Photoinduced, copper-catalyzed alkylation of amides with unactivated secondary alkyl halides at room temperature.

PubMed

Do, Hien-Quang; Bachman, Shoshana; Bissember, Alex C; Peters, Jonas C; Fu, Gregory C

2014-02-05

The development of a mild and general method for the alkylation of amides with relatively unreactive alkyl halides (i.e., poor substrates for SN2 reactions) is an ongoing challenge in organic synthesis. We describe herein a versatile transition-metal-catalyzed approach: in particular, a photoinduced, copper-catalyzed monoalkylation of primary amides. A broad array of alkyl and aryl amides (as well as a lactam and a 2-oxazolidinone) couple with unactivated secondary (and hindered primary) alkyl bromides and iodides using a single set of comparatively simple and mild conditions: inexpensive CuI as the catalyst, no separate added ligand, and C-N bond formation at room temperature. The method is compatible with a variety of functional groups, such as an olefin, a carbamate, a thiophene, and a pyridine, and it has been applied to the synthesis of an opioid receptor antagonist. A range of mechanistic observations, including reactivity and stereochemical studies, are consistent with a coupling pathway that includes photoexcitation of a copper-amidate complex, followed by electron transfer to form an alkyl radical.

A beta-keto ester as a novel, efficient, and versatile ligand for copper(I)-catalyzed C-N, C-O, and C-S coupling reactions.

PubMed

Lv, Xin; Bao, Weiliang

2007-05-11

Employing ethyl 2-oxocyclohexanecarboxylate as a novel, efficient, and versatile ligand, the copper-catalyzed coupling reactions of various N/O/S nucleophilic reagents with aryl halides could be successfully carried out under mild conditions. A variety of products including N-arylamides, N-arylimidazoles, aryl ethers, and aryl thioethers were synthesized in good to excellent yields.

Palladium-Catalyzed, Copper(I)-Mediated Coupling of Boronic Acids and Benzylthiocyanate. A Cyanide-Free Cyanation of Boronic Acids

PubMed Central

Zhang, Zhihui; Liebeskind, Lanny S.

2008-01-01

A new method for the synthesis of nitriles is described. As a complement to the classic cyanation of aryl halides using cyanide sources and a transition metal catalyst, the palladium-catalyzed cross-coupling of thiocyanates with boronic acids in the presence of copper(I) thiophene-2-carboxylate (CuTC) affords nitriles in good to excellent yields. PMID:16956219

Chemical Origin of the Stability Difference between Copper(I)- and Silver(I)-Based Halide Double Perovskites.

PubMed

Xiao, Zewen; Du, Ke-Zhao; Meng, Weiwei; Mitzi, David B; Yan, Yanfa

2017-09-25

Recently, Cu I - and Ag I -based halide double perovskites have been proposed as promising candidates for overcoming the toxicity and instability issues inherent within the emerging Pb-based halide perovskite absorbers. However, up to date, only Ag I -based halide double perovskites have been experimentally synthesized; there are no reports on successful synthesis of Cu I -based analogues. Here we show that, owing to the much higher energy level for the Cu 3d 10 orbitals than for the Ag 4d 10 orbitals, Cu I atoms energetically favor 4-fold coordination, forming [CuX 4 ] tetrahedra (X=halogen), but not 6-fold coordination as required for [CuX 6 ] octahedra. In contrast, Ag I atoms can have both 6- and 4-fold coordinations. Our density functional theory calculations reveal that the synthesis of Cu I halide double perovskites may instead lead to non-perovskites containing [CuX 4 ] tetrahedra, as confirmed by our material synthesis efforts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper-catalyzed radical carbooxygenation: alkylation and alkoxylation of styrenes.

PubMed

Liao, Zhixiong; Yi, Hong; Li, Zheng; Fan, Chao; Zhang, Xu; Liu, Jie; Deng, Zixin; Lei, Aiwen

2015-01-01

A simple copper-catalyzed direct radical carbooxygenation of styrenes is developed utilizing alkyl bromides as radical resources. This catalytic radical difunctionalization accomplishes both alkylation and alkoxylation of styrenes in one pot. A broad range of styrenes and alcohols are well tolerated in this transformation. The EPR experiment shows that alkyl halides could oxidize Cu(I) to Cu(II) in this transformation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

EFFECT OF (PSEUDO)HALIDE INITIATORS AND COPPER COMPLEXES WITH NON-HALOGEN ANIONS ON THE ATOM TRANSFER RADICAL POLYMERIZATION. (R829580)

EPA Science Inventory

The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

A highly active and magnetically retrievable nanoferrite-DOPA-copper catalyst for the coupling of thiophenols with aryl halides

EPA Science Inventory

Diaryl sulfides were synthesized using magnetically recoverable heterogeneous Cu catalyst via one-pot multi component reaction using MW irradiation; the use of isopropanol as a benign reaction medium, easy recovery of the catalyst using an external magnet, efficient recycling...

First application of an efficient and versatile ligand for copper-catalyzed cross-coupling reactions of vinyl halides with N-heterocycles and phenols.

PubMed

Kabir, M Shahjahan; Lorenz, Michael; Namjoshi, Ojas A; Cook, James M

2010-02-05

2-Pyridin-2-yl-1H-benzoimidazole L3 is presented as a new, efficient, and versatile bidentate N-donor ligand suitable for the copper-catalyzed formation of vinyl C-N and C-O bonds. This inexpensive and easily prepared ligand facilitates copper-catalyzed cross-coupling reactions of alkenyl bromides and iodides with N-heterocycles and phenols to afford the desired cross-coupled products in good to excellent yields with full retention of stereochemistry. This method is particularly noteworthy given its efficiency, that is, mild reaction conditions, low catalyst loading, simplicity, versatility, and exceptional level of functional group tolerance.

First Application of An Efficient and Versatile Ligand for Copper-Catalyzed Cross-Coupling Reactions of Vinyl Halides with N-Heterocycles and Phenols

PubMed Central

Kabir, M. Shahjahan; Lorenz, Michael; Namjoshi, Ojas A.; Cook, James M.

2010-01-01

2-Pyridin-2-yl-1H-benzoimidazole L3 is presented as a new, efficient, and versatile bidentate N-donor ligand suitable for the copper-catalyzed formation of vinyl C-N and C-O bonds. This inexpensive and easily prepared ligand facilitates copper-catalyzed cross-coupling reactions of alkenyl bromides and iodides with N-heterocycles and phenols to afford the desired cross-coupled products in good to excellent yields with full retention of stereochemistry. This method is particularly noteworthy given its efficiency i.e., mild reaction conditions, low catalyst loading, simplicity, versatility, and exceptional level of functional group tolerance. PMID:20039699

Copper sulfate-pentahydrate-1,10-phenanthroline catalyzed amidations of alkynyl bromides. Synthesis of heteroaromatic amine substituted ynamides.

PubMed

Zhang, Yanshi; Hsung, Richard P; Tracey, Michael R; Kurtz, Kimberly C M; Vera, Eymi L

2004-04-01

A practical cross-coupling of amides with alkynyl bromides using catalytic CuSO(4).5H(2)O and 1,10-phenanthroline is described here. This catalytic protocol is more environmentally friendly than the use of CuCN or copper halides and provides a general entry for syntheses of ynamides including various new sulfonyl and heteroaromatic amine substituted ynamides. Given the interest in ynamides, this N-alkynylation of amides should be significant for the future of ynamides in organic synthesis.

Photochemistry of copper(II) complexes with macrocyclic amine ligands

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

Muralidharan, S.; Ferraudi, G.

1981-07-01

The photochemical properties of Cu(dl-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ and Cu(rac-Me/sub 6/(14)aneN/sub 4/)/sup 2 +/ in the presence and absence of axially coordinated ligands have been investigated by continuous and flash irradiations. Flash photolysis of the complexes in deaerated aqueous solutions revealed the presence of copper-ligand radical complexes with closed- and open-cycle ligands. Flash photolysis of methanolic solutions of the complexes, in the presence of halides and pseudohalides, shows Cu(III) macrocyclic intermediates. The experimental observations can be explained in terms of two primary photoprocesses with origins in distinctive charge transfer to metal states. These states have been assigned as aminomore » to copper(II) charge-transfer state and acido to copper(II) charge-transfer state.« less

Heterobimetallic acetylide bridged Cu(I)/Ru(II)-halide/pseudohalide hybrid complexes: Synthesis, structural characterization, luminescence and electrochemical studies

NASA Astrophysics Data System (ADS)

Lolage, Sanjay; Pawal, Sandip; Chavan, Sanjay

2018-01-01

A new series of heterobimetallic complexes [Cu(PPh3)(NC5H4HCdbnd NC6H4Ctbnd CC6H4Ctbnd CRu (dppe)2Cl)X] (1a-5a) have been prepared by the reaction of trans-(NC5H4HCdbnd NC6H4Ctbnd CC6H4Ctbnd C Ru(dppe)2Cl) with copper salts in presence of triphenylphosphine (where X = Cl, Br, I, N3, NCS). Our synthetic attempts and successes are discussed in combination with spectroscopic and electronic characterization of the compounds. Comparison between halides and pseudohalides were studied by thermal and electrochemical analysis where, thermally robust complexes demonstrate quasireversible redox behaviour analogous to CuI/II/RuII/III couple. Room temperature luminescence with varying electron donating and quenching abilities of halides and pseudohalides in blue-green region were observed. Concentration and solvent dependant emission displays positive solvatochromism at ambient temperature.

How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

NASA Astrophysics Data System (ADS)

Kam, K.; Lemke, K.

2014-12-01

The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with results from molecular simulations of metal halides that are aimed at characterizing the nature (i.e. relativistic structures and energies) of metal clusters in water vapor.

Polynuclear complexes of copper(I) halides: coordination chemistry and catalytic transformations of alkynes

NASA Astrophysics Data System (ADS)

Mykhalichko, B. M.; Temkin, Oleg N.; Mys'kiv, M. G.

2000-11-01

Characteristic features of the coordination chemistry of Cu(I) and mechanisms of catalytic conversions of alkynes in the CuCl-MCl-H2O-HC≡CR system (MCl is alkali metal or ammonium chloride or amine hydrochloride; R=H, CH2OH, CH=CH2, etc.) are analysed based on studies of the compositions and structures of copper(I) chloride (bromide) complexes, alkyne π-complexes and ethynyl organometallic polynuclear compounds formed in this system in solutions and in the crystalline state. The role of polynuclear complexes in various reactions of alkynes is discussed. The bibliography includes 149 references.

Copper-Catalyzed Cyclopropanol Ring Opening Csp(3)-Csp(3) Cross-Couplings with (Fluoro)Alkyl Halides.

PubMed

Ye, Zhishi; Gettys, Kristen E; Shen, Xingyu; Dai, Mingji

2015-12-18

Novel and general copper-catalyzed cyclopropanol ring opening cross-coupling reactions with difluoroalkyl bromides, perfluoroalkyl iodides, monofluoroalkyl bromides, and 2-bromo-2-alkylesters to synthesize various β-(fluoro)alkylated ketones are reported. The reactions feature mild conditions and excellent functional group compatibility and can be scaled up to gram scale. Preliminary mechanistic studies suggest the involvement of radical intermediates. The difluoroalkyl-alkyl cross-coupling products can also be readily converted to more valuable and diverse gem-difluoro-containing compounds by taking advantage of the carbonyl group resulting from cyclopropanol ring opening.

Copper(II)-Catalyzed Conversion of Aryl/Heteroaryl Boronic Acids, Boronates, and Trifluoroborates into the Corresponding Azides: Substrate Scope and Limitations.

PubMed

Grimes, Kimberly D; Gupte, Amol; Aldrich, Courtney C

2010-05-01

We report the copper(II)-catalyzed conversion of organoboron compounds into the corresponding azide derivatives. A systematic series of phenylboronic acid derivatives is evaluated to examine the importance of steric and electronic effects of the substituents on reaction yield as well as functional group compatibility. Heterocyclic substrates are also shown to participate in this mild reaction while compounds incorporating B-C(sp(3)) bonds are unreactive under the reaction conditions. The copper(II)-catalyzed boronic acid-azide coupling reaction is further extended to both boronate esters and potassium organotrifluoroborate salts. The method described herein complements existing procedures for the preparation of aryl azides from the respective amino, triazene, and halide derivatives and we expect that it will greatly facilitate copper- and ruthenium-catalyzed azide-alkyne cycloaddition reactions for the preparation of diversely functionalized 1-aryl- or 1-heteroaryl-1,2,3-triazoles derivatives.

Cadmium-free junction fabrication process for CuInSe.sub.2 thin film solar cells

DOEpatents

Ramanathan, Kannan V.; Contreras, Miguel A.; Bhattacharya, Raghu N.; Keane, James; Noufi, Rommel

1999-01-01

The present invention provides an economical, simple, dry and controllable semiconductor layer junction forming process to make cadmium free high efficiency photovoltaic cells having a first layer comprised primarily of copper indium diselenide having a thin doped copper indium diselenide n-type region, generated by thermal diffusion with a group II(b) element such as zinc, and a halide, such as chlorine, and a second layer comprised of a conventional zinc oxide bilayer. A photovoltaic device according the present invention includes a first thin film layer of semiconductor material formed primarily from copper indium diselenide. Doping of the copper indium diselenide with zinc chloride is accomplished using either a zinc chloride solution or a solid zinc chloride material. Thermal diffusion of zinc chloride into the copper indium diselenide upper region creates the thin n-type copper indium diselenide surface. A second thin film layer of semiconductor material comprising zinc oxide is then applied in two layers. The first layer comprises a thin layer of high resistivity zinc oxide. The second relatively thick layer of zinc oxide is doped to exhibit low resistivity.

Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4-Hydroxythiophenol

PubMed Central

Troyano, Javier; Perles, Josefina; Amo-Ochoa, Pilar; Martínez, Jose Ignacio; Concepción Gimeno, Maria; Fernández-Moreira, Vanesa; Zamora, Félix; Delgado, Salomé

2016-01-01

Solvothermal reactions between copper(I) halides and 4-mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu3X(HT)2]n (X= Cl, 1; Br, 2; and I, 3). The structures of these coordination polymers have been determined by X-ray diffraction at both room temperature and low temperature (110 K), showing a general shortening in Cu-S, Cu-X and Cu···Cu bond distances at low temperatures. 1 and 2 are isostructural consisting of layers in which the halogen ligands act as μ3-bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ4-mode but the layers are quasi-isostructural with 1 or 2. These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2, but weaker for 3 at room temperature, while upon cooling at 77 K 1 and 2 show stronger yellow as well as 3 displays stronger green emission. DFT calculations have been used to rationalise these observations. These results suggest a high potential for this novel and promising stimuli-responsive materials. PMID:27809369

Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4-Hydroxythiophenol.

PubMed

Troyano, Javier; Perles, Josefina; Amo-Ochoa, Pilar; Martínez, Jose Ignacio; Concepción Gimeno, Maria; Fernández-Moreira, Vanesa; Zamora, Félix; Delgado, Salomé

2016-12-12

Solvothermal reactions between copper(I) halides and 4-mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu 3 X(HT) 2 ] n (X=Cl, 1; Br, 2; and I, 3). The structures of these coordination polymers have been determined by X-ray diffraction at both room- and low temperature (110 K), showing a general shortening in Cu-S, Cu-X and Cu-Cu bond lengths at low temperatures. 1 and 2 are isostructural, consisting of layers in which the halogen ligands act as μ 3 -bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ 4 -mode but the layers are quasi-isostructural with 1 or 2. These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2, but weaker for 3 at room temperature, whereas upon cooling at 77 K 1 and 2 show stronger yellow emission, and 3 displays stronger green emission. DFT calculations have been used to rationalize these observations. These results suggest a high potential for this novel and promising stimuli-responsive materials. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Copper-Substituted Lead Perovskite Materials Constructed with Different Halides for Working (CH3NH3)2CuX4-Based Perovskite Solar Cells from Experimental and Theoretical View.

PubMed

Elseman, Ahmed Mourtada; Shalan, Ahmed Esmail; Sajid, Sajid; Rashad, Mohamed Mohamed; Hassan, Ali Mostafa; Li, Meicheng

2018-04-11

Toxicity and chemical instability issues of halide perovskites based on organic-inorganic lead-containing materials still remain as the main drawbacks for perovskite solar cells (PSCs). Herein, we discuss the preparation of copper (Cu)-based hybrid materials, where we replace lead (Pb) with nontoxic Cu metal for lead-free PSCs, and investigate their potential toward solar cell applications based on experimental and theoretical studies. The formation of (CH 3 NH 3 ) 2 CuX 4 [(CH 3 NH 3 ) 2 CuCl 4 , (CH 3 NH 3 ) 2 CuCl 2 I 2 , and (CH 3 NH 3 ) 2 CuCl 2 Br 2 ] was discussed in details. Furthermore, it was found that chlorine (Cl - ) in the structure is critical for the stabilization of the formed compounds. Cu-based perovskite-like materials showed attractive absorbance features extended to the near-infrared range, with appropriate band gaps. Green photoluminescence of these materials was obtained because of Cu + ions. The power conversion efficiency was measured experimentally and estimated theoretically for different architectures of solar cell devices.

Advances in copper-catalyzed C-C coupling reactions and related domino reactions based on active methylene compounds.

PubMed

Liu, Yunyun; Wan, Jie-Ping

2012-06-01

Active methylene compounds are a major class of reaction partners for C-C bond formation with sp(2) C-X (X = halide) fragments. As one of the most-classical versions of the Ullmann-type coupling reaction, activated-methylene-based C-C coupling reactions have been efficiently employed in a large number of syntheses. Although this type of reaction has long relied on noble-metal catalysis, the renaissance of copper catalysis at the end of last century has led to dramatic developments in Ullmann C-C coupling reactions. Owing to its low cost, abundance, as well as excellent catalytic activity, the exceptional atom economy of copper catalysis is gaining widespread attention in various organic synthesis. This review summarizes the advances in copper-catalyzed intermolecular and intramolecular C-C coupling reactions that use activated methylene species as well as in tandem reactions that are initiated by this transformation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bacteriostatic and anti-collagenolytic dental materials through the incorporation of polyacrylic acid modified CuI nanoparticles

DOEpatents

Renne, Walter George; Mennito, Anthony Samuel; Schmidt, Michael Gerard; Vuthiganon, Jompobe; Chumanov, George

2015-05-19

Provided are antibacterial and antimicrobial surface coatings and dental materials by utilizing the antimicrobial properties of copper chalcogenide and/or copper halide (CuQ, where Q=chalcogens including oxygen, or halogens, or nothing). An antimicrobial barrier is created by incorporation of CuQ nanoparticles of an appropriate size and at a concentration necessary and sufficient to create a unique bioelectrical environment. The unique bioelectrical environment results in biocidal effectiveness through a multi-factorial mechanism comprising a combination of the intrinsic quantum flux of copper (Cu.sup.0, Cu.sup.1+, Cu.sup.2+) ions and the high surface-to-volume electron sink facilitated by the nanoparticle. The result is the constant quantum flux of copper which manifests and establishes the antimicrobial environment preventing or inhibiting the growth of bacteria. The presence of CuQ results in inhibiting or delaying bacterial destruction and endogenous enzymatic breakdown of the zone of resin inter-diffusion, the integrity of which is essential for dental restoration longevity.

Electronic Devices With Diffusion Barrier and Process for Making Same

DTIC Science & Technology

2000-05-03

components. Diffusion is also a problem with other high 10 conductivity metallization materials such as gold , silver, and platinum. As can be...those of subgroup IB of the Periodic Table (i.e., copper, silver, gold ), as well as platinum. These metals are highly attractive 10 for...the metal halide molecules of the desired thickness, is formed upon the monolayer portion of the barrier -7- material. The monolayer ( monoatomic

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

Walroth, Richard C.; Miles, Kelsey C.; Lukens, James T.

