Lin; Guo, Lurong

1996-12-01

A new high-resolution-silver-halide (HRSH-II) material was produced, which has proper initial hardness for fabricating silver halide sensitized gelatin (SHSG) holograms. That would avoid high noise by seeking the gelatin in hot water. With different alkali halide component in B solution and its concentration (the ratio B/A), experiments were presented about bleaching effect with R-10 on processing for SHSG derived from this new material. High diffraction efficiency, as high as 81%, was achieved. Some of the observations are discussed.

Highly efficient hydrophosphonylation of aldehydes and unactivated ketones catalyzed by methylene-linked pyrrolyl rare earth metal amido complexes.

PubMed

Zhou, Shuangliu; Wu, Zhangshuan; Rong, Jiewei; Wang, Shaowu; Yang, Gaosheng; Zhu, Xiancui; Zhang, Lijun

2012-02-27

A series of rare earth metal amido complexes bearing methylene-linked pyrrolyl-amido ligands were prepared through silylamine elimination reactions and displayed high catalytic activities in hydrophosphonylations of aldehydes and unactivated ketones under solvent-free conditions for liquid substrates. Treatment of [(Me(3)Si)(2)N](3)Ln(μ-Cl)Li(THF)(3) with 2-(2,6-Me(2)C(6)H(3)NHCH(2))C(4)H(3)NH (1, 1 equiv) in toluene afforded the corresponding trivalent rare earth metal amides of formula {(μ-η(5):η(1)):η(1)-2-[(2,6-Me(2)C(6)H(3))NCH(2)](C(4)H(3)N)LnN(SiMe(3))(2)}(2) [Ln=Y (2), Nd (3), Sm (4), Dy (5), Yb (6)] in moderate to good yields. All compounds were fully characterized by spectroscopic methods and elemental analyses. The yttrium complex was also characterized by (1)H NMR spectroscopic analyses. The structures of complexes 2, 3, 4, and 6 were determined by single-crystal X-ray analyses. Study of the catalytic activities of the complexes showed that these rare earth metal amido complexes were excellent catalysts for hydrophosphonylations of aldehydes and unactivated ketones. The catalyzed reactions between diethyl phosphite and aldehydes in the presence of the rare earth metal amido complexes (0.1 mol%) afforded the products in high yields (up to 99%) at room temperature in short times of 5 to 10 min. Furthermore, the catalytic addition of diethyl phosphite to unactivated ketones also afforded the products in high yields of up to 99% with employment of low loadings (0.1 to 0.5 mol%) of the rare earth metal amido complexes at room temperature in short times of 20 min. The system works well for a wide range of unactivated aliphatic, aromatic or heteroaromatic ketones, especially for substituted benzophenones, giving the corresponding α-hydroxy diaryl phosphonates in moderate to high yields. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Production method for making rare earth compounds

DOEpatents

McCallum, R.W.; Ellis, T.W.; Dennis, K.W.; Hofer, R.J.; Branagan, D.J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g., a transition metal and optional boron), and a carbide-forming element (e.g., a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g., Nd{sub 2}Fe{sub 14}B or LaNi{sub 5}) and a carbide of the carbide-forming element are formed.

Production method for making rare earth compounds

DOEpatents

McCallum, R. William; Ellis, Timothy W.; Dennis, Kevin W.; Hofer, Robert J.; Branagan, Daniel J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g. a transition metal and optional boron), and a carbide-forming element (e.g. a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g. Nd.sub.2 Fe.sub.14 B or LaNi.sub.5) and a carbide of the carbide-forming element are formed.

PURIFICATION OF URANIUM FUELS

DOEpatents

Niedrach, L.W.; Glamm, A.C.

1959-09-01

An electrolytic process of refining or decontaminating uranium is presented. The impure uranium is made the anode of an electrolytic cell. The molten salt electrolyte of this cell comprises a uranium halide such as UF/sub 4/ or UCl/sub 3/ and an alkaline earth metal halide such as CaCl/sub 2/, BaF/sub 2/, or BaCl/sub 2/. The cathode of the cell is a metal such as Mn, Cr, Co, Fe, or Ni which forms a low melting eutectic with U. The cell is operated at a temperature below the melting point of U. In operation the electrodeposited uranium becomes alloyed with the metal of the cathode, and the low melting alloy thus formed drips from the cathode.

FUSED SALT METHOD FOR COATING URANIUM WITH A METAL

DOEpatents

Eubank, L.D.

1959-02-01

A method is presented for coating uranium with a less active metal such as Cr, Ni, or Cu comprising immersing the U in a substantially anhydrous molten solution of a halide of these less active metals in a ternary chloride composition which consists of selected percentages of KCl, NaCl and another chloride such as LiCl or CaCl/sub 2/.

Synthesis, structure and properties of bimetallic sodium rare-earth (RE) borohydrides, NaRE(BH4)4, RE = Ce, Pr, Er or Gd.

PubMed

Payandeh GharibDoust, SeyedHosein; Ravnsbæk, Dorthe B; Černý, Radovan; Jensen, Torben R

2017-10-10

Formation, stability and properties of new metal borohydrides within RE(BH 4 ) 3 -NaBH 4 , RE = Ce, Pr, Er or Gd is investigated. Three new bimetallic sodium rare-earth borohydrides, NaCe(BH 4 ) 4 , NaPr(BH 4 ) 4 and NaEr(BH 4 ) 4 are formed based on an addition reaction between NaBH 4 and halide free rare-earth metal borohydrides RE(BH 4 ) 3 , RE = Ce, Pr, Er. All the new compounds crystallize in the orthorhombic crystal system. NaCe(BH 4 ) 4 has unit cell parameters of a = 6.8028(5), b = 17.5181(13), c = 7.2841(5) Å and space group Pbcn. NaPr(BH 4 ) 4 is isostructural to NaCe(BH 4 ) 4 with unit cell parameters of a = 6.7617(2), b = 17.4678(7), c = 7.2522(3) Å. NaEr(BH 4 ) 4 crystallizes in space group Cmcm with unit cell parameters of a = 8.5379(2), b = 12.1570(4), c = 9.1652(3) Å. The structural relationships, also to the known RE(BH 4 ) 3 , are discussed in detail and related to the stability and synthesis conditions. Heat treatment of NaBH 4 -Gd(BH 4 ) 3 mixture forms an unstable amorphous phase, which decomposes after one day at RT. NaCe(BH 4 ) 4 and NaPr(BH 4 ) 4 show reversible hydrogen storage capacity of 1.65 and 1.04 wt% in the fourth H 2 release, whereas that of NaEr(BH 4 ) 4 continuously decreases. This is mainly assigned to formation of metal hydrides and possibly slower formation of sodium borohydride. The dehydrogenated state clearly contains rare-earth metal borides, which stabilize boron in the dehydrogenated state.

Metal-silicate Partitioning and Its Role in Core Formation and Composition on Super-Earths

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaefer, Laura; Petaev, M. I.; Sasselov, Dimitar D.

We use a thermodynamic framework for silicate-metal partitioning to determine the possible compositions of metallic cores on super-Earths. We compare results using literature values of the partition coefficients of Si and Ni, as well as new partition coefficients calculated using results from laser shock-induced melting of powdered metal-dunite targets at pressures up to 276 GPa, which approaches those found within the deep mantles of super-Earths. We find that larger planets may have little to no light elements in their cores because the Si partition coefficient decreases at high pressures. The planet mass at which this occurs will depend on themore » metal-silicate equilibration depth. We also extrapolate the equations of state (EOS) of FeO and FeSi alloys to high pressures, and present mass–radius diagrams using self-consistent planet compositions assuming equilibrated mantles and cores. We confirm the results of previous studies that the distribution of elements between mantle and core will not be detectable from mass and radius measurements alone. While observations may be insensitive to interior structure, further modeling is sensitive to compositionally dependent properties, such as mantle viscosity and core freeze-out properties. We therefore emphasize the need for additional high pressure measurements of partitioning as well as EOSs, and highlight the utility of the Sandia Z-facilities for this type of work.« less

Post-synthetic halide conversion and selective halogen capture in hybrid perovskites† †Electronic supplementary information (ESI) available. CCDC 1048945–1048947. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01135c

PubMed Central

Solis-Ibarra, D.; Smith, I. C.

2015-01-01

Reaction with halogen vapor allows us to post-synthetically exchange halides in both three- (3D) and two-dimensional (2D) organic–inorganic metal-halide perovskites. Films of 3D Pb–I perovskites cleanly convert to films of Pb–Br or Pb–Cl perovskites upon exposure to Br2 or Cl2 gas, respectively. This gas–solid reaction provides a simple method to produce the high-quality Pb–Br or Pb–Cl perovskite films required for optoelectronic applications. Reactivity with halogens can be extended to the organic layers in 2D metal-halide perovskites. Here, terminal alkene groups placed between the inorganic layers can capture Br2 gas through chemisorption to form dibromoalkanes. This reaction's selectivity for Br2 over I2 allows us to scrub Br2 to obtain high-purity I2 gas streams. We also observe unusual halogen transfer between the inorganic and organic layers within a single perovskite structure. Remarkably, the perovskite's crystallinity is retained during these massive structural rearrangements. PMID:29218171

Rationalizing the light-induced phase separation of mixed halide organic-inorganic perovskites.

PubMed

Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon; Brennan, Michael C; Morozov, Yurii V; Manser, Joseph S; Kamat, Prashant V; Schneider, William F; Kuno, Masaru

2017-08-04

Mixed halide hybrid perovskites, CH 3 NH 3 Pb(I 1-x Br x ) 3 , represent good candidates for low-cost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material's optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodide-rich phases. It additionally explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.Mixed halide hybrid perovskites possess tunable band gaps, however, under illumination they undergo phase separation. Using spectroscopic measurements and theoretical modelling, Draguta and Sharia et al. quantitatively rationalize the microscopic processes that occur during phase separation.

Effect of Halide Composition on the Photochemical Stability of Perovskite Photovoltaic Materials.

PubMed

Misra, Ravi K; Ciammaruchi, Laura; Aharon, Sigalit; Mogilyansky, Dmitry; Etgar, Lioz; Visoly-Fisher, Iris; Katz, Eugene A

2016-09-22

The photochemical stability of encapsulated films of mixed halide perovskites with a range of MAPb(I 1-x Br x ) 3 (MA=methylammonium) compositions (solid solutions) was investigated under accelerated stressing using concentrated sunlight. The relevance of accelerated testing to standard operational conditions of solar cells was confirmed by comparison to degradation experiments under outdoor sunlight exposure. We found that MAPbBr 3 films exhibited no degradation, while MAPbI 3 and mixed halide MAPb(I 1-x Br x ) 3 films decomposed yielding crystallization of inorganic PbI 2 accompanied by degradation of the perovskite solar light absorption, with faster absorption degradation in mixed halide films. The crystal coherence length was found to correlate with the stability of the films. We postulate that the introduction of Br into the mixed halide solid solution stressed its structure and induced more structural defects and/or grain boundaries compared to pure halide perovskites, which might be responsible for the accelerated degradation. Hence, the cause for accelerated degradation may be the increased defect density rather than the chemical composition of the perovskite materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Promoting effect of alkaline earth metal doping on catalytic activity of HC and NOx conversion over Pd-only three-way catalyst.