Copper/aminoxyl species are proposed as key intermediates in aerobic alcohol oxidation. Several possible electronic structural descriptions of these species are possible, and here we probe this issue by examining four crystallographically characterized Cu/aminoxyl halide complexes by Cu K-edge, Cu L 2,3- edge, and Cl K-edge X-ray absorption spectroscopy. The mixing coefficients between Cu, aminoxyl, and halide orbitals are determined via these techniques with support from density functional theory. The emergent electronic structure picture reveals that Cu coordination confers appreciable oxoammonium character to the aminoxyl ligand. The computational methodology is extended to one of the putative intermediates invoked in catalytic Cu/aminoxyl-drivenmore » alcohol oxidation reactions, with similar findings. On the whole, the results have important implications for the mechanism of alcohol oxidation and the underlying basis for cooperativity in this co- catalyst system.« less

Evidence of CuI/CuII Redox Process by X-ray Absorption and EPR Spectroscopy: Direct Synthesis of Dihydrofurans from b-Ketocarbonyl Derivatives and Olefins

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

Yi, Hong; Liao, Zhixiong; Zhang, Guanghui

Abstract: The CuI/CuII and CuI/CuIII catalytic cycles have been subject to intense debate in the field of copper-catalyzed oxidative coupling reactions. A mechanistic study on the CuI/CuII redox process, by X-ray absorption (XAS) and electron paramagnetic resonance (EPR) spectroscopies, has elucidated the reduction mechanism of CuII to CuI by 1,3-diketone and detailed investigation revealed that the halide ion is important for the reduction process. The oxidative nature of the thereby-formed CuI has also been studied by XAS and EPR spectroscopy. This mechanistic information is applicable to the copper-catalyzed oxidative cyclization of b-ketocarbonyl derivatives to dihydrofurans. This protocol provides an idealmore » route to highly substituted dihydrofuran rings from easily available 1,3-dicarbonyls and olefins. Copper« less

Photographic Processing Interpretation Facility Wastewater Conceptual Treatment Design.

DTIC Science & Technology

1983-03-01

Total Chromium (Cr) - - - ɘ.05 - Copper (Cu) - - - ɘ.05 - Iron (Fe) - - - - - Manganese (Mn) - - - ɘ.03 - Mercury (Hg) - - - ɘ.004 - Potassium (K...8.3 - Silver (Ag) 2.2 7.0 17 0.15 2.2 Sodium (Na) - - - 8.2 - Zinc (Zn) - - - 0.12 - Biochemical Oxygen " Demand (BOD_) - - - 40 - Sulfate (SO...nonconventional pollutants include boron, dissolved sol i halides, iron, ammonia, nitrogen, phenols, sulfate and TOC. ,P,, 99 percent of the 11,000

Microwave-assisted Ullmann C-S bond formation: synthesis of the P38alpha MAPK clinical candidate VX-745.

PubMed

Bagley, Mark C; Davis, Terence; Dix, Matthew C; Fusillo, Vincenzo; Pigeaux, Morgane; Rokicki, Michal J; Kipling, David

2009-11-06

Microwave irradiation promotes the rapid and efficient reaction of a thiophenol and aryl or heteroaryl halide using a copper or palladium catalyst and a range of ligands, depending upon substrate. Of particular utility is the use of copper(I) iodide (5 mol %) and trans-cyclohexane-1,2-diol as ligand under basic conditions and microwave irradiation to give the corresponding sulfide in high yield. This method for C-S bond formation is applied in the four-step synthesis of the clinical candidate VX-745 in 38% overall yield. The inhibitory activity of VX-745 against p38alpha MAPK is confirmed in Werner syndrome dermal fibroblasts at 1.0 microM concentration by immunoblot assay.

Carbon monoxide sensor and method of use

DOEpatents

Dutta, Prabir K.; Swartz, Scott L.; Holt, Christopher T.; Revur, Ramachandra Rao

2006-01-10

A sensor and method of use for detection of low levels of carbon monoxide in gas mixtures. The approach is based on the change in an electrical property (for example: resistance) that occurs when carbon monoxide is selectively absorbed by a film of copper chloride (or other metal halides). The electrical property change occurs rapidly with both increasing and decreasing CO contents, varies with the amount of CO from the gas stream, and is insensitive to the presence of hydrogen. To make a sensor using this approach, the metal halide film will deposited onto an alumina substrate with electrodes. The sensor may be maintained at the optimum temperature with a thick film platinum heater deposited onto the opposite face of the substrate. When the sensor is operating at an appropriate (and constant) temperature, the magnitude of the electrical property measured between the interdigital electrodes will provide a measure of the carbon monoxide content of the gas.

Regioselective copper-catalyzed alkylation of [2.2.2]-acylnitroso cycloadducts: remarkable effect of the halide of Grignard reagents.

PubMed

Crotti, Stefano; Bertolini, Ferruccio; di Bussolo, Valeria; Pineschi, Mauro

2010-04-16

Ring opening with organometallic reagents of [2.2.2]-acylnitroso cycloadducts, including an enantioselective kinetic resolution of these compounds, has been accomplished for the first time. By the careful choice of reaction conditions, it was possible to obtain new cyclohexenyl hydroxamic acids with complete anti-stereoselectivity and a nice regioalternating control. A remarkable effect of the halogen of the Grignard reagent was observed during ring opening.

Investigation of magnetic exchange via non-bonding halides and aromatic polyamines (1,2,4-triazine, 1,2,4,5-tetrazine and the related derivatives as ligands)

NASA Astrophysics Data System (ADS)

Li, Lixin

Low dimensional antiferromagnetic materials have received considerable attention from both chemists and physicists because of their potential application as functional materials, such as superconductors. Magnetic moments can propagate via multiple pathways such as via two-halide superexchange interactions in A2MX4 systems (where A is an organic cation and X is halides), or through bonding conjugated systems. One route for generating two-halide A2MX4 systems is via crystal packing of transition metal anions and organic cations. Following this method, we have prepared a series compounds in the (5-SAP)2CuX 4 family (where 5-SAP is a 5-substituted-2-aminopyridinium cation) and the A2CuX4 family. Eleven compounds have been prepared. They include bis(2-amino-5-fluoropyridinium) tetrachlorocuprate(II) (5-FAP) 2CuCl4 (1), bis(2-amino-5-fluoropyridinium) tetrabromocuprate(II) (5-FAP)2CuBr4 (2), bis(2-amino-5-iodopyridine) dibromocopper(II) (5-iap)2CuBr 2 dimer (3) and chain (4) forms, bis(2-amino-5-iodopyridine) dichlorocopper(II) hydrate (5-iap)2CuCl2·1.7H 2O (5), 2-amino-5-ammoniumpyridinium trichlorocuprate(II) chloride (DAP)(CuCl3)Cl (6), bis(2-amino-3-chloro-5-trifluoromethylpyridinium) tetrabromocuprate(II) (TMCAP)2CuBr4 (7) and its tetrachlorocuprate(II) analog (TMCAP)2CuCl4 (8), bis(4-aminopyridinium) tetrabromocuprate(II) monohydrate (4-AP) 2CuBr4-H2O (9), bis(3-methylpyridinium) tetrabromocuprate(II) (3-MP)2CuBr4 (10) and bis[methyl(2-phenylethyl)ammonium] tetrabromocuprate(II) (NMPH)2 CuBr4 (11). The structures and magnetic properties have been studied. Experimental data and theoretical calculations show that the strength of magnetic exchange is related to the geometric parameters of the non-bonding two-halide contacts, rather than direct contact between the copper(II) ions. The self-assembly technique can also be used to prepare magnetic networks. A variety of coordination polymers with magnetic properties have been synthesized based on different N-heterocyclic ligands such as pyrazine and its derivatives. Magnetic exchange can propagate through the conjugated system. As an extension of this method, we focused on using some new polyamines including 1,2,4,5-tetrazine (tetz), 1,2,4-triazine (tz) and the amino derivative 3-amino-1,2,4-triazine (atz) as ligands. Four new complexes have been prepared. They include bis(hexafluoroacetylacetonato)copper(II) Cu(hfac)2(C2H2N4) (13), bis(hexafluoroacetylacetonato)triazinecopper(II) Cu(hfac)2(tz) (15), bis(hexafluoroacetylacetonato)(3-aminotriazine)copper(II) Cu(hfac) 2(atz)2 (16) and hexakis(hexafluoroacetylacetonato)bis(3-aminotriazine)tricopper(II) Cu3(hfac)6(atz)2 (17). The crystal structures and magnetic properties have been studied. The magnetic data show they are paramagnetic materials because of the weak coordination bonds. To compare with its atz analog, 2-aminopyrazine (apz) was also used and three new complexes have been prepared. They include hexakis(hexafluoroacetylacetonato) bis(2-amino-pyrazine)tricopper(II) Cu3(hfac)6 (apz)2 (18), bis(hexafluoroacetylacetonato)aminopyrazinecopper(II) Cu(hfac)2(apz)2 (19) and bis(acetylacetonato)aminopyrazinecopper(II) Cu(acac)2(apz)2 (20). The structures and their magnetic properties have been investigated.

Syntheses, crystal structures, and properties of six new lanthanide(III) transition metal tellurium(IV) oxyhalides with three types of structures.

PubMed

Shen, Yue-Ling; Mao, Jiang-Gao

2005-07-25

Solid-state reactions of lanthanide(III) oxide (and lanthanide(III) oxyhalide), transition metal halide (and transition metal oxide), and TeO(2) at high temperature lead to six new lanthanide transition metal tellurium(IV) oxyhalides with three different types of structures, namely, DyCuTe(2)O(6)Cl, ErCuTe(2)O(6)Cl, ErCuTe(2)O(6)Br, Sm(2)Mn(Te(5)O(13))Cl(2), Dy(2)Cu(Te(5)O(13))Br(2), and Nd(4)Cu(TeO(3))(5)Cl(3). Compounds DyCuTe(2)O(6)Cl, ErCuTe(2)O(6)Cl, and ErCuTe(2)O(6)Br are isostructural. The lanthanide(III) ion is eight-coordinated by eight oxygen atoms, and the copper(II) ion is five-coordinated by four oxygens and a halide anion in a distorted square pyramidal geometry. The interconnection of Ln(III) and Cu(II) ions by bridging tellurite anions results in a three-dimensional (3D) network with tunnels along the a-axis; the halide anion and the lone-pair electrons of the tellurium(IV) ions are oriented toward the cavities of the tunnels. Compounds Sm(2)Mn(Te(5)O(13))Cl(2) and Dy(2)Cu(Te(5)O(13))Br(2) are isostructural. The lanthanide(III) ions are eight-coordinated by eight oxygens, and the divalent transition metal ion is octahedrally coordinated by six oxygens. Two types of polymeric tellurium(IV) oxide anions are formed: Te(3)O(8)(4)(-) and Te(4)O(10)(4)(-). The interconnection of the lanthanide(III) and divalent transition metal ions by the above two types of polymeric tellurium(IV) oxide anions leads to a 3D network with long, narrow-shaped tunnels along the b-axis. The halide anions remain isolated and are located at the above tunnels. Nd(4)Cu(TeO(3))(5)Cl(3) features a different structure. All five of the Nd(III) ions are eight-coordinated (NdO(8) for Nd(1), Nd(2), Nd(4), and Nd(5) and NdO(7)Cl for Nd(3)), and the copper(I) ion is tetrahedrally coordinated by four chloride anions. The interconnection of Nd(III) ions by bridging tellurite anions resulted in a 3D network with large tunnels along the b-axis. The CuCl(4) tetrahedra are interconnected into a 1D two-unit repeating (zweier) chain via corner-sharing. These 1D copper(I) chloride chains are inserted into the tunnels of the neodymium(III) tellurite via Nd-Cl-Cu bridges. Luminescent studies show that ErCuTe(2)O(6)Cl and Nd(4)Cu(TeO(3))(5)Cl(3) exhibit strong luminescence in the near-IR region. Magnetic measurements indicate the antiferromagnetic interactions between magnetic centers in these compounds.

Copper-catalyzed trifluoromethylthiolation of aryl halides with diverse directing groups.

PubMed

Xu, Jiabin; Mu, Xin; Chen, Pinhong; Ye, Jinxing; Liu, Guosheng

2014-08-01

The expansion of cross-coupling components in Cu-catalyzed C-X bond forming reactions have received much attention recently. A novel Cu-catalyzed trifluoromethylthiolation of aryl bromides and iodides with the assistance of versatile directing groups such as pyridyl, methyl ester, amide, imine and oxime was reported. CuBr was used as the catalyst, and 1,10-phenanthroline as the ligand. By changing the solvent from acetonitrile to DMF, the coupling process could even take place at room temperature.

CH functionalization of heteroaromatic compounds by transition metal catalysis

NASA Astrophysics Data System (ADS)

Tanba, Shunsuke; Fujiwara, Taiki; Monguchi, Daiki; Mori, Atsunori

2010-06-01

Transition metal-catalyzed CH functioanlization of thiazoles and thiophenes are carried out. The reaction of thiophene with aryl halide in the presence of a palladium catalyst underwent the CC bond forming reaction at the CH bond of thiophene. By employing the reaction head-to-tail-type oligothiophene is synthesized in a stepwise manner. When several azoles are treated with secondary amines and amides in the presence of a copper catalyst, oxidative CH-NH coupling took place to form the carbon-nitrogen bond.

Copper complexes of anionic nitrogen ligands in the amidation and imidation of aryl halides.

PubMed

Tye, Jesse W; Weng, Zhiqiang; Johns, Adam M; Incarvito, Christopher D; Hartwig, John F

2008-07-30

Copper(I) imidate and amidate complexes of chelating N,N-donor ligands, which are proposed intermediates in copper-catalyzed amidations of aryl halides, have been synthesized and characterized by X-ray diffraction and detailed solution-phase methods. In some cases, the complexes adopt neutral, three-coordinate trigonal planar structures in the solid state, but in other cases they adopt an ionic form consisting of an L 2Cu (+) cation and a CuX 2 (-) anion. A tetraalkylammonium salt of the CuX 2 (-) anion in which X = phthalimidate was also isolated. Conductivity measurements and (1)H NMR spectra of mixtures of two complexes all indicate that the complexes exist predominantly in the ionic form in DMSO and DMF solutions. One complex was sufficiently soluble for conductance measurements in less polar solvents and was shown to adopt some degree of the ionic form in THF and predominantly the neutral form in benzene. The complexes containing dative nitrogen ligands reacted with iodoarenes and bromoarenes to form products from C-N coupling, but the ammonium salt of [Cu(phth) 2] (-) did not. Similar selectivities for stoichiometric and catalytic reactions with two different iodoarenes and faster rates for the stoichiometric reactions implied that the isolated amidate and imidate complexes are intermediates in the reactions of amides and imides with haloarenes catalyzed by copper complexes containing dative N,N ligands. These amidates and imidates reacted much more slowly with chloroarenes, including chloroarenes that possess more favorable reduction potentials than some bromoarenes and that are known to undergo fast dissociation of chloride from the chloroarene radical anion. The reaction of o-(allyloxy)iodobenzene with [(phen) 2Cu][Cu(pyrr) 2] results in formation of the C-N coupled product in high yield and no detectable amount of the 3-methyl-2,3-dihydrobenzofuran or 3-methylene-2,3-dihydrobenzofuran products that would be expected from a reaction that generated free radicals. These data and computed reaction barriers argue against mechanisms in which the haloarene reacts with a two-coordinate anionic copper species and mechanisms that start with electron transfer to generate a free iodoarene radical anion. Instead, these data are more consistent with mechanisms involving cleavage of the carbon-halogen bond within the coordination sphere of the metal.

Design of a Photoredox Catalyst that Enables the Direct Synthesis of Carbamate-Protected Primary Amines via Photoinduced, Copper-Catalyzed N-Alkylation Reactions of Unactivated Secondary Halides.

PubMed

Ahn, Jun Myun; Peters, Jonas C; Fu, Gregory C

2017-12-13

Despite the long history of S N 2 reactions between nitrogen nucleophiles and alkyl electrophiles, many such substitution reactions remain out of reach. In recent years, efforts to develop transition-metal catalysts to address this deficiency have begun to emerge. In this report, we address the challenge of coupling a carbamate nucleophile with an unactivated secondary alkyl electrophile to generate a substituted carbamate, a process that has not been achieved effectively in the absence of a catalyst; the product carbamates can serve as useful intermediates in organic synthesis as well as bioactive compounds in their own right. Through the design and synthesis of a new copper-based photoredox catalyst, bearing a tridentate carbazolide/bisphosphine ligand, that can be activated upon irradiation by blue-LED lamps, we can achieve the coupling of a range of primary carbamates with unactivated secondary alkyl bromides at room temperature. Our mechanistic observations are consistent with the new copper complex serving its intended role as a photoredox catalyst, working in conjunction with a second copper complex that mediates C-N bond formation in an out-of-cage process.

Copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides

NASA Astrophysics Data System (ADS)

Peyronel, Giorgio; Malavasi, Wanda; Pignedoli, Anna

Some copper(I), silver(I) and gold(I) halide complexes with the dithioformamidinium dihalides (Tu 2X 2) were prepared and studied by infrared spectroscopy and conductometry: 3CuX.2Tu 2X 2(XCl,I), CuBr.Tu 2Br 2, 4CuBr.3.5Tu 2Br 2.MeOH, 2CuBr.Tu 2Br 2.0.66EtOH, 3CuI.2Tu 2I 2, 2AgCl.2.5Tu 2Cl 2, 3AgCl.2Tu 2Cl 2.0.5EtOH, 3AgCl.Tu 2Cl 2, 2AgBr.2Tu 2Br 2.0.5Tu 2(NO 3) 2.H 2O, AgBr.Tu 2Br 2, 4AgBr.Tu 2Br 2, 4AgI.0.5Tu 2I 2.EtOH, AuCl.1.5Tu 2Cl 2, 4AuCl.3.5Tu 2Cl 2.2DMF, AuBr.4Tu 2Br 2, AuBr.2Tu 2Br 2.1.5DMF, AuI.5Tu 2I 2, AuI.Tu 2I 2. A decrease of the ν(NH), δ(NH 2) and ν(CN 2) frequencies and an increase of the ν(CS) frequencies indicate an N-coordination of the dithioformamidinium cation to the metal ions; ν(MN) and ν(MX) frequencies are tentatively assigned in the far-infrared spectra.

Final Project Report for ER15351 “A Study of New Actinide Zintl Ion Materials”

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

Peter K. Dorhout

2007-11-12

The structural chemistry of actinide main-group metal materials provides the fundamental basis for the understanding of structural coordination chemistry and the formation of materials with desired or predicted structural features. The main-group metal building blocks, comprising sulfur-group, phosphorous-group, or silicon-group elements, have shown versatility in oxidation state, coordination, and bonding preferences. These building blocks have allowed us to elucidate a series of structures that are unique to the actinide elements, although we can find structural relationships to transition metal and 4f-element materials. In the past year, we investigated controlled metathesis and self-propagating reactions between actinide metal halides and alkali metalmore » salts of main-group metal chalcogenides such as K-P-S salts. Ternary plutonium thiophosphates have resulted from these reactions at low temperature in sealed ampules. we have also focused efforts to examine reactions of Th, U, and Pu halide salts with other alkali metal salts such as Na-Ge-S and Na-Si-Se and copper chloride to identify if self-propagating reactions may be used as a viable reaction to prepare new actinide materials and we prepared a series of U and Th copper chalcogenide materials. Magnetic measurements continued to be a focus of actinide materials prepared in our laboratory. We also contributed to the XANES work at Los Alamos by preparing materials for study and for comparison with environmental samples.« less

An efficient copper-based magnetic nanocatalyst for the fixation of carbon dioxide at atmospheric pressure.

PubMed

Sharma, Rakesh Kumar; Gaur, Rashmi; Yadav, Manavi; Goswami, Anandarup; Zbořil, Radek; Gawande, Manoj B

2018-01-30

In the last few decades, the emission of carbon dioxide (CO 2 ) in the environment has caused havoc across the globe. One of the most promising strategies for fixation of CO 2 is the cycloaddition reaction between epoxides and CO 2 to produce cyclic carbonates. For the first time, we have fabricated copper-based magnetic nanocatalyst and have applied for the CO 2 fixation. The prepared catalyst was thoroughly characterized using various techniques including XRD, FT-IR, TEM, FE-SEM, XPS, VSM, ICP-OES and elemental mapping. The reactions proceeded at atmospheric pressure, relatively lower temperature, short reaction time, solvent- less and organic halide free reaction conditions. Additionally, the ease of recovery through an external magnet, reusability of the catalyst and excellent yields of the obtained cyclic carbonates make the present protocol practical and sustainable.