PubMed

Yang, Linyan; Lin, Siyu; Yang, Xue; Fang, Weimin; Zhou, Renxian

2014-08-30

The influence of alkaline earth metal (M=Mg, Ca, Sr and Ba) promoter on the structural/textural properties of Ce0.67Zr0.33O2 (designated as CZ) and the catalytic behavior of its supported Pd-only three-way catalyst (Pd/CZM) have been investigated. The results show that the modification with alkaline earth metal obviously improves the catalytic activity for hydrocarbon (HC) and nitrogen oxides (NOx) conversion, especially the introduction of Ba. Furthermore, the operation window of the promoted catalysts has also been widened. The doping of alkaline earth metal leads to the formation of more homogeneous Ce-Zr-M ternary solid solution with higher surface area and smaller crystallite size, and the corresponding Pd/CZM catalysts present improved reducibility of PdO species. The modification with Ca, Sr and Ba improves the thermal aging resistance, especially Ba. DRIFTS results reveal that the doping of alkaline earth metal enhances the oxygen and electron transfer ability and favors the dissociation of NO, which promotes the activation and storage capacity of the acidic atoms like NOx, and leads to enhanced catalytic activity performance. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

DOE PAGES

Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; ...

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

Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou

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

Lanthanide doped strontium-barium cesium halide scintillators

DOEpatents

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.

Halide removal from aqueous solution by novel silver-polymeric materials.

PubMed

A M S, Polo; I, Velo-Gala; M, Sánchez-Polo; U, von Gunten; J J, López-Peñalver; J, Rivera-Utrilla

2016-12-15

The objective of this study was to analyze the behavior of a new material, silver-doped polymeric cloth (Ag-cloth), in the removal of bromide and iodide from waters. Silver is immobilized on the cloth, guaranteeing selective adsorption of the halide ions as retained silver halides that therefore do not pass into the solution. Results indicate that Ag 0 reacts with H 2 O 2 in the first phases of the process, yielding Ag + and superoxide radical; however, as the process advances, this radical favors Ag + reduction. Increases in the concentration of H 2 O 2 augment the capacity of the Ag-cloth to remove halides from the medium up to a maximum concentration (55μM), above which the removal capacity remains constant (Xm≅1.3-1.8mg halide/g Ag-cloth). Thus, when there is excess H 2 O 2 in the medium, secondary competitive reactions that take place in the process guarantee a constant Ag + concentration, which defines the maximum adsorption capacity of Ag-cloth, reducing its ability to remove halides. Ag-cloth has a higher capacity to remove iodide than bromide, and the presence of organic matter or chloride reduces its capacity to remove iodide or bromide from water. The results obtained shown that the capacity of Ag 0 with H 2 O 2 significantly varies as a function of the medium pH from 1mg Br - /g Ag-cloth at very low pH to 1.6mg/g Ag-cloth at pH9. Copyright © 2016 Elsevier B.V. All rights reserved.

Enrichment of rare earth metal ions by the highly selective adsorption of phytate intercalated layered double hydroxide.

PubMed

Jin, Cheng; Liu, Huimin; Kong, Xianggui; Yan, Hong; Lei, Xiaodong

2018-02-27

Phytate intercalated MgAl layered double hydroxide (MgAl-LDH) was prepared by an anion exchange method with the precursor NO 3 - containing MgAl-LDH. The final as-synthesized product [Mg 0.69 Al 0.31 (OH) 2 ] (phytateNa 6 ) 0.05 (NO 3 ) 0.01 ·mH 2 O (phytate-LDH) has highly selective adsorption ability for some metal ions and can be used to enrich rare earth metal ions in mixed solution, such as Pr 3+ and Ce 3+ from a mixed solution of them with Pb 2+ and Co 2+ . At first, phytate-LDH has good adsorption performance for these ions in single metal ion solutions. At low concentration (below 10 mg L -1 ), all the capture rates of the four metal ions were more than 97%, for highly toxic Pb 2+ it was even up to nearly 100%, and a high capture rate (99.87%) was maintained for Pb 2+ at a high concentration (100 mg L -1 ). When all the four metal ions are co-existing in aqueous solution, the selectivity order is Pb 2+ ≫ Pr 3+ ≈ Ce 3+ > Co 2+ . In a solution containing mixtures of the three metal ions of Pr 3+ , Ce 3+ , and Co 2+ , the selectivity order is Pr 3+ ≈ Ce 3+ ≫ Co 2+ , and in a solution containing mixtures of Pr 3+ with Co 2+ and Ce 3+ with Co 2+ , the selectivity orders are Pr 3+ ≫ Co 2+ and Ce 3+ ≫ Co 2+ , respectively. The high selectivity and adsorption capacities for Pb 2+ , Co 2+ , Pr 3+ , and Ce 3+ result in the efficient removal of Pb 2+ and enrichment of the rare earth metal ions Pr 3+ and Ce 3+ by phytate-LDH. Based on the elemental analysis, it is found that the difference of the adsorption capacities is mainly due to the different coordination number of them with phytate-LDH. With molecular simulation, we believe that the adsorption selectivity is due to the difference of the binding energy between the metal ion and phytate-LDH. Therefore, the phytate-LDH is promising for the enrichment and/or purification of the rare earth metal ions and removal of toxic metal ions from waste water.

Rare earth element and rare metal inventory of central Asia

USGS Publications Warehouse

Mihalasky, Mark J.; Tucker, Robert D.; Renaud, Karine; Verstraeten, Ingrid M.

2018-03-06

Rare earth elements (REE), with their unique physical and chemical properties, are an essential part of modern living. REE have enabled development and manufacture of high-performance materials, processes, and electronic technologies commonly used today in computing and communications, clean energy and transportation, medical treatment and health care, glass and ceramics, aerospace and defense, and metallurgy and chemical refining. Central Asia is an emerging REE and rare metals (RM) producing region. A newly compiled inventory of REE-RM-bearing mineral occurrences and delineation of areas-of-interest indicate this region may have considerable undiscovered resources.

Real-Time Observation of Iodide Ion Migration in Methylammonium Lead Halide Perovskites.

PubMed

Li, Cheng; Guerrero, Antonio; Zhong, Yu; Gräser, Anna; Luna, Carlos Andres Melo; Köhler, Jürgen; Bisquert, Juan; Hildner, Richard; Huettner, Sven

2017-11-01

Organic-inorganic metal halide perovskites (e.g., CH 3 NH 3 PbI 3- x Cl x ) emerge as a promising optoelectronic material. However, the Shockley-Queisser limit for the power conversion efficiency (PCE) of perovskite-based photovoltaic devices is still not reached. Nonradiative recombination pathways may play a significant role and appear as photoluminescence (PL) inactive (or dark) areas on perovskite films. Although these observations are related to the presence of ions/defects, the underlying fundamental physics and detailed microscopic processes, concerning trap/defect status, ion migration, etc., still remain poorly understood. Here correlated wide-field PL microscopy and impedance spectroscopy are utilized on perovskite films to in situ investigate both the spatial and the temporal evolution of these PL inactive areas under external electric fields. The formation of PL inactive domains is attributed to the migration and accumulation of iodide ions under external fields. Hence, we are able to characterize the kinetic processes and determine the drift velocities of these ions. In addition, it is shown that I 2 vapor directly affects the PL quenching of a perovskite film, which provides evidence that the migration/segregation of iodide ions plays an important role in the PL quenching and consequently limits the PCE of organometal halide-based perovskite photovoltaic devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Silyl Radical Activation of Alkyl Halides in Metallaphotoredox Catalysis: A Unique Pathway for Cross-Electrophile Coupling.

PubMed

Zhang, Patricia; Le, Chi Chip; MacMillan, David W C

2016-07-06

A strategy for cross-electrophile coupling has been developed via the merger of photoredox and transition metal catalysis. In this report, we demonstrate the use of commercially available tris(trimethylsilyl)silane with metallaphotoredox catalysis to efficiently couple alkyl bromides with aryl or heteroaryl bromides in excellent yields. We hypothesize that a photocatalytically generated silyl radical species can perform halogen-atom abstraction to activate alkyl halides as nucleophilic cross-coupling partners. This protocol allows the use of mild yet robust conditions to construct Csp(3)-Csp(2) bonds generically via a unique cross-coupling pathway.

Bond-length distributions for ions bonded to oxygen: alkali and alkaline-earth metals.

PubMed

Gagné, Olivier Charles; Hawthorne, Frank Christopher

2016-08-01

Bond-length distributions have been examined for 55 configurations of alkali-metal ions and 29 configurations of alkaline-earth-metal ions bonded to oxygen, for 4859 coordination polyhedra and 38 594 bond distances (alkali metals), and for 3038 coordination polyhedra and 24 487 bond distances (alkaline-earth metals). Bond lengths generally show a positively skewed Gaussian distribution that originates from the variation in Born repulsion and Coulomb attraction as a function of interatomic distance. The skewness and kurtosis of these distributions generally decrease with increasing coordination number of the central cation, a result of decreasing Born repulsion with increasing coordination number. We confirm the following minimum coordination numbers: ([3])Li(+), ([3])Na(+), ([4])K(+), ([4])Rb(+), ([6])Cs(+), ([3])Be(2+), ([4])Mg(2+), ([6])Ca(2+), ([6])Sr(2+) and ([6])Ba(2+), but note that some reported examples are the result of extensive dynamic and/or positional short-range disorder and are not ordered arrangements. Some distributions of bond lengths are distinctly multi-modal. This is commonly due to the occurrence of large numbers of structure refinements of a particular structure type in which a particular cation is always present, leading to an over-representation of a specific range of bond lengths. Outliers in the distributions of mean bond lengths are often associated with anomalous values of atomic displacement of the constituent cations and/or anions. For a sample of ([6])Na(+), the ratio Ueq(Na)/Ueq(bonded anions) is partially correlated with 〈([6])Na(+)-O(2-)〉 (R(2) = 0.57), suggesting that the mean bond length is correlated with vibrational/displacement characteristics of the constituent ions for a fixed coordination number. Mean bond lengths also show a weak correlation with bond-length distortion from the mean value in general, although some coordination numbers show the widest variation in mean bond length for zero distortion, e.g. Li(+) in

Fluorescent Properties of Manganese Halide Benzothiazole Inorganic-Organic Hybrids.

PubMed

Yu, Hui; Mei, YingXuan; Wei, ZhenHong; Mei, GuangQuan; Cai, Hu

2016-11-01

The reaction of manganese (II) halides MnX 2 and benzothiazole (btz) in the concentrated acids HX (X = Cl, Br) at 80 °C resulted in the formation of two inorganic-organic hybrid complexes: [(btz) 2 (MnX 4 )]·2H 2 O (X = Cl, 1; X = Br, 2). Both compounds showed green luminescence and exhibited moderate quantum yields of 43.17 % for 1 and 26.18 % for 2, which were directly originated from the tetrahedral coordination of Mn 2+ ion. Two organic - inorganic hybrids [(btz) 2 (MnX 4 )]·2H 2 O based on MnCl 2 , benzothiazole and halide acids emitted green light with the moderate quantum efficiencies when excited by 365 nm light. Graphical abstract Two organic-inorganic hybrids [(btz) 2 (MnX 4 )]·2H 2 O based on MnCl 2 , benzothiazole and halide acids emitted green light with the moderate quantum efficiencies when excited by 365 nm light.

Metallaphotoredox-Catalyzed sp3–sp3 Cross-Coupling of Carboxylic Acids with Alkyl Halides

PubMed Central

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

2017-01-01

Over the last half-century, transition metal-mediated cross-coupling reactions have changed the way in which complex organic molecules are synthesized. Indeed, the predictable and chemoselective nature of these transformations has led to their widespread adoption across a vast array of chemical research areas1. However, the construction of sp3–sp3 bonds, a fundamental unit of organic chemistry, remains an important yet elusive objective for cross-coupling reaction engineering2. In comparison to related procedures with sp2-hybridized species, the development of methods for sp3–sp3 bond formation via transition metal catalysis has been historically hampered by deleterious side-reactions, such as β-hydride elimination with Pd-catalysis, and the reluctance of alkyl halides to undergo oxidative addition3,4. To address this issue, a number of research groups have demonstrated the feasibility of nickel-catalyzed cross-coupling processes to form sp3–sp3 bonds that utilize organometallic nucleophiles and alkyl electrophiles5–7. In particular, the coupling of alkyl halides with pregenerated organozinc8–10, Grignard11,12, and organoborane13 species has been used to furnish diverse molecular structures. However, the poor step and atom economies along with the operational difficulties associated with making, carrying, and using these sensitive coupling partners has hindered their widespread adoption. The prospect of establishing a generically useful sp3–sp3 coupling technology that employs bench-stable, native organic functional groups, without the need for pre-functionalization or substrate derivatization, would therefore be a valuable addition to fields of research that rely on organic molecule construction. Here, we demonstrate that the synergistic merger of photoredox and nickel catalysis enables the direct formation of sp3–sp3 bonds using only simple carboxylic acids and alkyl halides as the nucleophilic and electrophilic coupling partners, respectively. The

Improved catalytic properties of halohydrin dehalogenase by modification of the halide-binding site.

PubMed

Tang, Lixia; Torres Pazmiño, Daniel E; Fraaije, Marco W; de Jong, René M; Dijkstra, Bauke W; Janssen, Dick B

2005-05-03

Halohydrin dehalogenase (HheC) from Agrobacterium radiobacter AD1 catalyzes the dehalogenation of vicinal haloalcohols by an intramolecular substitution reaction, resulting in the formation of the corresponding epoxide, a halide ion, and a proton. Halide release is rate-limiting during the catalytic cycle of the conversion of (R)-p-nitro-2-bromo-1-phenylethanol by the enzyme. The recent elucidation of the X-ray structure of HheC showed that hydrogen bonds between the OH group of Tyr187 and between the Odelta1 atom of Asn176 and Nepsilon1 atom of Trp249 could play a role in stabilizing the conformation of the halide-binding site. The possibility that these hydrogen bonds are important for halide binding and release was studied using site-directed mutagenesis. Steady-state kinetic studies revealed that mutant Y187F, which has lost both hydrogen bonds, has a higher catalytic activity (k(cat)) with two of the three tested substrates compared to the wild-type enzyme. Mutant W249F also shows an enhanced k(cat) value with these two substrates, as well as a remarkable increase in enantiopreference for (R)-p-nitro-2-bromo-1-phenylethanol. In case of a mutation at position 176 (N176A and N176D), a 1000-fold lower catalytic efficiency (k(cat)/K(m)) was obtained, which is mainly due to an increase of the K(m) value of the enzyme. Pre-steady-state kinetic studies showed that a burst of product formation precedes the steady state, indicating that halide release is still rate-limiting for mutants Y187F and W249F. Stopped-flow fluorescence experiments revealed that the rate of halide release is 5.6-fold higher for the Y187F mutant than for the wild-type enzyme and even higher for the W249F enzyme. Taken together, these results show that the disruption of two hydrogen bonds around the halide-binding site increases the rate of halide release and can enhance the overall catalytic activity of HheC.

Hydrometallurgical separation of rare earth elements, cobalt and nickel from spent nickel-metal-hydride batteries

NASA Astrophysics Data System (ADS)

Rodrigues, Luiz Eduardo Oliveira Carmo; Mansur, Marcelo Borges

The separation of rare earth elements, cobalt and nickel from NiMH battery residues is evaluated in this paper. Analysis of the internal content of the NiMH batteries shows that nickel is the main metal present in the residue (around 50% in weight), as well as potassium (2.2-10.9%), cobalt (5.1-5.5%), rare earth elements (15.3-29.0%) and cadmium (2.8%). The presence of cadmium reveals that some Ni-Cd batteries are possibly labeled as NiMH ones. The leaching of nickel and cobalt from the NiMH battery powder with sulfuric acid is efficient; operating variables temperature and concentration of H 2O 2 has no significant effect for the conditions studied. A mixture of rare earth elements is separated by precipitation with NaOH. Finally, solvent extraction with D2EHPA (di-2-ethylhexyl phosphoric acid) followed by Cyanex 272 (bis-2,4,4-trimethylpentyl phosphinic acid) can separate cadmium, cobalt and nickel from the leach liquor. The effect of the main operating variables of both leaching and solvent extraction steps are discussed aiming to maximize metal separation for recycling purposes.

Heterogeneous Delivery of Silicate and Metal to the Earth via Large Planetesimals

NASA Astrophysics Data System (ADS)

Marchi, S.; Canup, R. M.; Walker, R. J.

2017-12-01

Earth's mantle abundances of at least some highly siderophile elements, (HSE; Re, Os, Ir, Ru, Pt, Rh, Pd, and Au), are much higher than would result from metal-silicate equilibration during terrestrial core formation, and can be better explained as a result of late accretion of a minimum of 0.5% Earth's masses after core formation was complete. Traditional models assume that HSEs delivered by late projectiles completely mixed and chemically equilibrated with the Earth's mantle. This appears likely for undifferentiated, well-mixed projectiles, or for relatively small, differentiated projectiles. However several arguments suggest that late projectiles may have been large (> 1500 km in diameter) and differentiated, and in this case, portions of the projectile's core may merge with the Earth's core, rather than being mixed into the Earth's mantle. We investigate projectile mixing with a suite of SPH simulations of differentiated planetesimal colliding with the Earth. A range of outcomes emerge from our simulations suggesting that for large impactors (>1500 km), the delivery of HSE to the Earth's mantle may be disproportionate with the overall delivery of mass. For impacts with impact angles < 45° , between ˜ 20% to 80% of the impactor's core may merge directly with the Earth's core; while for impact angle > 60°, most of the impactor core escapes for moderate impact speeds. An implication is that the late accreted mass inferred from terrestrial HSE abundances may be a substantial underestimate, by a factor 2-5. In addition, partial mixing of projectiles result in an enrichment in mantle vs core material delivered to the bulk silicate Earth, implying substantial compositional variations in the accreted mass. Such variations could produce initially localized domains in Earth's mantle with distinct, mass independent isotopic signatures, given the isotopic variability resulting from nucleosynthetic heterogeneities among genetically diverse meteorites. In general we find

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.

Persistent dopants and phase segregation in organolead mixed-halide perovskites

DOE PAGES

Rosales, Bryan A.; Men, Long; Cady, Sarah D.; ...

2016-07-25

Organolead mixed-halide perovskites such as CH 3NH 3PbX 3–aX' a (X, X' = I, Br, Cl) are interesting semiconductors because of their low cost, high photovoltaic power conversion efficiencies, enhanced moisture stability, and band gap tunability. Using a combination of optical absorption spectroscopy, powder X-ray diffraction (XRD), and, for the first time, 207Pb solid state nuclear magnetic resonance (ssNMR), we probe the extent of alloying and phase segregation in these materials. Because 207Pb ssNMR chemical shifts are highly sensitive to local coordination and electronic structure, and vary linearly with halogen electronegativity and band gap, this technique can provide the truemore » chemical speciation and composition of organolead mixed-halide perovskites. We specifically investigate samples made by three different preparative methods: solution phase synthesis, thermal annealing, and solid phase synthesis. 207Pb ssNMR reveals that nonstoichiometric dopants and semicrystalline phases are prevalent in samples made by solution phase synthesis. We show that these nanodomains are persistent after thermal annealing up to 200 °C. Further, a novel solid phase synthesis that starts from the parent, single-halide perovskites can suppress phase segregation but not the formation of dopants. Our observations are consistent with the presence of miscibility gaps and spontaneous spinodal decomposition of the mixed-halide perovskites at room temperature. This underscores how strongly different synthetic procedures impact the nanostructuring and composition of organolead halide perovskites. In conclusion, better optoelectronic properties and improved device stability and performance may be achieved through careful manipulation of the different phases and nanodomains present in these materials.« less

Persistent dopants and phase segregation in organolead mixed-halide perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rosales, Bryan A.; Men, Long; Cady, Sarah D.

Organolead mixed-halide perovskites such as CH 3NH 3PbX 3–aX' a (X, X' = I, Br, Cl) are interesting semiconductors because of their low cost, high photovoltaic power conversion efficiencies, enhanced moisture stability, and band gap tunability. Using a combination of optical absorption spectroscopy, powder X-ray diffraction (XRD), and, for the first time, 207Pb solid state nuclear magnetic resonance (ssNMR), we probe the extent of alloying and phase segregation in these materials. Because 207Pb ssNMR chemical shifts are highly sensitive to local coordination and electronic structure, and vary linearly with halogen electronegativity and band gap, this technique can provide the truemore » chemical speciation and composition of organolead mixed-halide perovskites. We specifically investigate samples made by three different preparative methods: solution phase synthesis, thermal annealing, and solid phase synthesis. 207Pb ssNMR reveals that nonstoichiometric dopants and semicrystalline phases are prevalent in samples made by solution phase synthesis. We show that these nanodomains are persistent after thermal annealing up to 200 °C. Further, a novel solid phase synthesis that starts from the parent, single-halide perovskites can suppress phase segregation but not the formation of dopants. Our observations are consistent with the presence of miscibility gaps and spontaneous spinodal decomposition of the mixed-halide perovskites at room temperature. This underscores how strongly different synthetic procedures impact the nanostructuring and composition of organolead halide perovskites. In conclusion, better optoelectronic properties and improved device stability and performance may be achieved through careful manipulation of the different phases and nanodomains present in these materials.« less

Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon

Mixed halide hybrid perovskites, CH 3NH 3Pb(I 1-xBrx) 3' represent good candidates for lowcost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material’s optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodiderich phases. It additionallymore » explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.« less

Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites

DOE PAGES

Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon; ...