Palladium-Copper Catalyzed Alkyne Activation as an Entry to Multicomponent Syntheses of Heterocycles

NASA Astrophysics Data System (ADS)

Müller, Thomas J. J.

Alkynones and chalcones are of paramount importance in heterocyclic chemistry as three-carbon building blocks. In a very efficient manner, they can be easily generated by palladium-copper catalyzed reactions: ynones are formed from acid chlorides and terminal alkynes, and chalcones are synthesized in the sense of a coupling-isomerization (CI) sequence from (hetero)aryl halides and propargyl alcohols. Mild reaction conditions now open entries to sequential and consecutive transformations to heterocycles, such as furans, 3-halo furans, pyrroles, pyrazoles, substituted and annelated pyridines, annelated thiopyranones, pyridimines, meridianins, benzoheteroazepines and tetrahydro-β-carbolines, by consecutive coupling-cyclocondensation or CI-cyclocondensation sequences, as new diversity oriented routes to heterocycles. Domino reactions based upon the coupling-isomerization reaction (CIR) have been probed in the synthesis of antiparasital 2-substituted quinoline derivatives and highly luminescent spiro-benzofuranones and spiro-indolones.

SAD phasing of a structure based on cocrystallized iodides using an in-house Cu Kalpha X-ray source: effects of data redundancy and completeness on structure solution.

PubMed

Yogavel, Manickam; Gill, Jasmita; Mishra, Prakash Chandra; Sharma, Amit

2007-08-01

Superoxide dismutase (SOD) from Potentilla atrosanguinea (Wall. ex. Lehm.) was crystallized using 20% PEG 3350 and 0.2 M ammonium iodide and diffraction data were collected to 2.36 A resolution using an in-house Cu Kalpha X-ray source. Analyses show that data with a redundancy of 3.2 were sufficient to determine the structure by the SAD technique using the iodine anomalous signal. This redundancy is lower than that in previous cases in which protein structures were determined using iodines for phasing and in-house copper X-ray sources. Cocrystallization of proteins with halide salts such as ammonium iodide in combination with copper-anode X-ray radiation can therefore serve as a powerful and easy avenue for structure solution.

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.

Multicomponent click synthesis of new 1,2,3-triazole derivatives of pyrimidine nucleobases: promising acidic corrosion inhibitors for steel.

PubMed

González-Olvera, Rodrigo; Espinoza-Vázquez, Araceli; Negrón-Silva, Guillermo E; Palomar-Pardavé, Manuel E; Romero-Romo, Mario A; Santillan, Rosa

2013-12-06

A series of new mono-1,2,3-triazole derivatives of pyrimidine nucleobases were synthesized by one-pot copper(I)-catalyzed 1,3-dipolar cycloaddition reactions between N-1-propargyluracil and thymine, sodium azide and several benzyl halides. The desired heterocyclic compounds were obtained in good yields and characterized by NMR, IR, and high resolution mass spectrometry. These compounds were investigated as corrosion inhibitors for steel in 1 M HCl solution, using electrochemical impedance spectroscopy (EIS) technique. The results indicate that these heterocyclic compounds are promising acidic corrosion inhibitors for steel.

1 : 2 Adducts of copper(I) halides with 1,2-bis(di-2-pyridylphosphino)ethane: solid state and solution structural studies and antitumour activity.

PubMed

Bowen, Richard J; Navarro, Maribel; Shearwood, Anne-Marie J; Healy, Peter C; Skelton, Brian W; Filipovska, Aleksandra; Berners-Price, Susan J

2009-12-28

The 1 : 2 adducts of copper(I) halides with 1,2-bis(2-pyridylphosphino)ethane (d2pype) have been synthesized and solution properties characterized by variable temperature (1)H, (31)P and (65)Cu NMR spectroscopy. Single-crystal structure determinations for the chloride, bromide and iodide complexes show these to crystallize from acetonitrile in the triclinic space group P1 as isostructural centrosymmetric dimers [(d2pype)Cu(mu-d2pype)(2)Cu(d2pype)]X(2).(solvent) with a approximately 12.6, b approximately 12.7, c approximately 15.3 A, alpha approximately 84, beta approximately 67, gamma approximately 84 degrees. In contrast to the analogous AuCl:2(d2pype) and AgNO(3):2(d2pype) adducts, in solution these CuX:2(d2pype) adducts (where X = Cl, Br and I) exist almost exclusively as bis-chelated monomeric [Cu(d2pype)(2)]X; evidence for an equilibrium between monomeric and dimeric forms is detected only for the CuCl adduct in methanol. Cytotoxicity studies in two human breast cancer lines and two matched liver progenitor cell lines indicate that [Cu(d2pype)(2)]Cl is non selectively toxic to both non-tumourigenic and tumourigenic cells. However, the analogous Au(I) compound [Au(d2pype)(2)]Cl, is toxic to highly tumourigenic cells and more selective in its toxicity to tumourigenic cells compared to non-tumourigenic cells. The significance of these results to the further development of selective, mitochondria-targeted, Au(I) antitumour complexes is discussed.

Intermediate Temperature Fluids Life Tests - Experiments

NASA Technical Reports Server (NTRS)

Anderson, William G.; Bonner, Richard W.; Dussinger, Peter M.; Hartenstine, John R.; Sarraf, David B.; Locci, Ivan E.

2007-01-01

There are a number of different applications that could use heat pipes or loop heat pipes (LHPs) in the intermediate temperature range of 450 to 725 K (170 to 450 C), including space nuclear power system radiators, fuel cells, and high temperature electronics cooling. Historically, water has been used in heat pipes at temperatures up to about 425 K (150 C). Recent life tests, updated below, demonstrate that titanium/water and Monel/water heat pipes can be used at temperatures up to 550 K (277 C), due to water's favorable transport properties. At temperatures above roughly 570 K (300 C), water is no longer a suitable fluid, due to high vapor pressure and low surface tension as the critical point is approached. At higher temperatures, another working fluid/envelope combination is required, either an organic or halide working fluid. An electromotive force method was used to predict the compatibility of halide working fluids with envelope materials. This procedure was used to reject aluminum and aluminum alloys as envelope materials, due to their high decomposition potential. Titanium and three corrosion resistant superalloys were chosen as envelope materials. Life tests were conducted with these envelopes and six different working fluids: AlBr3, GaCl3, SnCl4, TiCl4, TiBr4, and eutectic diphenyl/diphenyl oxide (Therminol VP-1/Dowtherm A). All of the life tests except for the GaCl3 are ongoing; the GaCl3 was incompatible. As the temperature approaches 725 K (450 C), cesium is a potential heat pipe working fluid. Life tests results are also presented for cesium/Monel 400 and cesium/70-30 copper/nickel heat pipes operating near 750 K (477 C). These materials are not suitable for long term operation, due to copper transport from the condenser to the evaporator.

Biosorption of Heavy Metals from Aqueous Solution by Bacteria Isolated from Contaminated Soil.

PubMed

Dhanwal, Pradeep; Kumar, Anil; Dudeja, Shruti; Badgujar, Hemlata; Chauhan, Rohit; Kumar, Abhishek; Dhull, Poonam; Chhokar, Vinod; Beniwal, Vikas

2018-05-01

  This study was carried out to analyze the heavy metals biosorption potential of bacteria isolated from soil contaminated with electroplating industrial effluents. Bacterial isolates were screened for their multi-metal biosorption potential against copper, nickel, lead, and chromium. Bacterial isolate CU4A showed the maximum uptake of copper, nickel, lead, and chromium in aqueous solution, with a biosorption efficiency of 87.16 %, 79.62%, 84.92%, and 68.12%, respectively. The bacterial strain CU4A was identified as Bacillus cereus, following 16S rRNA gene sequence analysis. The surface chemical functional groups of bacterial biomass were identified by Fourier transform infrared (FTIR) spectroscopy as hydroxyl, carboxyl, amine, and halide, which may be involved in the biosorption of heavy metals. Analysis with scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) confirmed the adsorption of metals on the bacterial cell mass. The results of this study are significant and could be further investigated for the removal of heavy metals from contaminated environments.

Use of radiation in preparative chemistry

NASA Technical Reports Server (NTRS)

Philipp, W. H.; Marksik, S. J.; May, C. E.; Lad, R. A.

1971-01-01

A summary and updating of previous work on the use of radiation chemistry for the preparation of pure materials are presented. Work was chiefly concerned with the reduction of metal salts in solution to the free metal using 2 MeV electrons. Metals deposited from aqueous solution are copper, silver, zinc, cadmium, thallium, tin, lead, antimony, iron, nickel, cobalt, and palladium. Dry organic solvents were evaluated for the deposition of metals based on a study involving deposition of antimony from soltions of antimony (III) chloride. The use of organic liquids for the preparation of anhydrous metal halides is also presented. Reaction mechanisms for both organic liquids and aqueous system are discussed.

Electric polarization switching in an atomically thin binary rock salt structure

NASA Astrophysics Data System (ADS)

Martinez-Castro, Jose; Piantek, Marten; Schubert, Sonja; Persson, Mats; Serrate, David; Hirjibehedin, Cyrus F.

2018-01-01

Inducing and controlling electric dipoles is hindered in the ultrathin limit by the finite screening length of surface charges at metal-insulator junctions1-3, although this effect can be circumvented by specially designed interfaces4. Heterostructures of insulating materials hold great promise, as confirmed by perovskite oxide superlattices with compositional substitution to artificially break the structural inversion symmetry5-8. Bringing this concept to the ultrathin limit would substantially broaden the range of materials and functionalities that could be exploited in novel nanoscale device designs. Here, we report that non-zero electric polarization can be induced and reversed in a hysteretic manner in bilayers made of ultrathin insulators whose electric polarization cannot be switched individually. In particular, we explore the interface between ionic rock salt alkali halides such as NaCl or KBr and polar insulating Cu2N terminating bulk copper. The strong compositional asymmetry between the polar Cu2N and the vacuum gap breaks inversion symmetry in the alkali halide layer, inducing out-of-plane dipoles that are stabilized in one orientation (self-poling). The dipole orientation can be reversed by a critical electric field, producing sharp switching of the tunnel current passing through the junction.

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

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

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.

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.

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

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

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

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.

Method for producing hydrocarbon fuels and fuel gas from heavy polynuclear hydrocarbons by the use of molten metal halide catalysts

DOEpatents

Gorin, Everett

1979-01-01

In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst in a hydrocracking zone, thereafter separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide and thereafter regenerating the spent molten metal halide by incinerating the spent molten metal halide by combustion of carbon and sulfur compounds in the spent molten metal halide in an incineration zone, the improvement comprising: (a) contacting the heavy feedstocks and hydrogen in the presence of the molten metal halide in the hydrocracking zone at reaction conditions effective to convert from about 60 to about 90 weight percent of the feedstock to lighter hydrocarbon fuels; (b) separating at least a major portion of the lighter hydrocarbon fuels from the spent molten metal halide; (c) contacting the spent molten metal halide with oxygen in a liquid phase gasification zone at a temperature and pressure sufficient to vaporize from about 25 to about 75 weight percent of the spent metal halide, the oxygen being introduced in an amount sufficient to remove from about 60 to about 90 weight percent of the carbon contained in the spent molten metal halide to produce a fuel gas and regenerated metal halide; and (d) incinerating the spent molten metal halide by combusting carbon and sulfur compounds contained therein.

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.

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%.

TRANSURANIC METAL HALIDES AND A PROCESS FOR THE PRODUCTION THEREOF

DOEpatents

Fried, S.

1951-03-20

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

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)

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.

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)

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.

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/.

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.

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.

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.

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.

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

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...

PREPARATION OF URANIUM-ALUMINUM ALLOYS

DOEpatents

Moore, R.H.

1962-09-01

A process is given for preparing uranium--aluminum alloys from a solution of uranium halide in an about equimolar molten alkali metal halide-- aluminum halide mixture and excess aluminum. The uranium halide is reduced and the uranium is alloyed with the excess aluminum. The alloy and salt are separated from each other. (AEC)

Electrolytic systems and methods for making metal halides and refining metals

DOEpatents

Holland, Justin M.; Cecala, David M.

2015-05-26

Disclosed are electrochemical cells and methods for producing a halide of a non-alkali metal and for electrorefining the halide. The systems typically involve an electrochemical cell having a cathode structure configured for dissolving a hydrogen halide that forms the halide into a molten salt of the halogen and an alkali metal. Typically a direct current voltage is applied across the cathode and an anode that is fabricated with the non-alkali metal such that the halide of the non-alkali metal is formed adjacent the anode. Electrorefining cells and methods involve applying a direct current voltage across the anode where the halide of the non-alkali metal is formed and the cathode where the non-alkali metal is electro-deposited. In a representative embodiment the halogen is chlorine, the alkali metal is lithium and the non-alkali metal is uranium.

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.

METHOD OF MAKING ALLOYS OF BERYLLIUM WITH PLUTONIUM AND THE LIKE

DOEpatents

Runnals, O.J.C.

1959-02-24

The production of alloys of beryllium with one or more of the metals uranium, plutonium, actinium, americium, curium, thorium, and cerium are described. A halide salt of the metal to be alloyed with the beryllium is heated at 1300 deg C in the presence of beryllium to reduce the halide to metal and cause the latter to alloy directly with the beryllium. Although the heavy metal halides are more stable, thermodynamically, than the beryllium halides, the reducing reaction proceeds to completion if the beryllium halide product is continuously removed by vacuum distillation.

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.

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.

10 CFR Appendix B to Subpart S to... - Certification Report for Metal Halide Lamp Ballasts

Code of Federal Regulations, 2011 CFR

2011-01-01

... 10 Energy 3 2011-01-01 2011-01-01 false Certification Report for Metal Halide Lamp Ballasts B... PROGRAM FOR CERTAIN COMMERCIAL AND INDUSTRIAL EQUIPMENT Metal Halide Lamp Ballasts and Fixtures Pt. 431, Subpt. S, App. B Appendix B to Subpart S to Part 431—Certification Report for Metal Halide Lamp Ballasts...

Method for recovering hydrocarbons from molten metal halides

DOEpatents

Pell, Melvyn B.

1979-01-01

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

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.

Method of making alloys of beryllium with plutonium and the like

DOEpatents

Runnals, O J.C.

1959-02-24

The production or alloys of beryllium with one or more of the metals uranium, plutonium, actinium, americium, curium, thorium, and cerium is described. A halide salt or the metal to be alloyed with the beryllium is heated at l3O0 deg C in the presence of beryllium to reduce the halide to metal and cause the latter to alloy directly with the beryllium. Although the heavy metal halides are more stable, thermodynamically, than the beryllium halides, the reducing reaction proceeds to completion if the beryllium halide product is continuously removed by vacuum distillation.

Method for producing hydrocarbon fuels from heavy polynuclear hydrocarbons by use of molten metal halide catalyst

DOEpatents

Gorin, Everett

1979-01-01

In a process for hydrocracking heavy polynuclear carbonaceous feedstocks to produce lighter hydrocarbon fuels by contacting the heavy feedstocks with hydrogen in the presence of a molten metal halide catalyst, thereafter separating at least a substantial portion of the carbonaceous material associated with the reaction mixture from the spent molten metal halide and thereafter regenerating the metal halide catalyst, an improvement comprising contacting the spent molten metal halide catalyst after removal of a major portion of the carbonaceous material therefrom with an additional quantity of hydrogen is disclosed.

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.

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...

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...

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.

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

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.

Luminescent zero-dimensional organic metal halide hybrids with near-unity quantum efficiency.

PubMed

Zhou, Chenkun; Lin, Haoran; Tian, Yu; Yuan, Zhao; Clark, Ronald; Chen, Banghao; van de Burgt, Lambertus J; Wang, Jamie C; Zhou, Yan; Hanson, Kenneth; Meisner, Quinton J; Neu, Jennifer; Besara, Tiglet; Siegrist, Theo; Lambers, Eric; Djurovich, Peter; Ma, Biwu

2018-01-21

Single crystalline zero-dimensional (0D) organic-inorganic hybrid materials with perfect host-guest structures have been developed as a new generation of highly efficient light emitters. Here we report a series of lead-free organic metal halide hybrids with a 0D structure, (C 4 N 2 H 14 X) 4 SnX 6 (X = Br, I) and (C 9 NH 20 ) 2 SbX 5 (X = Cl), in which the individual metal halide octahedra (SnX 6 4- ) and quadrangular pyramids (SbX 5 2- ) are completely isolated from each other and surrounded by the organic ligands C 4 N 2 H 14 X + and C 9 NH 20 + , respectively. The isolation of the photoactive metal halide species by the wide band gap organic ligands leads to no interaction or electronic band formation between the metal halide species, allowing the bulk materials to exhibit the intrinsic properties of the individual metal halide species. These 0D organic metal halide hybrids can also be considered as perfect host-guest systems, with the metal halide species periodically doped in the wide band gap matrix. Highly luminescent, strongly Stokes shifted broadband emissions with photoluminescence quantum efficiencies (PLQEs) of close to unity were realized, as a result of excited state structural reorganization of the individual metal halide species. Our discovery of highly luminescent single crystalline 0D organic-inorganic hybrid materials as perfect host-guest systems opens up a new paradigm in functional materials design.

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 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 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 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...

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...

Deuterium separation by infrared-induced addition reaction

DOEpatents

Marling, John B.

1977-01-01

A method for deuterium enrichment by the infrared-induced addition reaction of a deuterium halide with an unsaturated aliphatic compound. A gaseous mixture of a hydrogen halide feedstock and an unsaturated aliphatic compound, particularly an olefin, is irradiated to selectively vibrationally excite the deuterium halide contained therein. The excited deuterium halide preferentially reacts with the unsaturated aliphatic compound to produce a deuterated addition product which is removed from the reaction mixture.

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.

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

Code of Federal Regulations, 2010 CFR

2010-01-01

... is produced by radiation of metal halides and their products of dissociation, possibly in combination... electromagnetic ballast that starts a pulse-start metal halide lamp with high voltage pulses, where lamps shall be...

Integration of CuAAC Polymerization and Controlled Radical Polymerization into Electron Transfer Mediated "Click-Radical" Concurrent Polymerization.

PubMed

Xue, Wentao; Wang, Jie; Wen, Ming; Chen, Gaojian; Zhang, Weidong

2017-03-01

The successful chain-growth copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization employing Cu(0)/pentamethyldiethylenetriamine (PMDETA) and alkyl halide as catalyst is first investigated by a combination of nuclear magnetic resonance, gel-permeation chromatography, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. In addition, the electron transfer mediated "click-radical" concurrent polymerization utilizing Cu(0)/PMDETA as catalyst is successfully employed to generate well-defined copolymers, where controlled CuAAC polymerization of clickable ester monomer is progressed in the main chain acting as the polymer backbone, the controlled radical polymerization (CRP) of acrylic monomer is carried out in the side chain. Furthermore, it is found that there is strong collaborative effect and compatibility between CRP and CuAAC polymerization to improve the controllability. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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+.

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

Systematic Introduction of Aromatic Rings to Diphosphine Ligands for Emission Color Tuning of Dinuclear Copper(I) Iodide Complexes.

PubMed

Okano, Yuka; Ohara, Hiroki; Kobayashi, Atsushi; Yoshida, Masaki; Kato, Masako

2016-06-06

We have newly synthesized two solution-stable luminescent dinuclear copper(I) complexes, [Cu2(μ-I)2(dpppy)2] (Cu-py) and [Cu2(μ-I)2(dpppyz)2] (Cu-pyz), where dpppy = 2,3-bis(diphenylphosphino)pyridine and dpppyz = 2,3-bis(diphenylphosphino)pyrazine, using chelating diphosphine ligands composed of N-heteroaromatic rings. X-ray analysis clearly indicates that the molecular structures of Cu-py and Cu-pyz are almost identical with that of the parent complex, [Cu2(μ-I)2(dppb)2] [Cu-bz; dppb = 2,3-bis(diphenylphosphino)benzene]. Complexes Cu-py and Cu-pyz exhibit luminescence [emission quantum yield (Φem) = 0.48 and 0.02, respectively] in the solid state at 298 K. A wide emission color tuning, from 497 to 638 nm (energy = 0.55 eV, with an emission color ranging from green to reddish-orange), was achieved in the solid state by the introduction of pyridinic N atoms into the bridging phenyl group between the two diphenylphosphine groups. Density functional theory calculations suggest that the emission could originate from the effective combination of the metal-to-ligand charge-transfer excited state with the halide-to-ligand charge-transfer excited state. Thus, the emission color change is due to stabilization of the π* levels of the central aryl group in the diphosphine ligand. Furthermore, these copper(I) complexes exhibit thermally activated delayed fluorescence at 298 K because of the small singlet-triplet energy difference (ΔE = 523 and 564 cm(-1) for Cu-py and Cu-pyz, respectively). The stability of these complexes in chloroform, due to the rigid bonds between the diphosphine ligands and the Cu(I) ions, enables the preparation of emissive poly(methyl methacrylate) films by the solution-doping technique.

10 CFR 431.329 - Enforcement.

Code of Federal Regulations, 2011 CFR

2011-01-01

... Metal Halide Lamp Ballasts and Fixtures Energy Conservation Standards § 431.329 Enforcement. Process for Metal Halide Lamp Ballasts. This section sets forth procedures DOE will follow in pursuing alleged... with the following statistical sampling procedures for metal halide lamp ballasts, with the methods...

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.

Adsorption of molecular additive onto lead halide perovskite surfaces: A computational study on Lewis base thiophene additive passivation

NASA Astrophysics Data System (ADS)

Zhang, Lei; Yu, Fengxi; Chen, Lihong; Li, Jingfa

2018-06-01

Organic additives, such as the Lewis base thiophene, have been successfully applied to passivate halide perovskite surfaces, improving the stability and properties of perovskite devices based on CH3NH3PbI3. Yet, the detailed nanostructure of the perovskite surface passivated by additives and the mechanisms of such passivation are not well understood. This study presents a nanoscopic view on the interfacial structure of an additive/perovskite interface, consisting of a Lewis base thiophene molecular additive and a lead halide perovskite surface substrate, providing insights on the mechanisms that molecular additives can passivate the halide perovskite surfaces and enhance the perovskite-based device performance. Molecular dynamics study on the interactions between water molecules and the perovskite surfaces passivated by the investigated additive reveal the effectiveness of employing the molecular additives to improve the stability of the halide perovskite materials. The additive/perovskite surface system is further probed via molecular engineering the perovskite surfaces. This study reveals the nanoscopic structure-property relationships of the halide perovskite surface passivated by molecular additives, which helps the fundamental understanding of the surface/interface engineering strategies for the development of halide perovskite based devices.

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.

FTIR Studies of Internal Water Molecules of Bacteriorhodopsin: Structural Analysis of Halide-bound D85S and D212N Mutants in the Schiff Base Region

NASA Astrophysics Data System (ADS)

Shibata, Mikihiro; Kandori, Hideki

2007-12-01

Bacteriorhodopsin (BR), a membrane protein found in Halobacterium salinarum, functions as a light-driven proton pump. The Schiff base region has a quadropolar structure with positive charges located at the protonated Schiff base and Arg82, and counterbalancing negative charges located at Asp85 and Asp212 (Figure 1A). It is known that BR lacks a proton-pumping activity if Asp85 or Asp212 is neutralized by mutation. On the other hand, binding of C1- brings different effects for pumping functions in mutants at D85 and D212 position. While C1--bound D85T and D85S pump C1-, photovoltage measurements suggested that C1--bound D212N pumps protons at low pH. In this study, we measured low-temperature FTIR spectra of D85S and D212N containing various halides to compare the halide binding site of both proteins. In the case of D85S, the N-D stretching vibrations of the Schiff base were halide-dependent. This result suggests that the halide is a hydrogen-bond acceptor of the Schiff base, being consistent with the X-ray crystal structure. On the other hand, no halide dependence was observed for vibrational bands of the retinal skeleton and the Schiff base in the D212N mutant. This result suggests that the halide does not form a hydrogen bond with the Schiff base directly, unlike the mutation at D85 position. Halide-dependent water bands in the Schiff base region also differ between D85S and D212N. From these results, halide binding site of both proteins and role of two negative charges in BR will be discussed.

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.

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 0.25% Cu). These surfaces were negatively impacted when tested under dry conditions with high organic content. At 0.25% Cu, the antibacterial activity of the powder coatings was not impacted by washing with several commercial cleaners; however, at concentrations of 0.05% Cu, antibacterial activity was reduced by washing with water, WindexRTM , and Pine SolRTM. Ultrasonic cleaning of the coatings appeared to decrease their antimicrobial efficacy. Despite this, CuI nanoparticles were found in all studies to have great potential as a new class of fast-acting, broad-spectrum antimicrobial.

Investigation of a light fixture fire

DOE PAGES

Jurney, James D.; Cournoyer, Michael E.; Trujillo, Stanley; ...

2016-04-16

Metal-halide lamps produce light by discharging an electric arc through a gaseous mixture of vaporized mercury and metal halides. Metal-halide lamps for use in spaces with lower mounting heights can produce excessive visual glare in the normal, higher field-of-view unless they are equipped with prismatic lenses. Should the bulb fail, high internal operating pressure of the arc tube can launch fragments of arc tube at high velocity in all directions, striking the outer bulb of the lamp with enough force to cause the outer bulb to break. This article reports an investigation of a light fixture fire and reviews amore » case study of a metal-halide lamp fire. We reported on causal analysis of the metal-halide lamp fire uncovered contributing factors that created the environment in which the incident occurred. Latent organizational conditions that created error-likely situations or weakened defenses were identified and controlled. Lastly, effective improvements that reduce the probability or consequence of similar metal-halide lamp fire incidents were implemented.« less

Investigation of a light fixture fire

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

Jurney, James D.; Cournoyer, Michael E.; Trujillo, Stanley

Metal-halide lamps produce light by discharging an electric arc through a gaseous mixture of vaporized mercury and metal halides. Metal-halide lamps for use in spaces with lower mounting heights can produce excessive visual glare in the normal, higher field-of-view unless they are equipped with prismatic lenses. Should the bulb fail, high internal operating pressure of the arc tube can launch fragments of arc tube at high velocity in all directions, striking the outer bulb of the lamp with enough force to cause the outer bulb to break. This article reports an investigation of a light fixture fire and reviews amore » case study of a metal-halide lamp fire. We reported on causal analysis of the metal-halide lamp fire uncovered contributing factors that created the environment in which the incident occurred. Latent organizational conditions that created error-likely situations or weakened defenses were identified and controlled. Lastly, effective improvements that reduce the probability or consequence of similar metal-halide lamp fire incidents were implemented.« less

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 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...

10 CFR 431.327 - Submission of data.

Code of Federal Regulations, 2011 CFR

2011-01-01

... EQUIPMENT Metal Halide Lamp Ballasts and Fixtures Energy Conservation Standards § 431.327 Submission of data.... (2) Each manufacturer or private labeler of a basic model of metal halide lamp ballast shall file a... certification report for each of its metal halide lamp ballast basic models. The certification report (for which...

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...

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.

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.

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.

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.

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...

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.

Bulk assembly of organic metal halide nanotubes

DOE PAGES

Lin, Haoran; Zhou, Chenkun; Tian, Yu; ...

2017-10-16

The organic metal halide hybrids welcome a new member with a one-dimensional (1D) tubular structure. Herein we report the synthesis and characterization of a single crystalline bulk assembly of organic metal halide nanotubes, (C 6H 13N 4) 3Pb 2Br 7. In a metal halide nanotube, six face-sharing metal halide dimers (Pb 2Br 9 5–) connect at the corners to form rings that extend in one dimension, of which the inside and outside surfaces are coated with protonated hexamethylenetetramine (HMTA) cations (C 6H 13N 4 +). This unique 1D tubular structure possesses highly localized electronic states with strong quantum confinement, resultingmore » in the formation of self-trapped excitons that give strongly Stokes shifted broadband yellowish-white emission with a photoluminescence quantum efficiency (PLQE) of ~7%. Finally, having realized single crystalline bulk assemblies of two-dimensional (2D) wells, 1D wires, and now 1D tubes using organic metal halide hybrids, our work significantly advances the research on bulk assemblies of quantum-confined materials.« less

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.

Ultrafast photochemistry of polyatomic molecules containing labile halogen atoms in solution

NASA Astrophysics Data System (ADS)

Mereshchenko, Andrey S.

Because breaking and making of chemical bonds lies at the heart of chemistry, this thesis focuses on dynamic studies of labile molecules in solutions using ultrafast transient absorption spectroscopy. Specifically, my interest is two-fold: (i) novel reaction intermediates of polyhalogenated carbon, boron and phosphorus compounds; (ii) photophysics and photochemistry of labile copper(II) halide complexes. Excitation of CH2Br2, CHBr3, BBr 3, and PBr3 into n(Br)sigma*(X-Br) states, where X=C, B, or P, leads to direct photoisomerization with formation of isomers having Br-Br bonds as well as rupture of one of X-Br bonds with the formation of a Br atom and a polyatomic radical fragment, which subsequently recombine to form similar isomer products. Nonpolar solvation stabilizes the isomers, consistent with intrinsic reaction coordinate calculations of the isomer ground state potential energy surfaces at the density functional level of theory, and consequently, the involvement of these highly energetic species on chemically-relevant time scales needs to be taken into account. Monochlorocomplexes in methanol solutions promoted to the ligand-to-metal charge transfer (LMCT) excited state predominantly undergo internal conversion via back electron transfer, giving rise to vibrationally hot ground-state parent complexes. Copper-chloride homolitical bond dissociation yielding the solvated copper(I) and Cl- atom/solvent CT complexes constitutes a minor pathway. Insights into ligand substitution mechanisms were acquired by monitoring the recovery of monochloro complexes at the expense of two unexcited dichloro- and unsubstituted forms of Cu(II) complexes also present in the solution. Detailed description of ultrafast excited-state dynamics of CuCl 42- complexes in acetonitrile upon excitation into all possible Ligand Field (LF) excited states and two most intense LMCT transitions is reported. The LF states were found to be nonreactive with lifetimes remarkably longer than those for copper(II) complexes studied so far, in particular, copper blue proteins. The highest 2A1 and lowest 2E LF states relax directly to the ground electronic state whereas the intermediate 2B1 LF state relaxes stepwise through the 2E state. The LMCT excited states are short-lived undergoing either ionic dissociation (CuCl3- + Cl-) or cascading relaxation through the manifold of vibrationally hot LF states to the ground state.

Methods for improved growth of group III nitride semiconductor compounds

DOEpatents

Melnik, Yuriy; Chen, Lu; Kojiri, Hidehiro

2015-03-17

Methods are disclosed for growing group III-nitride semiconductor compounds with advanced buffer layer technique. In an embodiment, a method includes providing a suitable substrate in a processing chamber of a hydride vapor phase epitaxy processing system. The method includes forming an AlN buffer layer by flowing an ammonia gas into a growth zone of the processing chamber, flowing an aluminum halide containing precursor to the growth zone and at the same time flowing additional hydrogen halide or halogen gas into the growth zone of the processing chamber. The additional hydrogen halide or halogen gas that is flowed into the growth zone during buffer layer deposition suppresses homogeneous AlN particle formation. The hydrogen halide or halogen gas may continue flowing for a time period while the flow of the aluminum halide containing precursor is turned off.

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.

Nitromethane with IBX/TBAF as a nitrosating agent: synthesis of nitrosamines from secondary or tertiary amines under mild conditions.

PubMed

Potturi, Hima K; Gurung, Ras K; Hou, Yuqing

2012-01-06

Aliphatic or aromatic N,N-disubstituted nitrosamine was generated in fair to excellent yield from the reaction of a secondary or tertiary amine with o-iodoxybenzoic acid (IBX) or o-iodosylbenzoic acid (IBA)/R(4)NX (X = halide) and nitromethane. The product yield was strongly influenced by both the halide of R(4)NX and iodanes. IBX gave a higher yield than IBA, while the halides follow F(-) > Cl(-) > Br(-) ∼ I(-). Nitrous acid formed in situ from nitromethane and IBX (or IBA)/halides is likely responsible for the observed reaction.

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.

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...

Continuous production of granular or powder Ti, Zr and Hf or their alloy products

DOEpatents

White, Jack C.; Oden, Laurance L.

1993-01-01

A continuous process for producing a granular metal selected from the group consisting of Ti, Zr or Hf under conditions that provide orderly growth of the metal free of halide inclusions comprising: a) dissolving a reducing metal selected from the group consisting of Na, Mg, Li or K in their respective halide salts to produce a reducing molten salt stream; b) preparing a second molten salt stream containing the halide salt of Ti, Zr or Hf; c) mixing and reacting the two molten streams of steps a) and b) in a continuous stirred tank reactor; d) wherein steps a) through c) are conducted at a temperature range of from about 800.degree. C. to about 1100.degree. C. so that a weight percent of equilibrium solubility of the reducing metal in its respective halide salt varies from about 1.6 weight percent at about 900.degree. C. to about 14.4 weight percent at about 1062.degree. C.; and wherein a range of concentration of the halide salt of Ti, Zn or Hf in molten halides of Na, Mg, Li or K is from about 1 to about 5 times the concentration of Na, Mg, Li or K; e) placing the reacted molten stream from step c) in a solid-liquid separator to recover an impure granular metal product by decantation, centrifugation, or filtration; and f) removing residual halide salt impurity by vacuum evaporator or inert gas sweep at temperatures from about 850.degree. C. to 1000.degree. C. or cooling the impure granular metal product to ambient temperature and water leaching off the residual metal halide salt.

Non-hydrolytic metal oxide films for perovskite halide overcoating and stabilization

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

Martinson, Alex B.; Kim, In Soo

A method of protecting a perovskite halide film from moisture and temperature includes positioning the perovskite halide film in a chamber. The chamber is maintained at a temperature of less than 200 degrees Celsius. An organo-metal compound is inserted into the chamber. A non-hydrolytic oxygen source is subsequently inserted into the chamber. The inserting of the organo-metal compound and subsequent inserting of the non-hydrolytic oxygen source into the chamber is repeated for a predetermined number of cycles. The non-hydrolytic oxygen source and the organo-metal compound interact in the chamber to deposit a non-hydrolytic metal oxide film on perovskite halide film.more » The non-hydrolytic metal oxide film protects the perovskite halide film from relative humidity of greater than 35% and a temperature of greater than 150 degrees Celsius, respectively.« less

Molecular dynamics simulations of the surface tension and structure of salt solutions and clusters.

PubMed

Sun, Lu; Li, Xin; Hede, Thomas; Tu, Yaoquan; Leck, Caroline; Ågren, Hans

2012-03-15

Sodium halides, which are abundant in sea salt aerosols, affect the optical properties of aerosols and are active in heterogeneous reactions that cause ozone depletion and acid rain problems. Interfacial properties, including surface tension and halide anion distributions, are crucial issues in the study of the aerosols. We present results from molecular dynamics simulations of water solutions and clusters containing sodium halides with the interatomic interactions described by a conventional force field. The simulations reproduce experimental observations that sodium halides increase the surface tension with respect to pure water and that iodide anions reach the outermost layer of water clusters or solutions. It is found that the van der Waals interactions have an impact on the distribution of the halide anions and that a conventional force field with optimized parameters can model the surface tension of the salt solutions with reasonable accuracy. © 2012 American Chemical Society

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.

Nuclear radiation-warning detector that measures impedance

DOEpatents

Savignac, Noel Felix; Gomez, Leo S; Yelton, William Graham; Robinson, Alex; Limmer, Steven

2013-06-04

This invention is a nuclear radiation-warning detector that measures impedance of silver-silver halide on an interdigitated electrode to detect light or radiation comprised of alpha particles, beta particles, gamma rays, X rays, and/or neutrons. The detector is comprised of an interdigitated electrode covered by a layer of silver halide. After exposure to alpha particles, beta particles, X rays, gamma rays, neutron radiation, or light, the silver halide is reduced to silver in the presence of a reducing solution. The change from the high electrical resistance (impedance) of silver halide to the low resistance of silver provides the radiation warning that detected radiation levels exceed a predetermined radiation dose threshold.

Alkali metal and alkali earth metal gadolinium halide scintillators

DOEpatents

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

2016-08-02

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

Metal-halide mixtures for latent heat energy storage

NASA Technical Reports Server (NTRS)

Chen, K.; Manvi, R.

1981-01-01

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

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.

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.

Laboratory determination of the carbon kinetic isotope effects (KIEs) for reactions of methyl halides with various nucleophiles in solution

USGS Publications Warehouse

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

2005-01-01

Large carbon kinetic isotope effects (KIEs) were measured for reactions of methyl bromide (MeBr), methyl chloride (MeCl), and methyl iodide (MeI) with various nucleophiles at 287 and 306 K in aqueous solutions. Rates of reaction of MeBr and MeI with H2O (neutral hydrolysis) or Cl- (halide substitution) were consistent with previous measurements. Hydrolysis rates increased with increasing temperature or pH (base hydrolysis). KIEs for hydrolysis were 51 ?? 6??? for MeBr and 38 ?? 8??? for MeI. Rates of halide substitution increased with increasing temperature and greater reactivity of the attacking nucleophile, with the fastest reaction being that of MeI with Br-. KIEs for halide substitution were independent of temperature but varied with the reactant methyl halide and the attacking nucleophile. KIEs were similar for MeBr substitution with Cl- and MeCl substitution with Br- (57 ?? 5 and 60 ?? 9??? respectively). The KIE for halide exchange of MeI was lower overall (33 ?? 8??? and was greater for substitution with Br- (46 ?? 6???) than with Cl- (29 ?? 6???). ?? Springer Science + Business Media, Inc. 2005.

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.

Postsynthetic Doping of MnCl2 Molecules into Preformed CsPbBr3 Perovskite Nanocrystals via a Halide Exchange-Driven Cation Exchange.

PubMed

Huang, Guangguang; Wang, Chunlei; Xu, Shuhong; Zong, Shenfei; Lu, Ju; Wang, Zhuyuan; Lu, Changgui; Cui, Yiping

2017-08-01

Unlike widely used postsynthetic halide exchange for CsPbX 3 (X is halide) perovskite nanocrystals (NCs), cation exchange of Pb is of a great challenge due to the rigid nature of the Pb cationic sublattice. Actually, cation exchange has more potential for rendering NCs with peculiar properties. Herein, a novel halide exchange-driven cation exchange (HEDCE) strategy is developed to prepare dually emitting Mn-doped CsPb(Cl/Br) 3 NCs via postsynthetic replacement of partial Pb in preformed perovskite NCs. The basic idea for HEDCE is that the partial cation exchange of Pb by Mn has a large probability to occur as a concomitant result for opening the rigid halide octahedron structure around Pb during halide exchange. Compared to traditional ionic exchange, HEDCE is featured by proceeding of halide exchange and cation exchange at the same time and lattice site. The time and space requirements make only MnCl 2 molecules (rather than mixture of Mn and Cl ions) capable of doping into perovskite NCs. This special molecular doping nature results in a series of unusual phenomenon, including long reaction time, core-shell structured mid states with triple emission bands, and dopant molecules composition-dependent doping process. As-prepared dual-emitting Mn-doped CsPb(Cl/Br) 3 NCs are available for ratiometric temperature sensing. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Low Pressure Vapor-assisted Solution Process for Tunable Band Gap Pinhole-free Methylammonium Lead Halide Perovskite Films

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

Sutter-Fella, Carolin M.; Li, Yanbo; Cefarin, Nicola

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, we present a protocol for the fabrication of this material via the low-pressure vapor assisted solution process (LP-VASP) method, which yields ~19% power conversion efficiency in planar heterojunction perovskite solar cells. First, we report the synthesis of methylammonium iodide (CH 3NH 3I) and methylammonium bromide (CH 3NH 3Br) from methylamine and the corresponding halide acid (HI or HBr). Then, we describe the fabrication of pinhole-free, continuous methylammonium-lead halide perovskite (CH 3NH 3PbX 3 with X = I, Br, Cl and their mixture) filmsmore » with the LP-VASP. This process is based on two steps: i) spin-coating of a homogenous layer of lead halide precursor onto a substrate, and ii) conversion of this layer to CH 3NH 3PbI 3-xBr x by exposing the substrate to vapors of a mixture of CH 3NH 3I and CH 3NH 3Br at reduced pressure and 120 °C. Through slow diffusion of the methylammonium halide vapor into the lead halide precursor, we achieve slow and controlled growth of a continuous, pinhole-free perovskite film. The LP-VASP allows synthetic access to the full halide composition space in CH 3NH 3PbI 3-xBr x with 0 ≤ x ≤ 3. Depending on the composition of the vapor phase, the bandgap can be tuned between 1.6 eV ≤ E g ≤ 2.3 eV. In addition, by varying the composition of the halide precursor and of the vapor phase, we can also obtain CH 3NH 3PbI 3-xCl x. Films obtained from the LP-VASP are reproducible, phase pure as confirmed by X-ray diffraction measurements, and show high photoluminescence quantum yield. The process does not require the use of a glovebox.« less

Low Pressure Vapor-assisted Solution Process for Tunable Band Gap Pinhole-free Methylammonium Lead Halide Perovskite Films

DOE PAGES

Sutter-Fella, Carolin M.; Li, Yanbo; Cefarin, Nicola; ...