2017-08-04

Mixed halide hybrid perovskites, CH 3NH 3Pb(I 1-xBrx) 3' represent good candidates for lowcost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material’s optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodiderich phases. It additionallymore » explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.« less

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.

Method for uniformly distributing carbon flakes in a positive electrode, the electrode made thereby and compositions

DOEpatents

Mrazek, Franklin C.; Smaga, John A.; Battles, James E.

1983-01-01

A positive electrode for a secondary electrochemical cell wherein an electrically conductive current collector is in electrical contact with a particulate mixture of gray cast iron and an alkali metal sulfide and an electrolyte including alkali metal halides or alkaline earth metal halides. Also present may be a transition metal sulfide and graphite flakes from the conversion of gray cast iron to iron sulfide. Also disclosed is a method of distributing carbon flakes in a cell wherein there is formed an electrochemical cell of a positive electrode structure of the type described and a suitable electrolyte and a second electrode containing a material capable of alloying with alkali metal ions. The cell is connected to a source of electrical potential to electrochemically convert gray cast iron to an iron sulfide and uniformly to distribute carbon flakes formerly in the gray cast iron throughout the positive electrode while forming an alkali metal alloy in the negative electrode. Also disclosed are compositions useful in preparing positive electrodes.

Method for uniformly distributing carbon flakes in a positive electrode, the electrode made thereby and compositions. [Patent application

DOEpatents

Mrazek, F.C.; Smaga, J.A.; Battles, J.E.

1981-01-19

A positive electrode for a secondary electrochemical cell is described wherein an electrically conductive current collector is in electrical contact with a particulate mixture of gray cast iron and an alkali metal sulfide and an electrolyte including alkali metal halides or alkaline earth metal halides. Also present may be a transition metal sulfide and graphite flakes from the conversion of gray cast iron to iron sulfide. Also disclosed is a method of distributing carbon flakes in a cell wherein there is formed an electrochemical cell of a positive electrode structure of the type described and a suitable electrolyte and a second electrode containing a material capable of alloying with alkali metal ions. The cell is connected to a source of electrical potential to electrochemically convert gray cast iron to an iron sulfide and uniformly to distribute carbon flakes formerly in the gray cast iron throughout the positive electrode while forming an alkali metal alloy in the negative electrode. Also disclosed are compositions useful in preparing positive electrodes.

Lithium-aluminum-iron electrode composition

DOEpatents

Kaun, Thomas D.

1979-01-01

A negative electrode composition is presented for use in a secondary electrochemical cell. The cell also includes an electrolyte with lithium ions such as a molten salt of alkali metal halides or alkaline earth metal halides that can be used in high-temperature cells. The cell's positive electrode contains a a chalcogen or a metal chalcogenide as the active electrode material. The negative electrode composition includes up to 50 atom percent lithium as the active electrode constituent in an alloy of aluminum-iron. Various binary and ternary intermetallic phases of lithium, aluminum and iron are formed. The lithium within the intermetallic phase of Al.sub.5 Fe.sub.2 exhibits increased activity over that of lithium within a lithium-aluminum alloy to provide an increased cell potential of up to about 0.25 volt.

Kinetics of the mechanochemical synthesis of alkaline-earth metal amides

NASA Astrophysics Data System (ADS)

Garroni, Sebastiano; Takacs, Laszlo; Leng, Haiyan; Delogu, Francesco

2014-07-01

A phenomenological framework is developed to model the kinetics of the formation of alkaline-earth metal amides by the ball milling induced reaction of their hydrides with gaseous ammonia. It is shown that the exponential character of the kinetic curves is modulated by the increase of the total volume of the powder inside the reactor due to the substantially larger molar volume of the products compared to the reactants. It is claimed that the volume of powder effectively processed during each collision connects the transformation rate to the physical and chemical processes underlying the mechanochemical transformations.

Extraction of trace metals from fly ash

DOEpatents

Blander, M.; Wai, C.M.; Nagy, Z.

1983-08-15

A process is described for recovering silver, gallium and/or other trace metals from a fine grained industrial fly ash associated with a process for producing phosphorous. The fly ash has a silicate base and contains surface deposits of the trace metals as oxides, chlorides or the like. The process is carried out by contacting the fly ash with AlCl/sub 3/ in an alkali halide melt to react the trace metals with the AlCl/sub 3/ to form compositions soluble in the melt and a residue containing the silicate and aluminum oxide or other aluminum precipitate, and separating the desired trace metal or metals from the melt by electrolysis or other separation techniques.

Extraction of trace metals from fly ash

DOEpatents

Blander, Milton; Wai, Chien M.; Nagy, Zoltan

1984-01-01

A process for recovering silver, gallium and/or other trace metals from a fine grained industrial fly ash associated with a process for producing phosphorous, the fly ash having a silicate base and containing surface deposits of the trace metals as oxides, chlorides or the like, with the process being carried out by contacting the fly ash with AlCl.sub.3 in an alkali halide melt to react the trace metals with the AlCl.sub.3 to form compositions soluble in the melt and a residue containing the silicate and aluminum oxide or other aluminum precipitate, and separating the desired trace metal or metals from the melt by electrolysis or other separation techniques.

Dehydrogenation of secondary amines: synthesis, and characterization of rare-earth metal complexes incorporating imino- or amido-functionalized pyrrolyl ligands.

PubMed

Li, Qinghai; Zhou, Shuangliu; Wang, Shaowu; Zhu, Xiancui; Zhang, Lijun; Feng, Zhijun; Guo, Liping; Wang, Fenhua; Wei, Yun

2013-02-28

The dehydrogenation of pyrrolyl-functionalized secondary amines initiated by rare-earth metal amides was systematically studied. Reactions of the rare-earth metal amides [(Me(3)Si)(2)N](3)RE(μ-Cl)Li(THF)(3) with pyrrolyl-functionalized secondary amines 2-(t)BuNHCH(2)-5-R-C(4)H(2)NH (R = H (1), R = (t)Bu (2)) led to dehydrogenation of the secondary amines with isolation of imino-functionalized pyrrolyl rare-earth metal complexes [2-(t)BuN=CH-5-R-C(4)H(2)N](2)REN(SiMe(3))(2) (R = H, RE = Y (3a), Dy (3b), Yb (3c), Eu (3d); R = (t)Bu, RE = Y (4a), Dy (4b), Er (4c)). The mixed ligands erbium complex [2-(t)BuNCH(2)-5-(t)Bu-C(4)H(2)N]Er[2-(t)BuN=CH-5-(t)BuC(4)H(2)N](2)ClLi(2)(THF) (4c') was isolated in a short reaction time for the synthesis of complex 4c. Reaction of the deuterated pyrrolyl-functionalized secondary amine 2-((t)BuNHCHD)C(4)H(3)NH with yttrium amide [(Me(3)Si)(2)N](3)Y(μ-Cl)Li(THF)(3) further proved that pyrrolyl-amino ligands were transferred to pyrrolyl-imino ligands. Treatment of 2-((t)BuNHCH(2))C(4)H(3)NH (1) with excess (Me(3)Si)(2)NLi gave the only pyrrole deprotonated product {[η(5):η(2):η(1)-2-((t)BuNHCH(2))C(4)H(3)N]Li(2)N(SiMe(3))(2)}(2) (5), indicating that LiN(SiMe(3))(2) could not dehydrogenate the secondary amines to imines and rare-earth metal ions had a decisive effect on the dehydrogenation. The reaction of the rare-earth metal amides [(Me(3)Si)(2)N](3)RE(μ-Cl)Li(THF)(3) with 1 equiv. of more bulky pyrrolyl-functionalized secondary amine 2-[(2,6-(i)Pr(2)C(6)H(3))NHCH(2)](C(4)H(3)NH) (6) in toluene afforded the only amine and pyrrole deprotonated dinuclear rare-earth metal amido complexes {(μ-η(5):η(1)):η(1)-2-[(2,6-(i)Pr(2)C(6)H(3))NCH(2)]C(4)H(3)N]LnN(SiMe(3))(2)}(2) (RE = Nd (7a), Sm (7b), Er (7c)), no dehydrogenation of secondary amine to imine products were observed. On the basis of experimental results, a plausible mechanism for the dehydrogenation of secondary amines to imines was proposed.

Extraction of trivalent rare-earth metal nitrates by solutions of tributyl phosphate and diisooctylmethylphosphonate in kerosene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pyartman, A.K.; Puzikov, E.A.; Kopyrin, A.A.

1995-01-01

Isotherms of extraction of trivalent rare-earth metal nitrates in the series lanthanum-lutetium, yttrium by 0.5-2.5 M solutions of tri-n-buty1 phosphate and diisooctyl methylphosphonate in kerosene at 298.15 K, pH 2 are presented. The influence of the ionic strength of aqueous phase and extractant concentration on the concentration extraction constants in the case of formation of metal(III) trisolvates in organic phase is given by equation.

Refined global methyl halide budgets with respect to rapeseed (Brassica napus) by life-cycle measurements

NASA Astrophysics Data System (ADS)

Jiao, Y.; Acdan, J.; Xu, R.; Deventer, M. J.; Rhew, R. C.

2017-12-01

A precise quantification of global methyl halide budgets is needed to evaluate the ozone depletion potential of these compounds and to predict future changes of stratospheric ozone. However, the global budgets of methyl halides are not balanced between currently identified and quantified sources and sinks. Our study re-evaluated the methyl bromide budget from global cultivated rapeseed (Brassica napus) through life-cycle flux measurements both in the greenhouse and in the field, yielding a methyl bromide emission rate that scales globally to 1.0 - 1.2 Gg yr-1. While this indicates a globally significant source, it is much smaller than the previously widely cited value of 5 - 6 Gg yr-1(Mead et al., 2008), even taking into account the near tripling of annual global yield of rapeseed since the previous evaluation was conducted. Our study also evaluated the methyl chloride and methyl iodide emission levels from rapeseed, yielding emission rates that scale to 5.4 Gg yr-1 for methyl chloride and 1.8 Gg yr-1 of methyl iodide. The concentrations of the methyl donor SAM (S-adenosyl methionine) and the resultant product SAH (S-Adenosyl-L-homocysteine) were also analyzed to explore their role in biogenic methyl halide formation. Halide gradient incubations showed that the magnitude of methyl halide emissions from rapeseed is highly correlated to soil halide levels, thus raising the concern that the heterogeneity of soil halide contents geographically should be considered when extrapolating to global budget.

The adsorption kinetics of metal ions onto different microalgae and siliceous earth.