2017-09-08

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, we present a protocol for the fabrication of this material via the low-pressure vapor assisted solution process (LP-VASP) method, which yields ~19% power conversion efficiency in planar heterojunction perovskite solar cells. First, we report the synthesis of methylammonium iodide (CH 3NH 3I) and methylammonium bromide (CH 3NH 3Br) from methylamine and the corresponding halide acid (HI or HBr). Then, we describe the fabrication of pinhole-free, continuous methylammonium-lead halide perovskite (CH 3NH 3PbX 3 with X = I, Br, Cl and their mixture) filmsmore » with the LP-VASP. This process is based on two steps: i) spin-coating of a homogenous layer of lead halide precursor onto a substrate, and ii) conversion of this layer to CH 3NH 3PbI 3-xBr x by exposing the substrate to vapors of a mixture of CH 3NH 3I and CH 3NH 3Br at reduced pressure and 120 °C. Through slow diffusion of the methylammonium halide vapor into the lead halide precursor, we achieve slow and controlled growth of a continuous, pinhole-free perovskite film. The LP-VASP allows synthetic access to the full halide composition space in CH 3NH 3PbI 3-xBr x with 0 ≤ x ≤ 3. Depending on the composition of the vapor phase, the bandgap can be tuned between 1.6 eV ≤ E g ≤ 2.3 eV. In addition, by varying the composition of the halide precursor and of the vapor phase, we can also obtain CH 3NH 3PbI 3-xCl x. Films obtained from the LP-VASP are reproducible, phase pure as confirmed by X-ray diffraction measurements, and show high photoluminescence quantum yield. The process does not require the use of a glovebox.« less

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.

The thermodynamics of latent fingerprint corrosion of metal elements and alloys.

PubMed

Bond, John W

2008-11-01

Redox reactions taking place between the surface of a metal and fingerprint residue have been expressed thermodynamically in terms of both the Nernst equation for reduction potential and the complexation constant for the formation of complex metal halide ions in aqueous solution. These expressions are used to explain experimental results for the corrosion of 10 different metal elements by fingerprint residue in air at room temperature. Corrosion of noble metals, such as silver and gold, supports the proposition that the degree of metal corrosion is enhanced by the presence of chloride ions in eccrine sweat. Extending the experiments to include 10 metal alloys enabled the construction of a fingerprint corrosion series for 20 different metals. Fingerprint corrosion on metals alloyed with > approximately 40% copper was found to display third level fingerprint detail. A comparison of both conventional ink on paper and digital (Livescan) fingerprinting techniques with fingerprints deposited on 9 Karat gold alloy has shown that gold alloy depositions are least susceptible to third level detail obliteration by poor fingerprint capturing techniques.

Trace element partitioning during the retorting of Julia Creek oil shale

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

Patterson, J.H.; Dale, L.S.; Chapman, J.f.

1987-05-01

A bulk sample of oil shale from the Julia Creek deposit in Queensland was retorted under Fischer assay conditions at temperatures ranging from 250 to 550 /sup 0/C. The distributions of the trace elements detected in the shale oil and retort water were determined at each temperature. Oil distillation commenced at 300 /sup 0/C and was essentially complete at 500 /sup 0/C. A number of trace elements were progressively mobilized with increasing retort temperature up to 450 /sup 0/C. The following trace elements partitioned mainly to the oil: vanadium, arsenic, selenium, iron, nickel, titanium, copper, cobalt, and aluminum. Elements thatmore » also partitioned to the retort waters included arsenic, selenium, chlorine, and bromine. Element mobilization is considered to be caused by the volatilization of organometallic compounds, sulfide minerals, and sodium halides present in the oil shale. The results have important implications for shale oil refining and for the disposal of retort waters. 22 references, 5 tables.« less

Magnetic phase transition in layered inorganic-organic hybrid (C12H25NH3)2CuCl4

NASA Astrophysics Data System (ADS)

Bochalya, Madhu; Kumar, Sunil; Kanaujia, Pawan K.; Prakash, G. Vijaya

2018-05-01

Inorganic-organic (IO) hybrids are material systems which have become an interesting theme of research for physicist and chemists recently due to the possibility of engineering specific magnetic, thermal or optoelectronic properties by playing around with the transition metal, halides and the organic components. Our experiments on (C12H25NH3)2CuCl4 show that the system exhibits a long range ferromagnetic order below ˜11 K. In such an inorganic-organic hybrid system, Jahn-Teller distortion of the copper ions results into a weak ferromagnetic order as compared to the antiferromagnetic spin-spin exchange in the pure inorganic CuCl2 compound. Moreover, this particular hybrid system also exhibits photoluminescence when excited below absorption maximum related to charge transfer peak though the effect is much weaker as compared to that in extensively studied other MX4-based (M = Sn, Pb; X = Cl, Br, I) counterparts.

23.6%-efficient monolithic perovskite/silicon tandem solar cells with improved stability

NASA Astrophysics Data System (ADS)

Bush, Kevin A.; Palmstrom, Axel F.; Yu, Zhengshan J.; Boccard, Mathieu; Cheacharoen, Rongrong; Mailoa, Jonathan P.; McMeekin, David P.; Hoye, Robert L. Z.; Bailie, Colin D.; Leijtens, Tomas; Peters, Ian Marius; Minichetti, Maxmillian C.; Rolston, Nicholas; Prasanna, Rohit; Sofia, Sarah; Harwood, Duncan; Ma, Wen; Moghadam, Farhad; Snaith, Henry J.; Buonassisi, Tonio; Holman, Zachary C.; Bent, Stacey F.; McGehee, Michael D.

2017-02-01

As the record single-junction efficiencies of perovskite solar cells now rival those of copper indium gallium selenide, cadmium telluride and multicrystalline silicon, they are becoming increasingly attractive for use in tandem solar cells due to their wide, tunable bandgap and solution processability. Previously, perovskite/silicon tandems were limited by significant parasitic absorption and poor environmental stability. Here, we improve the efficiency of monolithic, two-terminal, 1-cm2 perovskite/silicon tandems to 23.6% by combining an infrared-tuned silicon heterojunction bottom cell with the recently developed caesium formamidinium lead halide perovskite. This more-stable perovskite tolerates deposition of a tin oxide buffer layer via atomic layer deposition that prevents shunts, has negligible parasitic absorption, and allows for the sputter deposition of a transparent top electrode. Furthermore, the window layer doubles as a diffusion barrier, increasing the thermal and environmental stability to enable perovskite devices that withstand a 1,000-hour damp heat test at 85 ∘C and 85% relative humidity.

Propitious Dendritic Cu2O-Pt Nanostructured Anodes for Direct Formic Acid Fuel Cells.

PubMed

El-Nagar, Gumaa A; Mohammad, Ahmad M; El-Deab, Mohamed S; El-Anadouli, Bahgat E

2017-06-14

This study introduces a novel competent dendritic copper oxide-platinum nanocatalyst (nano-Cu 2 O-Pt) immobilized onto a glassy carbon (GC) substrate for formic acid (FA) electro-oxidation (FAO); the prime reaction in the anodic compartment of direct formic acid fuel cells (DFAFCs). Interestingly, the proposed catalyst exhibited an outstanding improvement for FAO compared to the traditional platinum nanoparticles (nano-Pt) modified GC (nano-Pt/GC) catalyst. This was evaluated from steering the reaction mechanism toward the desired direct route producing carbon dioxide (CO 2 ); consistently with mitigating the other undesired indirect pathway producing carbon monoxide (CO); the potential poison deteriorating the catalytic activity of typical Pt-based catalysts. Moreover, the developed catalyst showed a reasonable long-term catalytic stability along with a significant lowering in onset potential of direct FAO that ultimately reduces the polarization and amplifies the fuel cell's voltage. The observed catalytic enhancement was believed to originate bifunctionally; while nano-Pt represented the base for the FA adsorption, nanostructured copper oxide (nano-Cu 2 O) behaved as a catalytic mediator facilitating the charge transfer during FAO and providing the oxygen atmosphere inspiring the poison's (CO) oxidation at relatively lower potential. Surprisingly, moreover, nano-Cu 2 O induced a surface retrieval of nano-Pt active sites by capturing the poisoning CO via "a spillover mechanism" to renovate the Pt surface for the direct FAO. Finally, the catalytic tolerance of the developed catalyst toward halides' poisoning was discussed.

The local structure and EPR parameter of compressed tetrahedral CuIIX4 components in proteins, liquid precursors and nanomaterials

NASA Astrophysics Data System (ADS)

Kuang, Min-Quan; Yuan, Hong-Kuan; Chen, Hong; Wang, Li-Dan; Duan, Shu-Kai

2017-11-01

The local structures and EPR parameters of flatten CuIIX4 (X = N, O, S, Se, Cl and Br) compositions in proteins, liquid precursors and nanocrystals are analyzed and computed based on the cluster approach and perturbation method. The g and A components of copper(II) under D2d symmetry are well explained in terms of a global parameter β characterizing the local angular distortion away from the ideal Td tetrahedron where β0 ≈ 109.4712°. The calculated isotropy and anisotropy of g factors (gav and Δg) are found suffering an increase with the enlargement of the obtained βcal, which is consistent with the increasing trends of both experimental Δg and gav. The variation trend of gav can also be interpreted by the decreasing covalence of the studied system (or the increasing covalency factor ρ). On the other hand, the hyperfine structure constant A‖ decreases with increasing βcal. The obtained cubic crystal field parameter Dq and the core polarization constant κ experience the dropping and growing tendencies, respectively, with the enlarging copper-ligand bond length R. The above correlations are appropriate for all the studied CuIIX4 complexes and thus this work would be helpful to establish the complete physical scheme for uniform analysis on spectroscopic and magnetic behaviours of MX4 (M = transition metal and X = halides and pseudohalides) compounds.

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

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.

Anti-perovskite solid electrolyte compositions

DOEpatents

Zhao, Yusheng; Daemen, Luc Louis

2015-12-26

Solid electrolyte antiperovskite compositions for batteries, capacitors, and other electrochemical devices have chemical formula Li.sub.3OA, Li.sub.(3-x)M.sub.x/2OA, Li.sub.(3-x)N.sub.x/3OA, or LiCOX.sub.zY.sub.(1-z), wherein M and N are divalent and trivalent metals respectively and wherein A is a halide or mixture of halides, and X and Y are halides.

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...

Influence of Halide Solutions on Collagen Networks: Measurements of Physical Properties by Atomic Force Microscopy

PubMed Central

Kempe, André; Lackner, Maximilian

2016-01-01

The influence of aqueous halide solutions on collagen coatings was tested. The effects on resistance against indentation/penetration on adhesion forces were measured by atomic force microscopy (AFM) and the change of Young's modulus of the coating was derived. Comparative measurements over time were conducted with halide solutions of various concentrations. Physical properties of the mesh-like coating generally showed large variability. Starting with a compact set of physical properties, data disperse after minutes. A trend of increase in elasticity and permeability was found for all halide solutions. These changes were largest in NaI, displaying a logical trend with ion size. However a correlation with concentration was not measured. Adhesion properties were found to be independent of mechanical properties. The paper also presents practical experience for AFM measurements of soft tissue under liquids, particularly related to data evaluation. The weakening in physical strength found after exposure to halide solutions may be interpreted as widening of the network structure or change in the chemical properties in part of the collagen fibres (swelling). In order to design customized surface coatings at optimized conditions also for medical applications, halide solutions might be used as agents with little impact on the safety of patients. PMID:27721994

The thermo-elastic instability model of melting of alkali halides in the Debye approximation

NASA Astrophysics Data System (ADS)

Owens, Frank J.

2018-05-01

The Debye model of lattice vibrations of alkali halides is used to show that there is a temperature below the melting temperature where the vibrational pressure exceeds the electrostatic pressure. The onset temperature of this thermo-elastic instability scales as the melting temperature of NaCl, KCl, and KBr, suggesting its role in the melting of the alkali halides in agreement with a previous more rigorous model.

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.

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.

Picosecond pulse radiolysis of direct and indirect radiolytic effects in highly concentrated halide aqueous solutions.

PubMed

Balcerzyk, Anna; Schmidhammer, Uli; El Omar, Abdel Karim; Jeunesse, Pierre; Larbre, Jean-Philippe; Mostafavi, Mehran

2011-08-25

Recently we measured the amount of the single product, Br(3)(-), of steady-state radiolysis of highly concentrated Br(-) aqueous solutions, and we showed the effect of the direct ionization of Br(-) on the yield of Br(3)(-). Here, we report the first picosecond pulse-probe radiolysis measurements of ionization of highly concentrated Br(-) and Cl(-) aqueous solutions to describe the oxidation mechanism of the halide anions. The transient absorption spectra are reported from 350 to 750 nm on the picosecond range for halide solutions at different concentrations. In the highly concentrated halide solutions, we observed that, due to the presence of Na(+), the absorption band of the solvated electron is shifted to shorter wavelengths, but its decay, taking place during the spur reactions, is not affected within the first 4 ns. The kinetic measurements in the UV reveal the direct ionization of halide ions. The analysis of pulse-probe measurements show that after the electron pulse, the main reactions in solutions containing 1 M of Cl(-) and 2 M of Br(-) are the formation of ClOH(-•) and BrOH(-•), respectively. In contrast, in highly concentrated halide solutions, containing 5 M of Cl(-) and 6 M of Br(-), mainly Cl(2)(-•) and Br(2)(-•) are formed within the electron pulse without formation of ClOH(-•) and BrOH(-•). The results suggest that, not only Br(-) and Cl(-) are directly ionized into Br(•) and Cl(•) by the electron pulse, the halide atoms can also be rapidly generated through the reactions initiated by excitation and ionization of water, such as the prompt oxidation by the hole, H(2)O(+•), generated in the coordination sphere of the anion. © 2011 American Chemical Society

Modeling and Investigation of Heavy Oxide and Alkali-Halide Scintillators for Potential Use in Neutron and Gamma Detection Systems

DTIC Science & Technology

2015-06-01

INVESTIGATION OF HEAVY OXIDE AND ALKALI-HALIDE SCINTILLATORS FOR POTENTIAL USE IN NEUTRON AND GAMMA DETECTION SYSTEMS by Jeremy S. Cadiente June...AND ALKALI- HALIDE SCINTILLATORS FOR POTENTIAL USE IN NEUTRON AND GAMMA DETECTION SYSTEMS 5. FUNDING NUMBERS 6. AUTHOR(S) Jeremy S. Cadiente 7...fast neutron detection efficiencies well over 40%, were investigated for potential use as highly efficient gamma- neutron radiation detectors. The

Single-step synthesis of styryl phosphonic acids via palladium-catalyzed Heck coupling of vinyl phosphonic acid with aryl halides

DOE PAGES

McNichols, Brett W.; Koubek, Joshua T.; Sellinger, Alan

2017-10-27

Here, we have developed a single step palladium-catalyzed Heck coupling of aryl halides with vinyl phosphonic acid to produce functionalized (E)-styryl phosphonic acids. This pathway utilizes a variety of commercially available aryl halides, vinyl phosphonic acid and Pd(P(tBu) 3) 2 as catalyst. These conditions produce a wide range of styryl phosphonic acids with high purities and good to excellent yields (31–80%).

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 %.

Single-step synthesis of styryl phosphonic acids via palladium-catalyzed Heck coupling of vinyl phosphonic acid with aryl halides

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

McNichols, Brett W.; Koubek, Joshua T.; Sellinger, Alan

Here, we have developed a single step palladium-catalyzed Heck coupling of aryl halides with vinyl phosphonic acid to produce functionalized (E)-styryl phosphonic acids. This pathway utilizes a variety of commercially available aryl halides, vinyl phosphonic acid and Pd(P(tBu) 3) 2 as catalyst. These conditions produce a wide range of styryl phosphonic acids with high purities and good to excellent yields (31–80%).

Synthesis and luminescence of Mn-doped Cs2AgInCl6 double perovskites.

PubMed

K, Nila Nandha; Nag, Angshuman

2018-05-17

Metal halide double perovskites (DPs) are being explored as stable and non-toxic alternatives of Pb-halide perovskites. Typically DPs exhibit a wide (>2.5 eV) and/or indirect bandgap, limiting their applications in the visible region. Here we impart the visible-light emission property in direct bandgap Cs2AgInCl6 DPs by doping Mn2+ ions. Synthesis, characterization and luminescence of metal halide double perovskites are reported.

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

Intermediate Temperature Fluids Life Tests - Theory

NASA Technical Reports Server (NTRS)

Tarau, Calin; Sarraf, David B.; Locci, Ivan E.; Anderson, William G.

2008-01-01

There are a number of different applications that could use heat pipes or loop heat pipes (LHPs) in the intermediate temperature range of 450 to 750 K, including space nuclear power system radiators, and high temperature electronics cooling. Potential working fluids include organic fluids, elements, and halides, with halides being the least understood, with only a few life tests conducted. Potential envelope materials for halide working fluids include pure aluminum, aluminum alloys, commercially pure (CP) titanium, titanium alloys, and corrosion resistant superalloys. Life tests were conducted with three halides (AlBr3, SbBr3, and TiCl4) and water in three different envelopes: two aluminum alloys (Al-5052, Al-6061) and Cp-2 titanium. The AlBr3 attacked the grain boundaries in the aluminum envelopes, and formed TiAl compounds in the titanium. The SbBr3 was incompatible with the only envelope material that it was tested with, Al-6061. TiCl4 and water were both compatible with CP2-titanium. A theoretical model was developed that uses electromotive force differences to predict the compatibility of halide working fluids with envelope materials. This theory predicts that iron, nickel, and molybdenum are good envelope materials, while aluminum and titanium halides are good working fluids. The model is in good agreement with results form previous life tests, as well as the current life tests.

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.

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.

Global expression for representing cohesive-energy curves. II

NASA Technical Reports Server (NTRS)

Schlosser, Herbert; Ferrante, John

1993-01-01

Schlosser et al. (1991) showed that the R dependence of the cohesive energy of partially ionic solids may be characterized by a two-term energy relationship consisting of a Coulomb term arising from the charge transfer, delta-Z, and a scaled universal energy function, E*(a *), which accounts for the partially covalent character of the bond and for repulsion between the atomic cores for small R; a* is a scaled length. In the paper by Schlosser et al., the normalized cohesive-energy curves of NaCl-structure alkali-halide crystals were generated with this expression. In this paper we generate the cohesive-energy curves of several families of partially ionic solids with different crystal structures and differing degrees of ionicity. These include the CsCl-structure Cs halides, and the Tl and Ag halides, which have weaker ionic bonding than the alkali halides, and which have the CsCl and NaCl structures, respectively. The cohesive-energy-curve parameters are then used to generate theoretical isothermal compression curves for the Li, Na, K, Cs, and Ag halides. We find good agreement with the available experimental compression data.

Inverse kinetic solvent isotope effect in TiO2 photocatalytic dehalogenation of non-adsorbable aromatic halides: a proton-induced pathway.

PubMed

Chang, Wei; Sun, Chunyan; Pang, Xibin; Sheng, Hua; Li, Yue; Ji, Hongwei; Song, Wenjing; Chen, Chuncheng; Ma, Wanhong; Zhao, Jincai

2015-02-09

An efficient redox reaction between organic substrates in solution and photoinduced h(+) vb /e(-) cb on the surface of photocatalysts requires the substrates or solvent to be adsorbed onto the surface, and is consequentially marked by a normal kinetic solvent isotope effect (KSIE ≥ 1). Reported herein is a universal inverse KSIE (0.6-0.8 at 298 K) for the reductive dehalogenation of aromatic halides which cannot adsorb onto TiO2 in a [D0 ]methanol/[D4 ]methanol solution. Combined with in situ ATR-FTIR spectroscopy investigations, a previously unknown pathway for the transformation of these aromatic halides in TiO2 photocatalysis was identified: a proton adduct intermediate, induced by released H(+) /D(+) from solvent oxidation, accompanies a change in hybridization from sp(2) to sp(3) at a carbon atom of the aromatic halides. The protonation event leads these aromatic halides to adsorb onto the TiO2 surface and an ET reaction to form dehalogenated products follows. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Defect-induced band-edge reconstruction of a bismuth-halide double perovskite for visible-light absorption

DOE PAGES

Slavney, Adam H.; Leppert, Linn; Bartesaghi, Davide; ...

2017-03-29

In this study, halide double perovskites have recently been developed as less toxic analogs of the lead perovskite solar-cell absorbers APbX 3 (A = monovalent cation; X = Br or I). However, all known halide double perovskites have large bandgaps that afford weak visible-light absorption. The first halide double perovskite evaluated as an absorber, Cs 2AgBiBr 6 (1), has a bandgap of 1.95 eV. Here, we show that dilute alloying decreases 1’s bandgap by ca. 0.5 eV. Importantly, time-resolved photoconductivity measurements reveal long-lived carriers with microsecond lifetimes in the alloyed material, which is very promising for photovoltaic applications. The alloyedmore » perovskite described herein is the first double perovskite to show comparable bandgap energy and carrier lifetime to those of (CH 3NH 3)PbI 3. By describing how energy- and symmetry-matched impurity orbitals, at low concentrations, dramatically alter 1’s band edges, we open a potential pathway for the large and diverse family of halide double perovskites to compete with APbX 3 absorbers.« less

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.

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

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.

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.

THERMAL DECOMPOSITION OF URANIUM COMPOUNDS

DOEpatents

Magel, T.T.; Brewer, L.

1959-02-10

A method is presented of preparing uranium metal of high purity consisting contacting impure U metal with halogen vapor at between 450 and 550 C to form uranium halide vapor, contacting the uranium halide vapor in the presence of H/sub 2/ with a refractory surface at about 1400 C to thermally decompose the uranium halides and deposit molten U on the refractory surface and collecting the molten U dripping from the surface. The entire operation is carried on at a sub-atmospheric pressure of below 1 mm mercury.

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.

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.

Unique properties of halide perovskites as possible origins of the superior solar cell performance.

PubMed

Yin, Wan-Jian; Shi, Tingting; Yan, Yanfa

2014-07-16

Halide perovskites solar cells have the potential to exhibit higher energy conversion efficiencies with ultrathin films than conventional thin-film solar cells based on CdTe, CuInSe2 , and Cu2 ZnSnSe4 . The superior solar-cell performance of halide perovskites may originate from its high optical absorption, comparable electron and hole effective mass, and electrically clean defect properties, including point defects and grain boundaries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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 compared with fractionation achieved during the uptake of methyl halides by live and heat-killed soils.

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.

Halogen radicals contribute to photooxidation in coastal and estuarine waters

PubMed Central

Parker, Kimberly M.; Mitch, William A.

2016-01-01

Although halogen radicals are recognized to form as products of hydroxyl radical (•OH) scavenging by halides, their contribution to the phototransformation of marine organic compounds has received little attention. We demonstrate that, relative to freshwater conditions, seawater halides can increase photodegradation rates of domoic acid, a marine algal toxin, and dimethyl sulfide, a volatile precursor to cloud condensation nuclei, up to fivefold. Using synthetic seawater solutions, we show that the increased photodegradation is specific to dissolved organic matter (DOM) and halides, rather than other seawater salt constituents (e.g., carbonates) or photoactive species (e.g., iron and nitrate). Experiments in synthetic and natural coastal and estuarine water samples demonstrate that the halide-specific increase in photodegradation could be attributed to photochemically generated halogen radicals rather than other photoproduced reactive intermediates [e.g., excited-state triplet DOM (3DOM*), reactive oxygen species]. Computational kinetic modeling indicates that seawater halogen radical concentrations are two to three orders of magnitude greater than freshwater •OH concentrations and sufficient to account for the observed halide-specific increase in photodegradation. Dark •OH generation by gamma radiolysis demonstrates that halogen radical production via •OH scavenging by halides is insufficient to explain the observed effect. Using sensitizer models for DOM chromophores, we show that halogen radicals are formed predominantly by direct oxidation of Cl− and Br− by 3DOM*, an •OH-independent pathway. Our results indicate that halogen radicals significantly contribute to the phototransformation of algal products in coastal or estuarine surface waters. PMID:27162335

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.

FRACTIONAL DISTILLATION SEPARATION OF PLUTONIUM VALUES FROM LIGHT ELEMENT VALUES

DOEpatents

Cunningham, B.B.

1957-12-17

A process is described for removing light element impurities from plutonium. It has been found that plutonium contaminated with impurities may be purified by converting the plutonium to a halide and purifying the halide by a fractional distillation whereby impurities may be distilled from the plutonium halide. A particularly effective method includes the step of forming a lower halide such as the trior tetrahalide and distilling the halide under conditions such that no decomposition of the halide occurs. Molecular distillation methods are particularly suitable for this process. The apparatus may comprise an evaporation plate with means for heating it and a condenser surface with means for cooling it. The condenser surface is placed at a distance from the evaporating surface less than the mean free path of molecular travel of the material being distilled at the pressure and temperature used. The entire evaporating system is evacuated until the pressure is about 10/sup -4/ millimeters of mercury. A high temperuture method is presented for sealing porous materials such as carbon or graphite that may be used as a support or a moderator in a nuclear reactor. The carbon body is subjected to two surface heats simultaneously in an inert atmosphere; the surface to be sealed is heated to 1500 degrees centigrade; and another surface is heated to 300 degrees centigrade, whereupon the carbon vaporizes and flows to the cooler surface where it is deposited to seal that surface. This method may be used to seal a nuclear fuel in the carbon structure.

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.

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.

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.

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.

Rocksalt or cesium chloride: Investigating the relative stability of the cesium halide structures with random phase approximation based methods

NASA Astrophysics Data System (ADS)

Nepal, Niraj K.; Ruzsinszky, Adrienn; Bates, Jefferson E.

2018-03-01

The ground state structural and energetic properties for rocksalt and cesium chloride phases of the cesium halides were explored using the random phase approximation (RPA) and beyond-RPA methods to benchmark the nonempirical SCAN meta-GGA and its empirical dispersion corrections. The importance of nonadditivity and higher-order multipole moments of dispersion in these systems is discussed. RPA generally predicts the equilibrium volume for these halides within 2.4% of the experimental value, while beyond-RPA methods utilizing the renormalized adiabatic LDA (rALDA) exchange-correlation kernel are typically within 1.8%. The zero-point vibrational energy is small and shows that the stability of these halides is purely due to electronic correlation effects. The rAPBE kernel as a correction to RPA overestimates the equilibrium volume and could not predict the correct phase ordering in the case of cesium chloride, while the rALDA kernel consistently predicted results in agreement with the experiment for all of the halides. However, due to its reasonable accuracy with lower computational cost, SCAN+rVV10 proved to be a good alternative to the RPA-like methods for describing the properties of these ionic solids.

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

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.

Effect of various halide salts on the incompatibility of cyanocobalamin and ascorbic acid in aqueous solution.

PubMed

Ichikawa, Makoto; Ide, Nagatoshi; Shiraishi, Sumihiro; Ono, Kazuhisa

2005-06-01

Combination of cyanocobalamin (VB12) and ascorbic acid (VC) has been widely seen in pharmaceutical products and dietary supplements. However, VB12 has been reported that its behavior in stability in aqueous solution is quite different when VC is mixed. In the present study, we examined the stabilities of these vitamins in acetate buffer (pH 4.8) using high performance liquid chromatography. Degradation of VB12 was not observed in the absence of VC in the buffer. However, when VC was mixed in the VB12 solution, VB12 concentrations decreased in accordance with VC degradation. VB12 and VC degradations were inhibited by adding sodium halides to acetate buffer at pH 4.8. These stabilization effects were also observed in the range from pH 3.5 to 5.3 and by adding potassium, magnesium, and calcium halides. Furthermore, our data demonstrated that increases in the halide anion concentrations and atomic number (Cl-

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.

Clues from defect photochemistry

NASA Astrophysics Data System (ADS)

De Angelis, Filippo; Petrozza, Annamaria

2018-05-01

Charge carriers in metal halide perovskites seem to be only marginally affected by defect-related trap states. Filippo De Angelis and Annamaria Petrozza suggest that the key to this behaviour lies in the redox chemistry of halide defects.

10 CFR 431.321 - Purpose and scope.

Code of Federal Regulations, 2012 CFR

2012-01-01

... EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.321 Purpose and scope. This subpart contains energy conservation requirements for metal halide lamp ballasts and fixtures, pursuant to Part A of Title III of the...

10 CFR 431.321 - Purpose and scope.

Code of Federal Regulations, 2010 CFR

2010-01-01

... EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.321 Purpose and scope. This subpart contains energy conservation requirements for metal halide lamp ballasts and fixtures, pursuant to Part A-1 of Title III of the...

10 CFR 431.321 - Purpose and scope.

Code of Federal Regulations, 2014 CFR

2014-01-01

... EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.321 Purpose and scope. This subpart contains energy conservation requirements for metal halide lamp ballasts and fixtures, pursuant to Part A of Title III of the...

10 CFR 431.321 - Purpose and scope.

Code of Federal Regulations, 2013 CFR

2013-01-01

... EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.321 Purpose and scope. This subpart contains energy conservation requirements for metal halide lamp ballasts and fixtures, pursuant to Part A of Title III of the...

10 CFR 431.321 - Purpose and scope.

Code of Federal Regulations, 2011 CFR

2011-01-01

... EQUIPMENT Metal Halide Lamp Ballasts and Fixtures § 431.321 Purpose and scope. This subpart contains energy conservation requirements for metal halide lamp ballasts and fixtures, pursuant to Part A of Title III of the...

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.

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

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.

Nanostructure of propylammonium nitrate in the presence of poly(ethylene oxide) and halide salts

NASA Astrophysics Data System (ADS)

Stefanovic, Ryan; Webber, Grant B.; Page, Alister J.

2018-05-01

Nanoscale structure of protic ionic liquids is critical to their utility as molecular electrochemical solvents since it determines the capacity to dissolve salts and polymers such as poly(ethylene oxide) (PEO). Here we use quantum chemical molecular dynamics simulations to investigate the impact of dissolved halide anions on the nanostructure of an archetypal nanostructured protic ionic liquid, propylammonium nitrate (PAN), and how this impacts the solvation of a model PEO polymer. At the molecular level, PAN is nanostructured, consisting of charged/polar and uncharged/nonpolar domains. The charged domain consists of the cation/anion charge groups, and is formed by their electrostatic interaction. This domain solvophobically excludes the propyl chains on the cation, which form a distinct, self-assembled nonpolar domain within the liquid. Our simulations demonstrate that the addition of Cl- and Br- anions to PAN disrupts the structure within the PAN charged domain due to competition between nitrate and halide anions for the ammonium charge centre. This disruption increases with halide concentration (up to 10 mol. %). However, at these concentrations, halide addition has little effect on the structure of the PAN nonpolar domain. Addition of PEO to pure PAN also disrupts the structure within the charged domain of the liquid due to hydrogen bonding between the charge groups and the terminal PEO hydroxyl groups. There is little other association between the PEO structure and the surrounding ionic liquid solvent, with strong PEO self-interaction yielding a compact, coiled polymer morphology. Halide addition results in greater association between the ionic liquid charge centres and the ethylene oxide components of the PEO structure, resulting in reduced conformational flexibility, compared to that observed in pure PAN. Similarly, PEO self-interactions increase in the presence of Cl- and Br- anions, compared to PAN, indicating that the addition of halide salts to PAN decreases its utility as a molecular solvent for polymers such as PEO.

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.

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.

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

Method for removing acid gases from a gaseous stream

DOEpatents

Gorin, Everett; Zielke, Clyde W.

1981-01-01

In a process for hydrocracking a heavy aromatic polynuclear carbonaceous feedstock containing reactive alkaline constituents to produce liquid hydrocarbon fuels boiling below about 475.degree. C. at atmospheric pressure by contacting the feedstock with hydrogen in the presence of a molten metal halide catalyst, thereafter separating a gaseous stream containing hydrogen, at least a portion of the hydrocarbon fuels and acid gases from the molten metal halide and regenerating the molten metal halide, thereby producing a purified molten metal halide stream for recycle to the hydrocracking zone, an improvement comprising; contacting the gaseous acid gas, hydrogen and hydrocarbon fuels-containing stream with the feedstock containing reactive alkaline constituents to remove acid gases from the acid gas containing stream. Optionally at least a portion of the hydrocarbon fuels are separated from gaseous stream containing hydrogen, hydrocarbon fuels and acid gases prior to contacting the gaseous stream with the feedstock.

Surface passivation of mixed-halide perovskite CsPb(BrxI1-x)3 nanocrystals by selective etching for improved stability.

PubMed

Jing, Qiang; Zhang, Mian; Huang, Xiang; Ren, Xiaoming; Wang, Peng; Lu, Zhenda

2017-06-08

In recent years, there has been an unprecedented rise in the research of halide perovskites because of their important optoelectronic applications, including photovoltaic cells, light-emitting diodes, photodetectors and lasers. The most pressing question concerns the stability of these materials. Here faster degradation and PL quenching are observed at higher iodine content for mixed-halide perovskite CsPb(Br x I 1-x ) 3 nanocrystals, and a simple yet effective method is reported to significantly enhance their stability. After selective etching with acetone, surface iodine is partially etched away to form a bromine-rich surface passivation layer on mixed-halide perovskite nanocrystals. This passivation layer remarkably stabilizes the nanocrystals, making their PL intensity improved by almost three orders of magnitude. It is expected that a similar passivation layer can also be applied to various other kinds of perovskite materials with poor stability issues.

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.

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

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

PubMed

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

2016-10-01

The occurrence of sulfonamide antibiotics (SAs) in estuarine waters urges insights into their environmental fate for ecological risk assessment. Although many studies focused on the photochemical behavior of SAs, yet the effects of halide ions relevant to estuarine and marine environments on their photodegradation have been poorly understood. Here, we investigated the effects of halide ions on the photodegradation of SAs with sulfapyridine, sulfamethazine, and sulfamethoxazole as representative compounds. Results showed that halide ions did not significantly impact the photodegradation of sulfapyridine and sulfamethoxazole, while they significantly promoted the photodegradation of sulfamethazine. Further experiments found that ionic strength applied with NaClO4 significantly enhanced the photodegradation of the SAs, which was attributed to the decreased quenching rate constant of the triplet-excited SAs ((3)SA(∗)). Compared with ionic strength, specific Cl(-) effects retarded the photodegradation of the SAs. Our study found that triplet-excited sulfamethazine can oxidize halide ions to produce halogen radicals, subsequently leading to the halogenation of sulfamethazine, which was confirmed by the identification of both chlorinated and brominated intermediates. These results indicate that halide ions play an important role in the photochemical behavior of some SAs in estuarine waters and seawater. The occurrence of halogenation for certain organic pollutants can be predicted by comparing the oxidation potentials of triplet-excited contaminants with those of halogen radicals. Our findings are helpful in understanding the photochemical behavior and assessing the ecological risks of SAs and other organic pollutants in estuarine and marine environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

ESI-MS of Cucurbituril Complexes Under Negative Polarity.

PubMed

Rodrigues, Maria A A; Mendes, Débora C; Ramamurthy, Vaidhyanathan; Da Silva, José P

2017-11-01

Electrospray ionization mass spectrometry (ESI-MS) is a powerful tool to study host-guest supramolecular interactions. ESI-MS can be used for detailed gas-phase reactivity studies, to clarify the structure, or simply to verify the formation of complexes. Depending on the structure of the host and of the guest, negative and/or positive ESI are used. Here we report the unexpected formation of host-guest complexes between cucurbit[n]urils (n = 7, 8, CB[n]) and amine, styryl pyridine, and styryl pyridine dimer cations, under negative ESI. Non-complexed CB[n] form double charged halide (Br - , Cl - , F - ) adducts. Under negative ESI, halide ions interact with CB[n] outer surface hydrogen atoms. One to one host-guest complexes (1:1) of CB[n] with positive charged guests were also observed as single and double charged ions under negative ESI. The positive charge of guests is neutralized by ion-pairing with halide anions. Depending on the number of positive charges guests retain in the gas phase, one or two additional halide ions are required for neutralization. Complexes 1:2 of CB[8] with styryl pyridines retain two halide ions in the gas phase, one per guest. Styryl pyridine dimers form 1:1 complexes possessing a single extra halide ion and therefore a single positive charge. Negative ESI is sensitive to small structural differences between complexes, distinguishing between 1:2 complexes of styryl pyridine-CB[8] and corresponding 1:1 complexes with the dimer. Negative ESI gives simpler spectra than positive ESI and allows the determination of guest charge state of CB[n] complexes in the gas phase. Graphical Abstract ᅟ.

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

Decolorization and Detoxification of Textile Dyes with a Laccase from Trametes hirsuta

PubMed Central

Abadulla, Elias; Tzanov, Tzanko; Costa, Silgia; Robra, Karl-Heinz; Cavaco-Paulo, Artur; Gübitz, Georg M.

2000-01-01

Trametes hirsuta and a purified laccase from this organism were able to degrade triarylmethane, indigoid, azo, and anthraquinonic dyes. Initial decolorization velocities depended on the substituents on the phenolic rings of the dyes. Immobilization of the T. hirsuta laccase on alumina enhanced the thermal stabilities of the enzyme and its tolerance against some enzyme inhibitors, such as halides, copper chelators, and dyeing additives. The laccase lost 50% of its activity at 50 mM NaCl while the 50% inhibitory concentration (IC50) of the immobilized enzyme was 85 mM. Treatment of dyes with the immobilized laccase reduced their toxicities (based on the oxygen consumption rate of Pseudomonas putida) by up to 80% (anthraquinonic dyes). Textile effluents decolorized with T. hirsuta or the laccase were used for dyeing. Metabolites and/or enzyme protein strongly interacted with the dyeing process indicated by lower staining levels (K/S) values than obtained with a blank using water. However, when the effluents were decolorized with immobilized laccase, they could be used for dyeing and acceptable color differences (ΔE*) below 1.1 were measured for most dyes. PMID:10919791

An Icosidodecahedral Supramolecule Based on Pentaphosphaferrocene: From a Disordered Average Structure to Individual Isomers

PubMed Central

Heindl, Claudia; Peresypkina, Eugenia; Virovets, Alexander V.; Bushmarinov, Ivan S.; Medvedev, Michael G.; Krämer, Barbara; Dittrich, Birger

2017-01-01

Abstract Pentaphosphaferrocenes [CpRFe(η5‐P5)] (1) and CuI halides are excellent building blocks for the formation of discrete supramolecules. Herein, we demonstrate the potential of Cu(CF3SO3) for the construction of the novel 2D polymer [{Cp*Fe(μ4,η5:1:1:1‐P5)}{Cu(CF3SO3)}]n (2) and the unprecedented nanosphere (CH2Cl2)1.4@[{CpBnFe(η5‐P5)}12{Cu(CF3SO3)}19.6] (3). The supramolecule 3 has a unique scaffold beyond the fullerene topology, with 20 copper atoms statistically distributed over the 30 vertices of an icosidodecahedron. Combinatorics was used to interpret the average disordered structure of the supramolecules. In this case, only two pairs of enantiomers with D5 and D2 symmetry are possible for bidentate bridging coordination of the triflate ligands. DFT calculations showed that differences in the energies of the isomers are negligible. The benzyl ligands enhance the solubility of 3, enabling NMR‐spectroscopic and mass‐spectrometric investigations. PMID:28793182

SOLVENT-FREE SONOCHEMICAL PREPARATION OF IONIC LIQUIDS

EPA Science Inventory

An ultrasound-assisted preparation of a series of ambient temperature ionic liquids, 1-alkyl-3-methylimidazolium (AMIM) halides, that proceeds via efficient reaction of 1-methyl imidazole with alkyl halides/terminal dihalides under solvent-free conditions, is described.