PubMed

Schmitt, D; Müller, A; Csögör, Z; Frimmel, F H; Posten, C

2001-03-01

In the present work the adsorption kinetics of the six metal ions aluminum, zinc, mercury, lead, copper, and cadmium onto living microalgae were measured. The freshwater green microalga Scenedesmus subspicatus, the brackish water diatom Cyclotella cryptica, the seawater diatom Phaeodactylum tricornutum, and the seawater red alga Porphyridium purpureum were the subject of investigation. In most cases the adsorption rate of the metals could be well described by using the equation of the Langmuir adsorption rate expression. Inverse parameter estimation allowed the determination of the rate constants of the adsorption process and the maximum metal content of the algae. The highest values for the rate constant were obtained for Porphyridium purpureum followed by Phaeodactylum tricornutum. High values for the maximum content were obtained for Cyclotella cryptica and Scenedesmus subspicatus. The maximum rate constant was 24.21 h-1 for the adsorption of Hg to Porphyridium purpureum whereas the maximum metal content (0.243 g g-1) was obtained for Zn on Cyclotella cryptica. A comparison of these values with those obtained for the mineral siliceous earth exhibiting low maximum content and high adsorption rates reveals that the mechanism of adsorption onto the algae is a mixture of adsorption and accumulation.

A volatile topic: Parsing out the details of Earth's formation through experimental metal-silicate partitioning of volatile and moderately volatile elements

NASA Astrophysics Data System (ADS)

Mahan, B. M.; Siebert, J.; Blanchard, I.; Badro, J.; Sossi, P.; Moynier, F.

2017-12-01

Volatile and moderately volatile elements display different volatilities and siderophilities, as well as varying sensitivity to thermodynamic controls (X, P, T, fO2) during metal-silicate differentiation. The experimental determination of the metal-silicate partitioning of these elements permits us to evaluate processes controlling the distribution of these elements in Earth. In this work, we have combined metal-silicate partitioning data and results for S, Sn, Zn and Cu, and input these characterizations into Earth formation models. Model parameters such as source material, timing of volatile delivery, fO2 path, and degree of impactor equilibration were varied to encompass an array of possible formation scenarios. These models were then assessed to discern plausible sets of conditions that can produce current observed element-to-element ratios (e.g. S/Zn) in the Earth's present-day mantle, while also satisfying current estimates on the S content of the core, at no more than 2 wt%. The results of our models indicate two modes of accretion that can maintain chondritic element-to-element ratios for the bulk Earth and can arrive at present-day mantle abundances of these elements. The first mode requires the late addition of Earth's entire inventory of these elements (assuming a CI-chondritic composition) and late-stage accretion that is marked by partial equilibration of large impactors. The second, possibly more intuitive mode, requires that Earth accreted - at least initially - from volatile poor material preferentially depleted in S relative to Sn, Zn, and Cu. From a chemical standpoint, this source material is most similar to type I chondrule rich (and S poor) materials (Hewins and Herzberg, 1996; Mahan et al., 2017; Amsellem et al., 2017), such as the metal-bearing carbonaceous chondrites.

Metal oxide films on metal

DOEpatents

Wu, Xin D.; Tiwari, Prabhat

1995-01-01

A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

Lattice vibrations and electronic transitions in the rare-earth metals: yttrium, gadolinium and lutetium.

PubMed

Olijnyk, Helmut

2005-01-12

Lattice vibrations in high-pressure phases of Y, Gd and Lu were studied by Raman spectroscopy. The observed phonon frequencies decrease towards the transitions to the dhcp and fcc phases. There is evidence that the entire structural sequence [Formula: see text] under pressure for the individual regular rare-earth metals and along the lanthanide series at ambient pressure involve softening of certain acoustic and optical phonon modes and of the elastic shear modulus C(44). Comparison is made to transitions between close-packed lattices in other metals, and possible correlations to s-d electron transfer are discussed.

Depletion-mode vertical Ga2O3 trench MOSFETs fabricated using Ga2O3 homoepitaxial films grown by halide vapor phase epitaxy

NASA Astrophysics Data System (ADS)

Sasaki, Kohei; Thieu, Quang Tu; Wakimoto, Daiki; Koishikawa, Yuki; Kuramata, Akito; Yamakoshi, Shigenobu

2017-12-01

We developed depletion-mode vertical Ga2O3 trench metal-oxide-semiconductor field-effect transistors by using n+ contact and n- drift layers. These epilayers were grown on an n+ (001) Ga2O3 single-crystal substrate by halide vapor phase epitaxy. Cu and HfO2 were used for the gate metal and dielectric film, respectively. The mesa width and gate length were approximately 2 and 1 µm, respectively. The devices showed good DC characteristics, with a specific on-resistance of 3.7 mΩ cm2 and clear current modulation. An on-off ratio of approximately 103 was obtained.

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…

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

Lasing in robust cesium lead halide perovskite nanowires

DOE PAGES

Eaton, Samuel W.; Lai, Minliang; Gibson, Natalie A.; ...

2016-02-09

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 andmore » handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry-Pérot lasing occurs in CsPbBr 3 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.« less

Using Perovskite Nanoparticles as Halide Reservoirs in Catalysis and as Spectrochemical Probes of Ions in Solution

DOE PAGES

Doane, Tennyson L.; Ryan, Kayla L.; Pathade, Laxmikant; ...

2016-05-05

The ability of cesium lead halide (CsPbX 3; 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. Also, the exchange of CsPbI 3 with Cl – or Br – causes a significant blue-shift in absorption and photoluminescence, whereas reacting I – with CsPbBr 3 causesmore » 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. Finally, 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.« less

Phonon Speed, Not Scattering, Differentiates Thermal Transport in Lead Halide Perovskites.

PubMed

Elbaz, Giselle A; Ong, Wee-Liat; Doud, Evan A; Kim, Philip; Paley, Daniel W; Roy, Xavier; Malen, Jonathan A

2017-09-13

Thermal management plays a critical role in the design of solid state materials for energy conversion. Lead halide perovskites have emerged as promising candidates for photovoltaic, thermoelectric, and optoelectronic applications, but their thermal properties are still poorly understood. Here, we report on the thermal conductivity, elastic modulus, and sound speed of a series of lead halide perovskites MAPbX 3 (X = Cl, Br, I), CsPbBr 3 , and FAPbBr 3 (MA = methylammonium, FA = formamidinium). Using frequency domain thermoreflectance, we find that the room temperature thermal conductivities of single crystal lead halide perovskites range from 0.34 to 0.73 W/m·K and scale with sound speed. These results indicate that regardless of composition, thermal transport arises from acoustic phonons having similar mean free path distributions. A modified Callaway model with Born von Karmen-based acoustic phonon dispersion predicts that at least ∼70% of thermal conductivity results from phonons having mean free paths shorter than 100 nm, regardless of whether resonant scattering is invoked. Hence, nanostructures or crystal grains with dimensions smaller than 100 nm will appreciably reduce thermal transport. These results are important design considerations to optimize future lead halide perovskite-based photovoltaic, optoelectronic, and thermoelectric devices.

Shape Evolution and Single Particle Luminescence of Organometal Halide Perovskite Nanocrystals

DOE PAGES

Zhu, Feng; Men, Long; Guo, Yijun; ...

2015-02-09

Organometallic halide perovskites CH 3NH 3PbX 3 (X = I, Br, Cl) have quickly become one of the most promising semiconductors for solar cells, with photovoltaics made of these materials reaching power conversion efficiencies of near 20%. Improving our ability to harness the full potential of organometal halide perovskites will require more controllable syntheses that permit a detailed understanding of their fundamental chemistry and photophysics. In our manuscript, we systematically synthesize CH 3NH 3PbX 3 (X = I, Br) nanocrystals with different morphologies (dots, rods, plates or sheets) by using different solvents and capping ligands. CH 3NH 3PbX 3 nanowiresmore » and nanorods capped with octylammonium halides show relatively higher photoluminescence (PL) quantum yields and long PL lifetimes. CH 3NH 3PbI 3 nanowires monitored at the single particle level show shape-correlated PL emission across whole particles, with little photobleaching observed and very few off periods. Our work highlights the potential of low-dimensional organometal halide perovskite semiconductors in constructing new porous and nanostructured solar cell architectures, as well as in applying these materials to other fields such as light-emitting devices and single particle imaging and tracking.« less

Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

NASA Astrophysics Data System (ADS)

Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J.; Poblet, Josep M.; Galan-Mascaros, J. R.

2018-01-01

Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.

Super earth interiors and validity of Birch's Law for ultra-high pressure metals and ionic solids

NASA Astrophysics Data System (ADS)

Ware, Lucas Andrew

2015-01-01

Super Earths, recently detected by the Kepler Mission, expand the ensemble of known terrestrial planets beyond our Solar System's limited group. Birch's Law and velocity-density systematics have been crucial in constraining our knowledge of the composition of Earth's mantle and core. Recently published static diamond anvil cell experimental measurements of sound velocities in iron, a key deep element in most super Earth models, are inconsistent with each other with regard to the validity of Birch's Law. We examine the range of validity of Birch's Law for several metallic elements, including iron, and ionic solids shocked with a two-stage light gas gun into the ultra-high pressure, temperature fluid state and make comparisons to the recent static data.

Laser post-processing of halide perovskites for enhanced photoluminescence and absorbance

NASA Astrophysics Data System (ADS)

Tiguntseva, E. Y.; Saraeva, I. N.; Kudryashov, S. I.; Ushakova, E. V.; Komissarenko, F. E.; Ishteev, A. R.; Tsypkin, A. N.; Haroldson, R.; Milichko, V. A.; Zuev, D. A.; Makarov, S. V.; Zakhidov, A. A.

2017-11-01

Hybrid halide perovskites have emerged as one of the most promising type of materials for thin-film photovoltaic and light-emitting devices. Further boosting their performance is critically important for commercialization. Here we use femtosecond laser for post-processing of organo-metalic perovskite (MAPbI3) films. The high throughput laser approaches include both ablative silicon nanoparticles integration and laser-induced annealing. By using these techniques, we achieve strong enhancement of photoluminescence as well as useful light absorption. As a result, we observed experimentally 10-fold enhancement of absorbance in a perovskite layer with the silicon nanoparticles. Direct laser annealing allows for increasing of photoluminescence over 130%, and increase absorbance over 300% in near-IR range. We believe that the developed approaches pave the way to novel scalable and highly effective designs of perovskite based devices.

Processing of Phosphorus Slag with Recovery of Rare Earth Metals and Obtaining Silicon Containing Cake

NASA Astrophysics Data System (ADS)

Karshigina, Zaure; Abisheva, Zinesh; Bochevskaya, Yelena; Akcil, Ata; Sharipova, Aynash; Sargelova, Elmira

2016-10-01

The present research is devoted to the processing of slag generating during the yellow phosphorus production. In this paper are presented studies on leaching of phosphorus production slag by nitric acid with recovery of rare earth metals (REMs) into solution. REMs recovery into the solution achieved 98 % during the leaching process with using 7.5 mol/L of HNO3, liquid-to-solid ratio is 2.6:1, temperature is 60°C, process duration is 1 hour and stirrer speed is 500 rpm. Behaviour during the leaching of associated components such as calcium, aluminium, and iron was studied. After the leaching cake contains ∼⃒75-85 % of SiO2 and it might be useful for obtaining of precipitated silicon dioxide. With the purpose of separation from the impurities, recovery and concentrating of REMs, the obtained solution after leaching was subjected to extraction processing methods. The influence of ratio of organic and aqueous phases (O: A) on the extraction of rare earth metals by tributyl phosphate (TBP) with concentrations from 20 up to 100 % was studied. The REMs extraction with increasing TBP concentration under changes O:A ratio from 1:20 down to 1:1 into the organic phase from the solutions after nitric acid leaching increased from 22.2 up to 99.3%. The duration effect of REMs extraction process was studied by tributyl phosphate. It is revealed that with increasing of duration of the extraction process from 10 to 30 minutes REMs recovery into the organic phase almost did not changed. The behaviour of iron in the extraction process by TBP was studied. It was found that such accompanying components as calcium and aluminium by tributyl phosphate didn't extracted. To construct isotherm of REMs extraction of by tributyl phosphate was used variable volume method. It was calculated three-step extraction is needed for REMs recovery from the solutions after nitric acid leaching of phosphorus production slag. The process of the three-steps counter current extraction of rare earth

Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex.

PubMed

You, Tingjie; Wang, Zhenrong; Chen, Jiajia; Xia, Yuanzhi

2017-02-03

A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.

Large tunable photoeffect on ion conduction in halide perovskites and implications for photodecomposition

NASA Astrophysics Data System (ADS)

Kim, Gee Yeong; Senocrate, Alessandro; Yang, Tae-Youl; Gregori, Giuliano; Grätzel, Michael; Maier, Joachim

2018-05-01

In the same way as electron transport is crucial for information technology, ion transport is a key phenomenon in the context of energy research. To be able to tune ion conduction by light would open up opportunities for a wide realm of new applications, but it has been challenging to provide clear evidence for such an effect. Here we show through various techniques, such as transference-number measurements, permeation studies, stoichiometric variations, Hall effect experiments and the use of blocking electrodes, that light excitation enhances by several orders of magnitude the ionic conductivity of methylammonium lead iodide, the archetypal metal halide photovoltaic material. We provide a rationale for this unexpected phenomenon and show that it straightforwardly leads to a hitherto unconsidered photodecomposition path of the perovskite.

Copper/amino acid catalyzed cross-couplings of aryl and vinyl halides with nucleophiles.

PubMed

Ma, Dawei; Cai, Qian

2008-11-18

Copper-assisted Ullmann-type coupling reactions are valuable transformations for organic synthesis. Researchers have extensively applied these reactions in both academic and industrial settings. However, two important issues, the high reaction temperatures (normally above 150 degrees C) and the stoichiometric amounts of copper necessary, have greatly limited the reaction scope. To solve these problems, we and other groups have recently explored the use of special ligands to promote these coupling reactions. We first showed that the structure of alpha-amino acids can accelerate Cu-assisted Ullmann reactions, leading to the coupling reactions of aryl halides and alpha-amino acids at 80-90 degrees C. In response to these encouraging results, we also discovered that an l-proline ligand facilitated the following transformations: (1) coupling of aryl halides with primary amines, cyclic secondary amines, and N-containing heterocycles at 40-90 degrees C; (2) coupling of aryl halides with sulfinic acid salts at 80-95 degrees C; (3) azidation of aryl halides and vinyl halides with sodium azide at 40-95 degrees C; (4) coupling of aryl halides with activated methylene compounds at 25-50 degrees C. In addition, we found that N,N-dimethylglycine as a ligand facilitated Cu-catalyzed biaryl ether formation at 90 degrees C. Moreover, Sonogashira reactions worked in the absence of palladium and phosphine ligands, forming enamides from vinyl halides and amides at temperatures ranging from ambient temperature up to 80 degrees C. Furthermore, we discovered that an ortho-amide group can accelerate some Ullmann-type reactions. This functional group in combination with other ligand effects allowed for aryl amination or biaryl ether formation at ambient temperature. The coupling between aryl halides and activated methylene compounds even proceeded at -45 degrees C to enantioselectively form a quaternary carbon center. Taking advantage of these results, we developed several novel approaches

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...

METHOD FOR THE REDUCTION OF URANIUM COMPOUNDS

DOEpatents

Cooke, W.H.; Crawford, J.W.C.

1959-05-12

An improved technique of preparing massive metallic uranium by the reaction at elevated temperature between an excess of alkali in alkaline earth metal and a uranium halide, such ss uranium tetrafluoride is presented. The improvement comprises employing a reducing atmosphere of hydrogen or the like, such as coal gas, in the vessel during the reduction stage and then replacing the reducing atmosphere with argon gas prior to cooling to ambient temperature.

New stable ternary alkaline-earth metal Pb(II) oxides: Ca / Sr / BaPb 2 O 3 and BaPbO 2

DOE PAGES

Li, Yuwei; Zhang, Lijun; Singh, David J.

2017-10-16

The different but related chemical behaviors of Pb(II) oxides compared to Sn(II) oxides, and the existence of known alkali/alkali-earth metal Sn(II) ternary phases, suggest that there should be additional ternary Pb(II) oxide phases. Here, we report structure searches on the ternary alkaline-earth metal Pb(II) oxides leading to four new phases. These are two ternary Pb(II) oxides, SrPb 2O 3 and BaPb 2O 3, which have larger chemical potential stability ranges compared with the corresponding Sn(II) oxides, and additionally two other ternary Pb(II) oxides, CaPb 2O 3 and BaPbO 2, for which there are no corresponding Sn(II) oxides. Those Pb(II) oxidesmore » are stabilized by Pb-rich conditions. These structures follow the Zintl behavior and consist of basic structural motifs of (PbO 3) 4- anionic units separated and stabilized by the alkaline-earth metal ions. They show wide band gaps ranging from 2.86 to 3.12 eV, and two compounds (CaPb 2O 3 and SrPb 2O 3) show rather light hole effective masses (around 2m 0). The valence band maxima of these compounds have a Pb-6s/O-2p antibonding character, which may lead to p-type defect (or doping) tolerant behavior. This then suggests alkaline-earth metal Pb(II) oxides may be potential p-type transparent conducting oxides.« less

New stable ternary alkaline-earth metal Pb(II) oxides: Ca / Sr / BaPb 2 O 3 and BaPbO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yuwei; Zhang, Lijun; Singh, David J.

The different but related chemical behaviors of Pb(II) oxides compared to Sn(II) oxides, and the existence of known alkali/alkali-earth metal Sn(II) ternary phases, suggest that there should be additional ternary Pb(II) oxide phases. Here, we report structure searches on the ternary alkaline-earth metal Pb(II) oxides leading to four new phases. These are two ternary Pb(II) oxides, SrPb 2O 3 and BaPb 2O 3, which have larger chemical potential stability ranges compared with the corresponding Sn(II) oxides, and additionally two other ternary Pb(II) oxides, CaPb 2O 3 and BaPbO 2, for which there are no corresponding Sn(II) oxides. Those Pb(II) oxidesmore » are stabilized by Pb-rich conditions. These structures follow the Zintl behavior and consist of basic structural motifs of (PbO 3) 4- anionic units separated and stabilized by the alkaline-earth metal ions. They show wide band gaps ranging from 2.86 to 3.12 eV, and two compounds (CaPb 2O 3 and SrPb 2O 3) show rather light hole effective masses (around 2m 0). The valence band maxima of these compounds have a Pb-6s/O-2p antibonding character, which may lead to p-type defect (or doping) tolerant behavior. This then suggests alkaline-earth metal Pb(II) oxides may be potential p-type transparent conducting oxides.« less

Environmental Effects on the Photophysics of Organic-Inorganic Halide Perovskites.

PubMed

Galisteo-López, Juan F; Anaya, M; Calvo, M E; Míguez, H

2015-06-18

The photophysical properties of films of organic-inorganic lead halide perovskites under different ambient conditions are herein reported. We demonstrate that their luminescent properties are determined by the interplay between photoinduced activation and darkening processes, which strongly depend on the atmosphere surrounding the samples. We have isolated oxygen and moisture as the key elements in each process, activation and darkening, both of which involve the interaction with photogenerated carriers. These findings show that environmental factors play a key role in the performance of lead halide perovskites as efficient luminescent materials.

Environmental Effects on the Photophysics of Organic–Inorganic Halide Perovskites

PubMed Central

2015-01-01

The photophysical properties of films of organic–inorganic lead halide perovskites under different ambient conditions are herein reported. We demonstrate that their luminescent properties are determined by the interplay between photoinduced activation and darkening processes, which strongly depend on the atmosphere surrounding the samples. We have isolated oxygen and moisture as the key elements in each process, activation and darkening, both of which involve the interaction with photogenerated carriers. These findings show that environmental factors play a key role in the performance of lead halide perovskites as efficient luminescent materials. PMID:26266592

Lattice vibrations and electronic transitions in the rare-earth metals: yttrium, gadolinium and lutetium

NASA Astrophysics Data System (ADS)

Olijnyk, Helmut

2005-01-01

Lattice vibrations in high-pressure phases of Y, Gd and Lu were studied by Raman spectroscopy. The observed phonon frequencies decrease towards the transitions to the dhcp and fcc phases. There is evidence that the entire structural sequence {\\mathrm {hcp \\to Sm\\mbox {-}type \\to dhcp \\to fcc}} under pressure for the individual regular rare-earth metals and along the lanthanide series at ambient pressure involve softening of certain acoustic and optical phonon modes and of the elastic shear modulus C44. Comparison is made to transitions between close-packed lattices in other metals, and possible correlations to s-d electron transfer are discussed.

The composition of Earth's core from equations of state, metal-silicate partitioning, and core formation modeling

NASA Astrophysics Data System (ADS)

Fischer, Rebecca; Campbell, Andrew; Ciesla, Fred

2016-04-01

The Earth accreted in a series of increasingly large and violent collisions. Simultaneously, the metallic core segregated from the silicate mantle, acquiring its modern composition through high pressure (P), high temperature (T) partitioning reactions. Here we present a model that couples these aspects of early planetary evolution, building on recent accretion simulations and metal-silicate partitioning experiments, constrained by density measurements of Fe-rich alloys. Previously, the equations of state of FeO, Fe-9Si, Fe-16Si, and FeSi were measured to megabar pressures and several thousand K using a laser-heated diamond anvil cell. With these equations of state, we determined that the core's density can be reproduced through the addition of 11.3 +/- 0.6 wt% silicon or 8.1 +/- 1.1 wt% oxygen to an Fe-Ni alloy (Fischer et al., 2011, 2014). Metal-silicate partitioning experiments of Ni, Co, V, Cr, Si, and O have been performed in a diamond anvil cell to 100 GPa and 5700 K, allowing the effects of P, T, and composition on the partitioning behaviors of these elements to be parameterized (Fischer et al., 2015; Siebert et al., 2012). Here we apply those experimental results to model Earth's core formation, using N-body simulations to describe the delivery, masses, and original locations of planetary building blocks (Fischer and Ciesla, 2014). As planets accrete, their core and mantle compositions are modified by high P-T reactions with each collision (Rubie et al., 2011). For partial equilibration of the mantle at 55% of the evolving core-mantle boundary pressure and the liquidus temperature, we find that the core contains 5.4 wt% Si and 1.9 wt% O. This composition is consistent with the seismologically-inferred density of Earth's core, based on comparisons to our equations of state, and indicate that the core cannot contain more than ~2 wt% S or C. Earth analogues experience 1.2 +/- 0.2 log units of oxidation during accretion, due to both the effects of high P

Chiral Alkyl Halides: Underexplored Motifs in Medicine

PubMed Central

Gál, Bálint; Bucher, Cyril; Burns, Noah Z.