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 multistate emission in [W(6)X(8)X'(6)](2-) clusters. The inapplicability of isoelectronic analogies between clusters of Group 6 and Group 7 is emphasized.

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.

Theoretical Studies in Chemical Kinetics - Annual Report, 1970.

DOE R&D Accomplishments Database

Karplus, Martin

1970-10-01

The research performed includes (a) Alkali-Halide, Alkali-Halide (MX, M?X?) Exchange Reactions; (b) Inversion Problem; (c) Quantum Mechanics of Scattering Processes, (d) Transition State Analysis of Classical Trajectories, (e) Differential Cross Sections from Classical Trajectories; and (f) Other Studies.

Methods for synthesizing alane without the formation of adducts and free of halides

DOEpatents

Zidan, Ragaiy; Knight, Douglas A; Dinh, Long V

2013-02-19

A process is provided to synthesize an alane without the formation of alane adducts as a precursor. The resulting product is a crystallized .alpha.-alane and is a highly stable product and is free of halides.

Molten salts in Nuclear Reactors (Bibliography); LES SELS FONDUS DANS LES REACTEURS NUCLEAIRES (BIBLIOGRAPHIE)

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

Dirian, J.; Saint-James, R.

1959-01-01

A collection is presented of references dealing with the physicochemical studies of fused salts, in partictular the alkali and alkali earth halides. Numerous binary, ternary and quaternary systems of these halides with those of uranium and thoriuna are examined, and the physical properties, density, viscosity, and vapor pressure going from the halides to the mixtures are also considered. References relating to the corrosion of materials by these salts are included and the treatment of the salts with a view to recovery after irradiation in a nuclear reactor is discussed. (auth)

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.

Plasmonic particles of colloidal silver in high-resolution recording media

NASA Astrophysics Data System (ADS)

Andreeva, O. V.; Andreeva, N. V.; Kuzmina, T. B.

2017-01-01

The optical properties of colloidal silver particles formed photographically in high-resolution silver halide photographic materials have been considered. The conditions that allow one to obtain exposed and developed light-sensitive silver halide particles in the form of colloidal particles of metallic silver having the properties of localized plasmons have been described. The results of the studies of the developed silver particles in traditional photographic materials for image holography and in nanoporous silver halide photographic materials for volume holography have been presented. The perspectives of using plasmonic silver nanoparticles produced photographically have been discussed.

Hydrosoluble Cu(i)-DAPTA complexes: synthesis, characterization, luminescence thermochromism and catalytic activity for microwave-assisted three-component azide-alkyne cycloaddition click reaction.

PubMed

Mahmoud, Abdallah G; Guedes da Silva, M Fátima C; Sokolnicki, Jerzy; Smoleński, Piotr; Pombeiro, Armando J L

2018-05-16

New hydrosoluble and air-stable Cu(i) halide compounds, viz. [CuX(DAPTA)3] (1) and (2), and [Cu(μ-X)(DAPTA)2]2 (3) and (4) (X = Br or I, in this order), have been prepared by reacting Cu(i) halide (i.e., bromide or iodide) with 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) under mild conditions. They represent the first examples of Cu(i) halide complexes bearing the DAPTA ligand, which have been fully characterized by elemental analysis, IR, 1H, 13C{1H} and 31P{1H} NMR spectroscopies, ESI-MS+ and, for 4, also by single-crystal X-ray diffraction (SCXRD) analyses. Complexes 1-4 are efficient catalysts for the one-pot microwave assisted three-component (terminal alkyne, organic halide and NaN3) Huisgen cycloaddition reaction in aqueous media to afford the corresponding disubstituted triazoles. The catalysis proceeds with a broad alkyne substrate scope and according to "click rules". Photophysical studies of compound 4 showed an unusual reversible thermochromic behaviour exhibiting a blue emission at 298 K due to the halide-to-ligand charge transfer (3XLCT) and a red emission at 77 K because of the {Cu2I2} unit.

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

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

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

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

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

Fractionation of Cl/Br during fluid phase separation in magmatic-hydrothermal fluids

NASA Astrophysics Data System (ADS)

Seo, Jung Hun; Zajacz, Zoltán

2016-06-01

Brine and vapor inclusions were synthesized to study Cl/Br fractionation during magmatic-hydrothermal fluid phase separation at 900 °C and pressures of 90, 120, and 150 MPa in Li/Na/K halide salt-H2O systems. Laser ablation ICP-MS microanalysis of high-density brine inclusions show an elevated Cl/Br ratio compared to the coexisting low-density vapor inclusions. The degree of Cl/Br fractionation between vapor and brine is significantly dependent on the identity of the alkali metal in the system: stronger vapor partitioning of Br occurs in the Li halide-H2O system compared to the systems of K and Na halide-H2O. The effect of the identity of alkali-metals in the system is stronger compared to the effect of vapor-brine density contrast. We infer that competition between alkali-halide and alkali-OH complexes in high-temperature fluids might cause the Cl/Br fractionation, consistent with the observed molar imbalances of alkali metals compared to halides in the analyzed brine inclusions. Our experiments show that the identity of alkali metals controls the degrees of Cl/Br fractionation between the separating aqueous fluid phases at 900 °C, and suggest that a significant variability in the Cl/Br ratios of magmatic fluids can arise in Li-rich systems.

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 approach the efficiency limits in tandem solar cells, coloured-light-emitting diodes and other optoelectronic applications.

Dry syngas purification process for coal gas produced in oxy-fuel type integrated gasification combined cycle power generation with carbon dioxide capturing feature.

PubMed

Kobayashi, Makoto; Akiho, Hiroyuki

2017-12-01

Electricity production from coal fuel with minimizing efficiency penalty for the carbon dioxide abatement will bring us sustainable and compatible energy utilization. One of the promising options is oxy-fuel type Integrated Gasification Combined Cycle (oxy-fuel IGCC) power generation that is estimated to achieve thermal efficiency of 44% at lower heating value (LHV) base and provide compressed carbon dioxide (CO 2 ) with concentration of 93 vol%. The proper operation of the plant is established by introducing dry syngas cleaning processes to control halide and sulfur compounds satisfying tolerate contaminants level of gas turbine. To realize the dry process, the bench scale test facility was planned to demonstrate the first-ever halide and sulfur removal with fixed bed reactor using actual syngas from O 2 -CO 2 blown gasifier for the oxy-fuel IGCC power generation. Design parameter for the test facility was required for the candidate sorbents for halide removal and sulfur removal. Breakthrough test was performed on two kinds of halide sorbents at accelerated condition and on honeycomb desulfurization sorbent at varied space velocity condition. The results for the both sorbents for halide and sulfur exhibited sufficient removal within the satisfactory short depth of sorbent bed, as well as superior bed conversion of the impurity removal reaction. These performance evaluation of the candidate sorbents of halide and sulfur removal provided rational and affordable design parameters for the bench scale test facility to demonstrate the dry syngas cleaning process for oxy-fuel IGCC system as the scaled up step of process development. Copyright © 2017 Elsevier Ltd. All rights reserved.

Halide peroxidase in tissues that interact with bacteria in the host squid Euprymna scolopes.

PubMed

Small, A L; McFall-Ngai, M J

1999-03-15

An enzyme with similarities to myeloperoxidase, the antimicrobial halide peroxidase in mammalian neutrophils, occurs abundantly in the light organ tissue of Euprymna scolopes, a squid that maintains a beneficial association with the luminous bacterium Vibrio fischeri. Using three independent assays typically applied to the analysis of halide peroxidase enzymes, we directly compared the activity of the squid enzyme with that of human myeloperoxidase. One of these methods, the diethanolamine assay, confirmed that the squid peroxidase requires halide ions for its activity. The identification of a halide peroxidase in a cooperative bacterial association suggested that this type of enzyme can function not only to control pathogens, but also to modulate the interactions of host animals with their beneficial partners. To determine whether the squid peroxidase functions under both circumstances, we examined its distribution in a variety of host tissues, including those that typically interact with bacteria and those that do not. Tissues interacting with bacteria included those that have specific cooperative associations with bacteria (i.e., the light organ and accessory nidamental gland) and those that have transient nonspecific interactions with bacteria (i.e., the gills, which clear the cephalopod circulatory system of invading microorganisms). These bacteria-associated tissues were compared with the eye, digestive gland, white body, and ink-producing tissues, which do not typically interact directly with bacteria. Peroxidase enzyme assays, immunocytochemical localization, and DNA-RNA hybridizations showed that the halide-dependent peroxidase is consistently expressed in high concentration in tissues that interact bacteria. Elevated levels of the peroxidase were also found in the ink-producing tissues, which are known to have enzymatic pathways associated with antimicrobial activity. Taken together, these data suggest that the host uses a common biochemical response to the variety of types of associations that it forms with microorganisms.

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 the efficiency limits in tandem solar cells, coloured-light-emitting diodes and other optoelectronic applications.

Kinetics of the iodine- and bromine-mediated transport of halide ions: demonstration of an interfacial complexation mechanism.

PubMed Central

Klotz, K H; Benz, R

1993-01-01

Stationary and kinetic experiments were performed on lipid bilayer membranes to study the mechanism of iodine- and bromine-mediated halide transport in detail. The stationary conductance data suggested that four different 1:1 complexes between I2 and Br2 and the halides I- and Br- were responsible for the observed conductance increase by iodine and bromine (I3-, I2Br-, Br2I-, and Br3-). Charge pulse experiments allowed the further elucidation of the transport mechanism. Only two of three exponential voltage relaxations predicted by the Läuger model could be resolved under all experimental conditions. This means that either the heterogeneous complexation reactions kR (association) and kD (dissociation) were too fast to be resolved or that the neutral carriers were always in equilibrium within the membrane. Experiments at different carrier and halide concentrations suggested that the translocation of the neutral carrier is much faster than the other processes involved in carrier-mediated ion transport. The model was modified accordingly. From the charge pulse data at different halide concentrations, the translocation rate constant of the complexed carriers, kAS, the dissociation constant, kD, and the total surface concentration of charged carriers, NAS, could be evaluated from one single charge pulse experiment. The association rate of the complex, kR, could be obtained in some cases from the plot of the stationary conductance data as a function of the halide concentration in the aqueous phase. The translocation rate constant, kAS, of the different complexes is a function of the image force and of the Born charging energy. It increases 5000-fold from Br3- to I3- because of an enlarged ion radius. PMID:8312500

Synthesis of triazole-based and imidazole-based zinc catalysts

DOEpatents

Valdez, Carlos A.; Satcher, Jr., Joe H.; Aines, Roger D.; Baker, Sarah E.

2013-03-12

Various methods and structures of complexes and molecules are described herein related to a zinc-centered catalyst for removing carbon dioxide from atmospheric or aqueous environments. According to one embodiment, a method for creating a tris(triazolyl)pentaerythritol molecule includes contacting a pentaerythritol molecule with a propargyl halide molecule to create a trialkyne molecule, and contacting the trialkyne molecule with an azide molecule to create the tris(triazolyl)pentaerythritol molecule. In another embodiment, a method for creating a tris(imidazolyl)pentaerythritol molecule includes alkylating an imidazole 2-carbaldehyde molecule to create a monoalkylated aldehyde molecule, reducing the monoalkylated aldehyde molecule to create an alcohol molecule, converting the alcohol molecule to create an alkyl halide molecule using thionyl halide, and reacting the alkyl halide molecule with a pentaerythritol molecule to create a tris(imidazolyl)pentaerythritol molecule. In another embodiment, zinc is bound to the tris(triazolyl)pentaerythritol molecule to create a zinc-centered tris(triazolyl)pentaerythritol catalyst for removing carbon dioxide from atmospheric or aqueous environments.

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.

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

Tailoring Oxygen Sensitivity with Halide Substitution in Difluoroboron Dibenzoylmethane Polylactide Materials

PubMed Central

DeRosa, Christopher A.; Kerr, Caroline; Fan, Ziyi; Kolpaczynska, Milena; Mathew, Alexander S.; Evans, Ruffin E.; Zhang, Guoqing; Fraser, Cassandra L.

2015-01-01

The dual-emissive properties of solid-state difluoroboron β-diketonate-poly(lactic acid) (BF2bdkPLA) materials have been utilized for biological oxygen sensing. In this work, BF2dbm(X)PLA materials were synthesized, where X = H, F, Cl, Br, and I. The effects of changing the halide substituent and PLA polymer chain length on the optical properties in dilute CH2Cl2 solutions and solid-state polymer films were studied. These luminescent materials show fluorescence, phosphorescence, and lifetime tunability on the basis of molecular weight, as well as lifetime modulation via the halide substituent. Short BF2dbm(Br)PLA (6.0 kDa) and both short and long BF2dbm(I)PLA polymers (6.0 or 20.3 kDa) have fluorescence and intense phosphorescence ideal for ratiometric oxygen sensing. The lighter halide-dye polymers with hydrogen, fluorine, and chlorine substitution have longer phosphorescence lifetimes and can be utilized as ultrasensitive oxygen sensors. Photostability was also analyzed for the polymer films. PMID:26480236

Role of Halides in the Ordered Structure Transitions of Heated Gold Nanocrystal Superlattices

PubMed Central

2015-01-01

Dodecanethiol-capped gold (Au) nanocrystal superlattices can undergo a surprisingly diverse series of ordered structure transitions when heated (Goodfellow, B. W.; Rasch, M. R.; Hessel, C. M.; Patel, R. N.; Smilgies, D.-M.; Korgel, B. A. Nano Lett.2013, 13, 5710–5714). These are the result of highly uniform changes in nanocrystal size, which subsequently force a spontaneous rearrangement of superlattice structure. Here, we show that halide-containing surfactants play an essential role in these transitions. In the absence of any halide-containing surfactant, superlattices of dodecanethiol-capped (1.9-nm-diameter) Au nanocrystals do not change size until reaching about 190–205 °C, at which point the gold cores coalesce. In the presence of halide-containing surfactant, such as tetraoctylphosphonium bromide (TOPB) or tetraoctylammounium bromide (TOAB), the nanocrystals ripen at much lower temperature and superlattices undergo various ordered structure transitions upon heating. Chloride- and iodide-containing surfactants induce similar behavior, destabilizing the Au–thiol bond and reducing the thermal stability of the nanocrystals. PMID:26013597

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

Holographic Optical Elements Recorded in Silver Halide Sensitized Gelatin Emulsions. Part I. Transmission Holographic Optical Elements

NASA Astrophysics Data System (ADS)

Kim, Jong Man; Choi, Byung So; Kim, Sun Il; Kim, Jong Min; Bjelkhagen, Hans I.; Phillips, Nicholas J.

2001-02-01

Silver halide sensitized gelatin (SHSG) holograms are similar to holograms recorded in dichromated gelatin (DCG), the main recording material for holographic optical elements (HOE s). The drawback of DCG is its low sensitivity and limited spectral response. Silver halide materials can be processed in such a way that the final hologram will have properties like a DCG hologram. Recently this technique has become more interesting since the introduction of new ultra-high-resolution silver halide emulsions. An optimized processing technique for transmission HOE s recorded in these materials is introduced. Diffraction efficiencies over 90% can be obtained for transmissive diffraction gratings. Understanding the importance of the selective hardening process has made it possible to obtain results similar to conventional DCG processing. The main advantage of the SHSG process is that high-sensitivity recording can be performed with laser wavelengths anywhere within the visible spectrum. This simplifies the manufacturing of high-quality, large-format HOE s.

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.

Manipulating Ion Migration for Highly Stable Light-Emitting Diodes with Single-Crystalline Organometal Halide Perovskite Microplatelets.

PubMed

Chen, Mingming; Shan, Xin; Geske, Thomas; Li, Junqiang; Yu, Zhibin

2017-06-27

Ion migration has been commonly observed as a detrimental phenomenon in organometal halide perovskite semiconductors, causing the measurement hysteresis in solar cells and ultrashort operation lifetimes in light-emitting diodes. In this work, ion migration is utilized for the formation of a p-i-n junction at ambient temperature in single-crystalline organometal halide perovskites. The junction is subsequently stabilized by quenching the ionic movement at a low temperature. Such a strategy of manipulating the ion migration has led to efficient single-crystalline light-emitting diodes that emit 2.3 eV photons starting at 1.8 V and sustain a continuous operation for 54 h at ∼5000 cd m -2 without degradation of brightness. In addition, a whispering-gallery-mode cavity and exciton-exciton interaction in the perovskite microplatelets have both been observed that can be potentially useful for achieving electrically driven laser diodes based on single-crystalline organometal halide perovskite semiconductors.

Methyl halide fluxes from tropical plants under controlled radiation and temperature regimes

NASA Astrophysics Data System (ADS)

Blei, Emanuel; Yokouchi, Yoko; Saito, Takuya; Nozoe, Susumu

2015-04-01

Methyl halides (CH3Cl, CH3Br, CH3I) contribute significantly to the halogen burden of the atmosphere and have the potential to influence the stratospheric ozone layer through their catalytic effect in the Chapman cycle. As such they have been studied over the years, and many plants and biota have been examined for their potential to act as a source of these gases. One of the potentially largest terrestrial sources identified was tropical vegetation such as tropical ferns and Dipterocarp trees. Most of these studies concentrated on the identification and quantification of such fluxes rather than their characteristics and often the chambers used in these studies were either opaque or only partially transparent to the full solar spectrum. Therefore it is not certain to which degree emissions of methyl halides are innate to the plants and how much they might vary due to radiation or temperature conditions inside the enclosures. In a separate development it had been proposed that UV-radiation could cause live plant materials to be become emitters of methane even under non-anoxic conditions. As methane is chemically very similar to methyl halides and had been proposed to be produced from methyl-groups ubiquitously found in plant cell material there is a relatively good chance that such a production mechanism would also apply to methyl halides. To test whether radiation can affect elevated emissions of methyl halides from plant materials and to distinguish this from temperature effects caused by heat build-up in chambers a set of controlled laboratory chamber enclosures under various radiation and temperature regimes was conducted on four different tropical plant species (Magnolia grandiflora, Cinnamonum camphora, Cyathea lepifera, Angiopteris lygodiifolia), the latter two of which had previously been identified as strong methyl halide emitters. Abscised leaf samples of these species were subjected to radiation treatments such UV-B, UV-A and broad spectrum radiation similar to natural sunlight without the UV-component and the emissions were compared to dark enclosures. Parallel to this temperature effects were studied in dark enclosures as well. The presentation will discuss the outcome of these experiments and what conclusions can be drawn from them.

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.

PROCESS OF PRODUCING REFRACTORY URANIUM OXIDE ARTICLES

DOEpatents

Hamilton, N.E.

1957-12-01

A method is presented for fabricating uranium oxide into a shaped refractory article by introducing a uranium halide fluxing reagent into the uranium oxide, and then mixing and compressing the materials into a shaped composite mass. The shaped mass of uranium oxide and uranium halide is then fired at an elevated temperature so as to form a refractory sintered article. It was found in the present invention that the introduction of a uraninm halide fluxing agent afforded a fluxing action with the uranium oxide particles and that excellent cohesion between these oxide particles was obtained. Approximately 90% of uranium dioxide and 10% of uranium tetrafluoride represent a preferred composition.