2016-01-01

While alkyl halides are valuable intermediates in synthetic organic chemistry, their use as bioactive motifs in drug discovery and medicinal chemistry is rare in comparison. This is likely attributable to the common misconception that these compounds are merely non-specific alkylators in biological systems. A number of chlorinated compounds in the pharmaceutical and food industries, as well as a growing number of halogenated marine natural products showing unique bioactivity, illustrate the role that chiral alkyl halides can play in drug discovery. Through a series of case studies, we demonstrate in this review that these motifs can indeed be stable under physiological conditions, and that halogenation can enhance bioactivity through both steric and electronic effects. Our hope is that, by placing such compounds in the minds of the chemical community, they may gain more traction in drug discovery and inspire more synthetic chemists to develop methods for selective halogenation. PMID:27827902

Hyperfine structure of 2Σ molecules containing alkaline-earth-metal atoms

NASA Astrophysics Data System (ADS)

Aldegunde, Jesus; Hutson, Jeremy M.

2018-04-01

Ultracold molecules with both electron spin and an electric dipole moment offer new possibilities in quantum science. We use density-functional theory to calculate hyperfine coupling constants for a selection of molecules important in this area, including RbSr, LiYb, RbYb, CaF, and SrF. We find substantial hyperfine coupling constants for the fermionic isotopes of the alkaline-earth-metal and Yb atoms. We discuss the hyperfine level patterns and Zeeman splittings expected for these molecules. The results will be important both to experiments aimed at forming ultracold open-shell molecules and to their applications.

Liquefaction process for solid carbonaceous materials containing alkaline earth metal humates

DOEpatents

Epperly, William R.; Deane, Barry C.; Brunson, Roy J.

1982-01-01

An improved liquefaction process wherein wall scale and particulate agglomeration during the liquefaction of solid carbonaceous materials containing alkaline earth metal humates is reduced and/or eliminated by subjecting the solid carbonaceous materials to controlled cyclic cavitation during liquefaction. It is important that the solid carbonaceous material be slurried in a suitable solvent or diluent during liquefaction. The cyclic cavitation may be imparted via pressure cycling, cyclic agitation and the like. When pressure cycling or the like is employed an amplitude equivalent to at least 25 psia is required to effectively remove scale from the liquefaction vessel walls.

Alkali Halide FLIR Lens Development

DTIC Science & Technology

1981-10-01

in the atmosphere. The main emphasis in this 3 report has been development of protective coatings for potassium bromide lenses. The most favorable...placed onto the bottom electrode. Pieces of single-crystalline potassium chloride of approximately the same thickness as coated alkali halide samples...none of the samples appeared to be degraded by the high humidity associated with the exposure. 2. UNITS TESTED Four coated potassium bromide lenses

Recovery of Rare Earths, Precious Metals and Other Critical Materials from Geothermal Waters with Advanced Sorbent Structures

DOE Data Explorer

Pamela M. Kinsey

2015-09-30

The work evaluates, develops and demonstrates flexible, scalable mineral extraction technology for geothermal brines based upon solid phase sorbent materials with a specific focus upon rare earth elements (REEs). The selected organic and inorganic sorbent materials demonstrated high performance for collection of trace REEs, precious and valuable metals. The nanostructured materials typically performed better than commercially available sorbents. Data contains organic and inorganic sorbent removal efficiency, Sharkey Hot Springs (Idaho) water chemsitry analysis, and rare earth removal efficiency from select sorbents.

Laser Direct Write Synthesis of Lead Halide Perovskites

DOE PAGES

Chou, Stanley S.; Swartzentruber, Brian S.; Janish, Matthew T.; ...

2016-09-05

Lead halide perovskites are increasingly considered for applications beyond photovoltaics, for example, light emission and detection, where an ability to pattern and prototype microscale geometries can facilitate the incorporation of this class of materials into devices. In this study, we demonstrate laser direct write of lead halide perovskites, a remarkably simple procedure that takes advantage of the inverse dependence between perovskite solubility and temperature by using a laser to induce localized heating of an absorbing substrate. We also demonstrate arbitrary pattern formation of crystalline CH 3NH 3PbBr 3 on a range of substrates and fabricate and characterize a microscale photodetectormore » using this approach. This direct write methodology provides a path forward for the prototyping and production of perovskite-based devices.« less

Laser Direct Write Synthesis of Lead Halide Perovskites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chou, Stanley S.; Swartzentruber, Brian S.; Janish, Matthew T.

Lead halide perovskites are increasingly considered for applications beyond photovoltaics, for example, light emission and detection, where an ability to pattern and prototype microscale geometries can facilitate the incorporation of this class of materials into devices. In this study, we demonstrate laser direct write of lead halide perovskites, a remarkably simple procedure that takes advantage of the inverse dependence between perovskite solubility and temperature by using a laser to induce localized heating of an absorbing substrate. We also demonstrate arbitrary pattern formation of crystalline CH 3NH 3PbBr 3 on a range of substrates and fabricate and characterize a microscale photodetectormore » using this approach. This direct write methodology provides a path forward for the prototyping and production of perovskite-based devices.« less

Permeation of halide anions through phospholipid bilayers occurs by the solubility-diffusion mechanism

NASA Technical Reports Server (NTRS)

Paula, S.; Volkov, A. G.; Deamer, D. W.

1998-01-01

Two alternative mechanisms are frequently used to describe ionic permeation of lipid bilayers. In the first, ions partition into the hydrophobic phase and then diffuse across (the solubility-diffusion mechanism). The second mechanism assumes that ions traverse the bilayer through transient hydrophilic defects caused by thermal fluctuations (the pore mechanism). The theoretical predictions made by both models were tested for halide anions by measuring the permeability coefficients for chloride, bromide, and iodide as a function of bilayer thickness, ionic radius, and sign of charge. To vary the bilayer thickness systematically, liposomes were prepared from monounsaturated phosphatidylcholines (PC) with chain lengths between 16 and 24 carbon atoms. The fluorescent dye MQAE (N-(ethoxycarbonylmethyl)-6-methoxyquinolinium bromide) served as an indicator for halide concentration inside the liposomes and was used to follow the kinetics of halide flux across the bilayer membranes. The observed permeability coefficients ranged from 10(-9) to 10(-7) cm/s and increased as the bilayer thickness was reduced. Bromide was found to permeate approximately six times faster than chloride through bilayers of identical thickness, and iodide permeated three to four times faster than bromide. The dependence of the halide permeability coefficients on bilayer thickness and on ionic size were consistent with permeation of hydrated ions by a solubility-diffusion mechanism rather than through transient pores. Halide permeation therefore differs from that of a monovalent cation such as potassium, which has been accounted for by a combination of the two mechanisms depending on bilayer thickness.

Alkali-earth metal bridges formed in biofilm matrices regulate the uptake of fluoroquinolone antibiotics and protect against bacterial apoptosis.

PubMed

Kang, Fuxing; Wang, Qian; Shou, Weijun; Collins, Chris D; Gao, Yanzheng

2017-01-01

Bacterially extracellular biofilms play a critical role in relieving toxicity of fluoroquinolone antibiotic (FQA) pollutants, yet it is unclear whether antibiotic attack may be defused by a bacterial one-two punch strategy associated with metal-reinforced detoxification efficiency. Our findings help to assign functions to specific structural features of biofilms, as they strongly imply a molecularly regulated mechanism by which freely accessed alkali-earth metals in natural waters affect the cellular uptake of FQAs at the water-biofilm interface. Specifically, formation of alkali-earth-metal (Ca 2+ or Mg 2+ ) bridge between modeling ciprofloxacin and biofilms of Escherichia coli regulates the trans-biofilm transport rate of FQAs towards cells (135-nm-thick biofilm). As the addition of Ca 2+ and Mg 2+ (0-3.5 mmol/L, CIP: 1.25 μmol/L), the transport rates were reduced to 52.4% and 63.0%, respectively. Computational chemistry analysis further demonstrated a deprotonated carboxyl in the tryptophan residues of biofilms acted as a major bridge site, of which one side is a metal and the other is a metal girder jointly connected to the carboxyl and carbonyl of a FQA. The bacterial growth rate depends on the bridging energy at anchoring site, which underlines the environmental importance of metal bridge formed in biofilm matrices in bacterially antibiotic resistance. Copyright © 2016 Elsevier Ltd. All rights reserved.

SHSG processing for three-wavelength HOEs recording in silver halide materials

NASA Astrophysics Data System (ADS)

Kim, Jong Man; Choi, Yoon S.; Bjelkhagen, Hans I.; Phillips, Nicholas J.

2002-06-01

The recording and processing technique for color HOEs in ultrafine-grain panchromatic silver halide emulsions is presented. It is possible to obtain high diffraction efficiency employing the silver halide sensitized gelatin (SHSG) process. SHSG holograms are similar to holograms recorded in dichromated gelatin (DCG). The drawback of DCG is its low sensitivity and limited spectral response. Panchromatic silver halide materials from Slavich can be processed in such a way that the final holograms have properties like a DCG hologram. The processing method or microvoid technique has been optimized for three laser- wavelength recordings in Slavich PFG-03C emulsion. For example, applying this new processing technique high- efficiency white holographic reflectors can be manufactured. The technique is also suitable for producing efficiency color display holograms. In particular, masters for mass production of color holograms or color HOEs can be performed by contact-copying into photopolymer materials because the reconstruction wavelengths are identical to the recording wavelengths.

Development and melt growth of novel scintillating halide crystals

NASA Astrophysics Data System (ADS)

Yoshikawa, Akira; Yokota, Yuui; Shoji, Yasuhiro; Kral, Robert; Kamada, Kei; Kurosawa, Shunsuke; Ohashi, Yuji; Arakawa, Mototaka; Chani, Valery I.; Kochurikhin, Vladimir V.; Yamaji, Akihiro; Andrey, Medvedev; Nikl, Martin

2017-12-01

Melt growth of scintillating halide crystals is reviewed. The vertical Bridgman growth technique is still considered as very popular method that enables production of relatively large and commercially attractive crystals. On the other hand, the micro-pulling-down method is preferable when fabrication of small samples, sufficient for preliminary characterization of their optical and/or scintillation performance, is required. Moreover, bulk crystal growth is also available using the micro-pulling-down furnace. The examples of growths of various halide crystals by industrially friendly melt growth techniques including Czochralski and edge-defined film-fed growth methods are also discussed. Finally, traveling molten zone growth that in some degree corresponds to horizontal zone melting is briefly overviewed.

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.

Experimental investigation of the partitioning of phosphorus between metal and silicate phases - Implications for the earth, moon and eucrite parent body

NASA Technical Reports Server (NTRS)

Newsom, H. E.; Drake, M. J.

1983-01-01

An experimental study is reported of the partitioning of Phosphorus between solid metal and basaltic silicate liquid as a function of temperature and oxygen fugacity and of the implications for the earth, moon and eucrite parent body (EPB). The relationship established between the partition coefficient and the fugacity is given at 1190 C by log D(P) = -1.12 log fO2 - 15.95 and by log D(P) = -1.53 log fO2 17.73 at 1300 C. The partition coefficient D(P) was determined, and it is found to be consistent with a valence state of 5 for P in the molten silicate. Using the determined coefficient the low P/La ratios of the earth, moon, and eucrites relative to C1 chondrites can be explained. The lowering of the P/La ratio in the eucrites relative to Cl chondrite by a factor of 40 can be explained by partitioning P into 20-25 wt% sulfur-bearing metallic liquid corresponding to 5-25% of the total metal plus silicate system. The low P/La and W/La ratios in the moon may be explained by the partitioning of P and W into metal during formation of a small core by separation of liquid metal from silicate at low degrees of partial melting of the silicates. These observations are consistent with independent formation of the moon and the earth.

Determination of the structural phase and octahedral rotation angle in halide perovskites

NASA Astrophysics Data System (ADS)

dos Reis, Roberto; Yang, Hao; Ophus, Colin; Ercius, Peter; Bizarri, Gregory; Perrodin, Didier; Shalapska, Tetiana; Bourret, Edith; Ciston, Jim; Dahmen, Ulrich

2018-02-01

A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurement of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). The approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.

Determination of the structural phase and octahedral rotation angle in halide perovskites

DOE PAGES

dos Reis, Roberto; Yang, Hao; Ophus, Colin; ...

2018-02-12

A key to the unique combination of electronic and optical properties in halide perovskite materials lies in their rich structural complexity. However, their radiation sensitive nature limits nanoscale structural characterization requiring dose efficient microscopic techniques in order to determine their structures precisely. In this work, we determine the space-group and directly image the Br halide sites of CsPbBr 3, a promising material for optoelectronic applications. Based on the symmetry of high-order Laue zone reflections of convergent-beam electron diffraction, we identify the tetragonal (I4/mcm) structural phase of CsPbBr 3 at cryogenic temperature. Electron ptychography provides a highly sensitive phase contrast measurementmore » of the halide positions under low electron-dose conditions, enabling imaging of the elongated Br sites originating from the out-of-phase octahedral rotation viewed along the [001] direction of I4/mcm persisting at room temperature. The measurement of these features and comparison with simulations yield an octahedral rotation angle of 6.5°(±1.5°). Finally, the approach demonstrated here opens up opportunities for understanding the atomic scale structural phenomena applying advanced characterization tools on a wide range of radiation sensitive halide-based all-inorganic and hybrid organic-inorganic perovskites.« less

Silver-halide photographic materials based on nanoporous glasses

NASA Astrophysics Data System (ADS)

Andreeva, O. V.; Obyknovennaya, I. E.; Gavrilyuk, E. R.; Paramonov, A. A.; Kushnarenko, A. P.

2005-12-01

This paper discusses the results of an investigation of the recording of composite nanoporous photographic materials with a photosensitive composite made from silver halide in gelatin, developed and created at S. I. Vavilov State Optical Institute.

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...

Enhanced pinning in mixed rare earth-123 films

DOEpatents

Driscoll, Judith L [Los Alamos, NM; Foltyn, Stephen R [Los Alamos, NM

2009-06-16

An superconductive article and method of forming such an article is disclosed, the article including a substrate and a layer of a rare earth barium cuprate film upon the substrate, the rare earth barium cuprate film including two or more rare earth metals capable of yielding a superconductive composition where ion size variance between the two or more rare earth metals is characterized as greater than zero and less than about 10.times.10.sup.-4, and the rare earth barium cuprate film including two or more rare earth metals is further characterized as having an enhanced critical current density in comparison to a standard YBa.sub.2Cu.sub.3O.sub.y composition under identical testing conditions.

Labile rhizosphere soil solution fraction for prediction of bioavailability of heavy metals and rare earth elements to plants.

PubMed

Shan, Xiao-Quan; Wang, Zhongwen; Wang, Weisheng; Zhang, Shuzhen; Wen, Bei

2003-02-01

A labile rhizosphere soil solution fraction has been recommended to predict the bioavailability of heavy metals and rare earth elements to plants. This method used moist rhizosphere soil in combination with a mixture of 0.01 mol L(-1) of low-molecular-weight organic acids (LMWOAs) as extractant. The extracted soil solutions were fractionated into two colloidal fractions of <0.45 microm (F(3)) and <0.2 microm (F(2)), and one truly dissolved fraction including free metal ions and inorganic and organic complexes (fractionmetals and rare earth elements in F(2) and F(3) were quite similar. However, the mean concentrations of Cr, Ni, Zn, Cu, Pb, Cd, La, Ce, Pr, and Nd in F(lrss) accounted for 79.9%, 91.3%, 90.8%, 60.1%, 77.5%, 75.3%, 81.2%, 77.2%, 80.3%, and 79.5%, respectively, of their concentrations in F(2). In contrast, there were no differences in the extractable metal concentrations between the three fractions while the first step of the method recommended by the European Community of Reference (BCR), where 0.1 mol L(-1) acetic acid was used as an extractant. The single correlation analysis was made between metal concentrations in the different fractions of soil solutions and their concentrations in wheat. If the first step of BCR method was used there was no good correlation between heavy metals in soil pools and that in wheat shoots and roots. When LMWAOs were used a good correlation was obtained between the concentrations of heavy metals in soil pools and that in wheat roots, which followed a general order of r(1 kD, LMWOAs) >r(0.2 microm, LMWOAs) approximately r(0.45 microm, LMWOAs). In the case of rare earth elements the good correlation was obtained for both the wheat roots and shoots. Generally, the correlation coefficients

Electron detachment energies in high-symmetry alkali halide solvated-electron anions

NASA Astrophysics Data System (ADS)

Anusiewicz, Iwona; Berdys, Joanna; Simons, Jack; Skurski, Piotr

2003-07-01

We decompose the vertical electron detachment energies (VDEs) in solvated-electron clusters of alkali halides in terms of (i) an electrostatic contribution that correlates with the dipole moment (μ) of the individual alkali halide molecule and (ii) a relaxation component that is related to the polarizability (α) of the alkali halide molecule. Detailed numerical ab initio results for twelve species (MX)n- (M=Li,Na; X=F,Cl,Br; n=2,3) are used to construct an interpolation model that relates the clusters' VDEs to their μ and α values as well as a cluster size parameter r that we show is closely related to the alkali cation's ionic radius. The interpolation formula is then tested by applying it to predict the VDEs of four systems [i.e., (KF)2-, (KF)3-, (KCl)2-, and (KCl)3-] that were not used in determining the parameters of the model. The average difference between the model's predicted VDEs and the ab initio calculated electron binding energies is less than 4% (for the twelve species studied). It is concluded that one can easily estimate the VDE of a given high-symmetry solvated electron system by employing the model put forth here if the α, μ and cation ionic radii are known. Alternatively, if VDEs are measured for an alkali halide cluster and the α and μ values are known, one can estimate the r parameter, which, in turn, determines the "size" of the cluster anion.

Electron–phonon coupling in hybrid lead halide perovskites

PubMed Central

Wright, Adam D.; Verdi, Carla; Milot, Rebecca L.; Eperon, Giles E.; Pérez-Osorio, Miguel A.; Snaith, Henry J.; Giustino, Feliciano; Johnston, Michael B.; Herz, Laura M.

2016-01-01

Phonon scattering limits charge-carrier mobilities and governs emission line broadening in hybrid metal halide perovskites. Establishing how charge carriers interact with phonons in these materials is therefore essential for the development of high-efficiency perovskite photovoltaics and low-cost lasers. Here we investigate the temperature dependence of emission line broadening in the four commonly studied formamidinium and methylammonium perovskites, HC(NH2)2PbI3, HC(NH2)2PbBr3, CH3NH3PbI3 and CH3NH3PbBr3, and discover that scattering from longitudinal optical phonons via the Fröhlich interaction is the dominant source of electron–phonon coupling near room temperature, with scattering off acoustic phonons negligible. We determine energies for the interacting longitudinal optical phonon modes to be 11.5 and 15.3 meV, and Fröhlich coupling constants of ∼40 and 60 meV for the lead iodide and bromide perovskites, respectively. Our findings correlate well with first-principles calculations based on many-body perturbation theory, which underlines the suitability of an electronic band-structure picture for describing charge carriers in hybrid perovskites. PMID:27225329

Cluster synthesis and direct ordering of rare-earth transition-metal nanomagnets.

PubMed

Balasubramanian, Balamurugan; Skomski, Ralph; Li, Xingzhong; Valloppilly, Shah R; Shield, Jeffrey E; Hadjipanayis, George C; Sellmyer, David J

2011-04-13

Rare-earth transition-metal (R-TM) alloys show superior permanent magnetic properties in the bulk, but the synthesis and application of R-TM nanoparticles remains a challenge due to the requirement of high-temperature annealing above about 800 °C for alloy formation and subsequent crystalline ordering. Here we report a single-step method to produce highly ordered R-TM nanoparticles such as YCo(5) and Y(2)Co(17), without high-temperature thermal annealing by employing a cluster-deposition system and investigate their structural and magnetic properties. The direct ordering is highly desirable to create and assemble R-TM nanoparticle building blocks for future permanent-magnet and other significant applications.

IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 1. Scandium Group (Sc, Y, La)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mioduski, Tomasz; Gumiński, Cezary, E-mail: cegie@chem.uw.edu.pl; Zeng, Dewen, E-mail: dewen-zeng@hotmail.com

2014-03-15

This work presents an assessment of solubility data for rare earth metal fluorides (generally of trivalent metals and of CeF{sub 4}) in water and in aqueous ternary systems. Compilations of all available experimental data are introduced for each rare earth metal fluoride with a corresponding critical evaluation. Every such evaluation contains a collection of all solubility results in water, a selection of suggested solubility data, and a brief discussion of the multicomponent systems. Because the ternary systems were seldom studied more than once, no critical evaluations of such data were possible. Only simple fluorides (no complexes or binary salts) aremore » treated as the input substances in this report. The literature has been covered through the end of 2013.« less

Local Polar Fluctuations in Lead Halide Perovskite Crystals