Reshaping and linking of molecules in ion-pair traps

NASA Astrophysics Data System (ADS)

Cochrane, Bryce; Naumkin, Fedor Y.

2016-01-01

A series of insertion complexes of small molecules trapped between alkali-halide counter-ions are investigated ab initio. The molecular shape is altered inside the complexes and varies in corresponding anions. Stabilities and charge distributions are investigated. Strong charge-transfer in the alkali-halide component effectively through the almost neutral molecule results in very large dipole moments. The most stable species is used to construct a dimer significantly bound via dipole-dipole interaction. Another complex with two alkali-halide diatoms trapping the molecule represents a unit of corresponding longer oligomer. This completes the array of systems with the molecule effectively in ion-pair, ion-dipole, dipole-pair electric fields.

High-Efficiency Flexible Solar Cells Based on Organometal Halide Perovskites.

PubMed

Wang, Yuming; Bai, Sai; Cheng, Lu; Wang, Nana; Wang, Jianpu; Gao, Feng; Huang, Wei

2016-06-01

Flexible and light-weight solar cells are important because they not only supply power to wearable and portable devices, but also reduce the transportation and installation cost of solar panels. High-efficiency organometal halide perovskite solar cells can be fabricated by a low-temperature solution process, and hence are promising for flexible-solar-cell applications. Here, the development of perovskite solar cells is briefly discussed, followed by the merits of organometal halide perovskites as promising candidates as high-efficiency, flexible, and light-weight photovoltaic materials. Afterward, recent developments of flexible solar cells based on perovskites are reviewed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Visible-Light-Promoted Trifluoromethylthiolation of Styrenes by Dual Photoredox/Halide Catalysis.

PubMed

Honeker, Roman; Garza-Sanchez, R Aleyda; Hopkinson, Matthew N; Glorius, Frank

2016-03-18

Herein, we report a new visible-light-promoted strategy to access radical trifluoromethylthiolation reactions by combining halide and photoredox catalysis. This approach allows for the synthesis of vinyl-SCF3 compounds of relevance in pharmaceutical chemistry directly from alkenes under mild conditions with irradiation from household light sources. Furthermore, alkyl-SCF3-containing cyclic ketone and oxindole derivatives can be accessed by radical-polar crossover semi-pinacol and cyclization processes. Inexpensive halide salts play a crucial role in activating the trifluoromethylthiolating reagent towards photoredox catalysis and aid the formation of the SCF3 radical. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Allylic and Allenic Halide Synthesis via NbCl5- and NbBr5-Mediated Alkoxide Rearrangements

PubMed Central

Ravikumar, P. C.; Yao, Lihua; Fleming, Fraser F.

2009-01-01

Addition of NbCl5, or NbBr5, to a series of magnesium, lithium, or potassium allylic or propargylic alkoxides directly provides allylic or allenic halides. Halogenation formally occurs through a metalla-halo-[3,3] rearrangement although concerted, ionic, and direct displacement mechanisms appear to operate competitively. Transposition of the olefin is equally effective for allylic alkoxides prepared by nucleophilic addition, deprotonation, or reduction. Experimentally, the niobium pentahalide halogenations are rapid, afford essentially pure E-allylic or allenic halides after extraction, and are applicable to a range of aliphatic and aromatic alcohols, aldehydes, and ketones. PMID:19739606

IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

EPA Science Inventory

A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

Perovskite Solar Cells | Photovoltaic Research | NREL

Science.gov Websites

& Devices pages: High-Efficiency Crystalline PV Polycrystalline Thin-Film PV Perovskite and Organic -Defect Hybrid Organic/Inorganic Perovskite Films as PV Absorbers. (FY 2015FY 2016). In collaboration with organic metal halide perovskite (see article). Ultrahigh-Efficiency and Low-Cost Polycrystalline Halide

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…

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.

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.

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.

Infrared evanescent field sensing with quantum cascade lasers and planar silver halide waveguides.

PubMed

Charlton, Christy; Katzir, Abraham; Mizaikoff, Boris

2005-07-15

We demonstrate the first midinfrared evanescent field absorption measurements with an InGaAs/AlInAs/InP distributed feedback (DFB) quantum cascade laser (QCL) light source operated at room temperature coupled to a free-standing, thin-film, planar, silver halide waveguide. Two different analytes, each matched to the emission frequency of a QCL, were investigated to verify the potential of this technique. The emission of a 1650 cm(-1) QCL overlaps with the amide absorption band of urea, which was deposited from methanol solution, forming urea crystals at the waveguide surface after solvent evaporation. Solid urea was detected down to 80.7 microg of precipitate at the waveguide surface. The emission frequency of a 974 cm(-1) QCL overlaps with the CH3-C absorption feature of acetic anhydride. Solutions of acetic anhydride in acetonitrile have been detected down to a volume of 0.01 microL (10.8 microg) of acetic anhydride solution after deposition at the planar waveguide (PWG) surface. Free-standing, thin-film, planar, silver halide waveguides were produced by press-tapering heated, cylindrical, silver halide fiber segments to create waveguides with a thickness of 300-190 microm, a width of 3 mm, and a length of 35 mm. In addition, Fourier transform infrared (FT-IR) evanescent field absorption measurements with planar silver halide waveguides and transmission absorption QCL measurements verify the obtained results.

Evidence for halogen bond covalency in acyclic and interlocked halogen-bonding receptor anion recognition

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

Robinson, Sean W.; Mustoe, Chantal L.; White, Nicholas G.

The synthesis and anion binding properties of novel halogen-bonding (XB) bis-iodotriazole-pyridinium-containing acyclic and [2]catenane anion host systems are described. The XB acyclic receptor displays selectivity for acetate over halides with enhanced anion recognition properties compared to the analogous hydrogen-bonding (HB) acyclic receptor. A reversal in halide selectivity is observed in the XB [2]catenane, in comparison to the acyclic XB receptor, due to the interlocked host’s unique three-dimensional binding cavity, and no binding is observed for oxoanions. Notable halide anion association constant values determined for the [2]catenane in competitive organic–aqueous solvent mixtures demonstrate considerable enhancement of anion recognition as compared tomore » the HB catenane analogue. X-ray crystallographic analysis of a series of halide catenane complexes reveal strong XB interactions in the solid state. These interactions were studied using Cl and Br K-edge X-ray Absorption Spectroscopy (XAS) indicating intense pre-edge features characteristic of charge transfer from the halide to its bonding partner (σ AX←X–* ← X1s), and providing a direct measure of the degree of covalency in the halogen bond(s). Lastly, the data reveal that the degree of covalency is similar to that which is observed in transition metal coordinate covalent bonds. These results are supported by DFT results, which correlate well with the experimental data.« less

Enhanced coagulation with powdered activated carbon or MIEX secondary treatment: a comparison of disinfection by-product formation and precursor removal.

PubMed

Watson, Kalinda; Farré, Maria José; Knight, Nicole

2015-01-01

The removal of both organic and inorganic disinfection by-product (DBP) precursors prior to disinfection is important in mitigating DBP formation, with halide removal being particularly important in salinity-impacted water sources. A matrix of waters of variable alkalinity, halide concentration and dissolved organic carbon (DOC) concentration were treated with enhanced coagulation (EC) followed by anion exchange (MIEX resin) or powdered activated carbon (PAC) and the subsequent disinfection by-product formation potentials (DBP-FPs) assessed and compared to DBP-FPs for untreated samples. Halide and DOC removal were also monitored for both treatment processes. Bromide and iodide adsorption by MIEX treatment ranged from 0 to 53% and 4-78%, respectively. As expected, EC and PAC treatments did not remove halides. DOC removal by EC/PAC was 70 ± 10%, while EC/MIEX enabled a DOC removal of 66 ± 12%. Despite the halide removals achieved by MIEX, increases in brominated disinfection by-product (Br-DBP) formation were observed relative to untreated samples, when favourable Br:DOC ratios were created by the treatment. However, the increases in formation were less than what was observed for the EC/PAC treated waters, which caused large increases in Br-DBP formation when high Br-DBP-forming water quality conditions occurred. The formation potential of fully chlorinated DBPs decreased after treatment in all cases.

Evidence for halogen bond covalency in acyclic and interlocked halogen-bonding receptor anion recognition

DOE PAGES

Robinson, Sean W.; Mustoe, Chantal L.; White, Nicholas G.; ...

2014-12-05

The synthesis and anion binding properties of novel halogen-bonding (XB) bis-iodotriazole-pyridinium-containing acyclic and [2]catenane anion host systems are described. The XB acyclic receptor displays selectivity for acetate over halides with enhanced anion recognition properties compared to the analogous hydrogen-bonding (HB) acyclic receptor. A reversal in halide selectivity is observed in the XB [2]catenane, in comparison to the acyclic XB receptor, due to the interlocked host’s unique three-dimensional binding cavity, and no binding is observed for oxoanions. Notable halide anion association constant values determined for the [2]catenane in competitive organic–aqueous solvent mixtures demonstrate considerable enhancement of anion recognition as compared tomore » the HB catenane analogue. X-ray crystallographic analysis of a series of halide catenane complexes reveal strong XB interactions in the solid state. These interactions were studied using Cl and Br K-edge X-ray Absorption Spectroscopy (XAS) indicating intense pre-edge features characteristic of charge transfer from the halide to its bonding partner (σ AX←X–* ← X1s), and providing a direct measure of the degree of covalency in the halogen bond(s). Lastly, the data reveal that the degree of covalency is similar to that which is observed in transition metal coordinate covalent bonds. These results are supported by DFT results, which correlate well with the experimental data.« less

Particle generator

DOEpatents

Hess, Wayne P.; Joly, Alan G.; Gerrity, Daniel P.; Beck, Kenneth M.; Sushko, Peter V.; Shlyuger, Alexander L.

2005-06-28

Energy tunable solid state sources of neutral particles are described. In a disclosed embodiment, a halogen particle source includes a solid halide sample, a photon source positioned to deliver photons to a surface of the halide, and a collimating means positioned to accept a spatially defined plume of hyperthermal halogen particles emitted from the sample surface.

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...

On the Boiling Points of the Alkyl Halides.

ERIC Educational Resources Information Center

Correia, John

1988-01-01

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

Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

ERIC Educational Resources Information Center

Cruz-Ramirez de Arellano, Daniel

2013-01-01

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

Students' Understanding of Alkyl Halide Reactions in Undergraduate Organic Chemistry

ERIC Educational Resources Information Center

Cruz-Ramírez de Arellano, Daniel; Towns, Marcy H.

2014-01-01

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

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)

Palladium-Catalyzed Conversion of Aryl and Vinyl Triflates to Bromides and Chlorides

PubMed Central

Shen, Xiaoqiang; Hyde, Alan M.; Buchwald, Stephen L.

2010-01-01

The palladium-catalyzed conversion of aryl and vinyl triflates to aryl and vinyl halides (bromides and chlorides) has been developed using dialkylbiaryl phosphine ligands. A variety of aryl, heteroaryl and vinyl halides can be prepared via this method in good to excellent yields. PMID:20857936

Formation of random and regular relief-phase structures on silver halide photographic emulsions by holographic methods

NASA Astrophysics Data System (ADS)

Ganzherli, N. M.; Gulyaev, S. N.; Gurin, A. S.; Kramushchenko, D. D.; Maurer, I. A.; Chernykh, D. F.

2009-07-01

The formation of diffusers and microlens rasters on silver halide emulsions by holographic methods is considered. Two techniques for converting amplitude holographic recording to relief-phase recording, selective curing and irradiation of the emulsion gelatin by short-wavelength UV radiation, are compared.

Ab initio calculations of the lattice dynamics of silver halides

NASA Astrophysics Data System (ADS)

Gordienko, A. B.; Kravchenko, N. G.; Sedelnikov, A. N.

2010-12-01

Based on ab initio pseudopotential calculations, the results of investigations of the lattice dynamics of silver halides AgHal (Hal = Cl, Br, I) are presented. Equilibrium lattice parameters, phonon spectra, frequency densities and effective atomic-charge values are obtained for all types of crystals under study.

Inhomogeneous degradation in metal halide perovskites

NASA Astrophysics Data System (ADS)

Yang, Rong; Zhang, Li; Cao, Yu; Miao, Yanfeng; Ke, You; Wei, Yingqiang; Guo, Qiang; Wang, Ying; Rong, Zhaohua; Wang, Nana; Li, Renzhi; Wang, Jianpu; Huang, Wei; Gao, Feng

2017-08-01

Although the rapid development of organic-inorganic metal halide perovskite solar cells has led to certified power conversion efficiencies of above 20%, their poor stability remains a major challenge, preventing their practical commercialization. In this paper, we investigate the intrinsic origin of the poor stability in perovskite solar cells by using a confocal fluorescence microscope. We find that the degradation of perovskite films starts from grain boundaries and gradually extend to the center of the grains. Firmly based on our findings, we further demonstrate that the device stability can be significantly enhanced by increasing the grain size of perovskite crystals. Our results have important implications to further enhance the stability of optoelectronic devices based on metal halide perovskites.

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.

The Electrical and Optical Properties of Organometal Halide Perovskites Relevant to Optoelectronic Performance.

PubMed

Adinolfi, Valerio; Peng, Wei; Walters, Grant; Bakr, Osman M; Sargent, Edward H

2018-01-01

Organometal halide perovskites are under intense study for use in optoelectronics. Methylammonium and formamidinium lead iodide show impressive performance as photovoltaic materials; a premise that has spurred investigations into light-emitting devices and photodetectors. Herein, the optical and electrical material properties of organometal halide perovskites are reviewed. An overview is given on how the material composition and morphology are tied to these properties, and how these properties ultimately affect device performance. Material attributes and techniques used to estimate them are analyzed for different perovskite materials, with a particular focus on the bandgap, mobility, diffusion length, carrier lifetime, and trap-state density. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Halide (Cl(super -)) Quenching of Quinine Sulfate Fluorescence: A Time-Resolved Fluorescence Experiment for Physical Chemistry

ERIC Educational Resources Information Center

Gutow, Jonathan H.

2005-01-01

The time-resolved fluorescence experiment investigating the halide quenching of fluorescence from quinine sulfate in water is described. The objectives of the experiment include reinforcing student understanding of the kinetics of competing pathways, making connections with microscopic theories of kinetics through comparison of experimental and…

NREL Postdoc Awarded for Work on Breakthrough Solar Technology | News |

Science.gov Websites

widespread, new research must further these trends. One type of materials-halide perovskites-shows promise to group of Joseph M. Luther, working to develop a better understanding of halide perovskite materials fostered," Christians said. "This fellowship gives me the freedom to interact with a wide group

Silver nanoparticles with planar twinned defects: effect of halides for precise tuning of plasmon resonance maxima from 400 to >900 nm.

PubMed

Cathcart, Nicole; Frank, Andrew J; Kitaev, Vladimir

2009-12-14

We studied effects of halides on morphology of planar twinned silver nanoparticles and demonstrated application of these effects to precisely tune silver surface plasmon resonance maxima in a broad vis-NIR range using a reliable two-stage modification protocol.

10 CFR 431.325 - Units to be tested.

Code of Federal Regulations, 2011 CFR

2011-01-01

... EQUIPMENT Metal Halide Lamp Ballasts and Fixtures Test Procedures § 431.325 Units to be tested. For each basic model of metal halide lamp ballast selected for testing, a sample of sufficient size, no less than... energy efficiency calculated as the measured output power to the lamp divided by the measured input power...

36 CFR § 1254.108 - What are NARA's requirements for the microfilming process?

Code of Federal Regulations, 2013 CFR

2013-07-01

... you leave unattended. (j) We inspect the microform output at scheduled intervals during the project to... images, you must provide NARA with a silver halide duplicate negative upon completion of the project. When the project involves more than 10,000 images, you must provide a silver halide duplicate negative...

Semiempirical and DFT Investigations of the Dissociation of Alkyl Halides

ERIC Educational Resources Information Center

Waas, Jack R.

2006-01-01

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

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...

Method of Obtaining Uniform Coatings on Graphite

DOEpatents

Campbell, I. E.

1961-04-01

A method is given for obtaining uniform carbide coatings on graphite bodies. According to the invention a metallic halide in vapor form is passed over the graphite body under such conditions of temperature and pressure that the halide reacts with the graphite to form a coating of the metal carbide on the surface of the graphite.

METHOD OF OBTAINING UNIFORM COATINGS ON GRAPHITE

DOEpatents

Campbell, I.E.

1961-04-01

A method is given for obtaining uniform carbide coatings on graphite bodies. According to the invention a metallic halide in vapor form is passed over the graphite body under such conditions of temperature and pressure that the halide reacts with the graphite to form a coating of the metal carbide on the surface of the graphite.

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...

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.

Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites.

PubMed

Bischak, Connor G; Hetherington, Craig L; Wu, Hao; Aloni, Shaul; Ogletree, D Frank; Limmer, David T; Ginsberg, Naomi S

2017-02-08

The distinct physical properties of hybrid organic-inorganic materials can lead to unexpected nonequilibrium phenomena that are difficult to characterize due to the broad range of length and time scales involved. For instance, mixed halide hybrid perovskites are promising materials for optoelectronics, yet bulk measurements suggest the halides reversibly phase separate upon photoexcitation. By combining nanoscale imaging and multiscale modeling, we find that the nature of halide demixing in these materials is distinct from macroscopic phase separation. We propose that the localized strain induced by a single photoexcited charge interacting with the soft, ionic lattice is sufficient to promote halide phase separation and nucleate a light-stabilized, low-bandgap, ∼8 nm iodide-rich cluster. The limited extent of this polaron is essential to promote demixing because by contrast bulk strain would simply be relaxed. Photoinduced phase separation is therefore a consequence of the unique electromechanical properties of this hybrid class of materials. Exploiting photoinduced phase separation and other nonequilibrium phenomena in hybrid materials more generally could expand applications in sensing, switching, memory, and energy storage.

Photon Transport in One-Dimensional Incommensurately Epitaxial CsPbX 3 Arrays

DOE PAGES

Wang, Yiping; Sun, Xin; Shivanna, Ravichandran; ...

2016-11-16

One-dimensional nanoscale epitaxial arrays serve as a great model in studying fundamental physics and for emerging applications. With an increasing focus laid on the Cs-based inorganic halide perovskite out of its outstanding material stability, we have applied vapor phase epitaxy to grow well aligned horizontal CsPbX 3 (X: Cl, Br, or I or their mixed) nanowire arrays in large scale on mica substrate. The as-grown nanowire features a triangular prism morphology with typical length ranging from a few tens of micrometers to a few millimeters. Structural analysis reveals that the wire arrays follow the symmetry of mica substrate through incommensuratemore » epitaxy, paving a way for a universally applicable method to grow a broad family of halide perovskite materials. We have studied the unique photon transport in the one-dimensional structure in the all-inorganic Cs-based perovskite wires via temperature dependent and spatially resolved photoluminescence. Furthermore, epitaxy of well oriented wire arrays in halide perovskite would be a promising direction for enabling the circuit-level applications of halide perovskite in high-performance electro-optics and optoelectronics.« less

Bication lead iodide 2D perovskite component to stabilize inorganic α-CsPbI3 perovskite phase for high-efficiency solar cells

PubMed Central

Zhang, Taiyang; Dar, M. Ibrahim; Li, Ge; Xu, Feng; Guo, Nanjie; Grätzel, Michael; Zhao, Yixin

2017-01-01

Among various all-inorganic halide perovskites exhibiting better stability than organic-inorganic halide perovskites, α-CsPbI3 with the most suitable band gap for tandem solar cell application faces an issue of phase instability under ambient conditions. We discovered that a small amount of two-dimensional (2D) EDAPbI4 perovskite containing the ethylenediamine (EDA) cation stabilizes the α-CsPbI3 to avoid the undesirable formation of the nonperovskite δ phase. Moreover, not only the 2D perovskite of EDAPbI4 facilitate the formation of α-CsPbI3 perovskite films exhibiting high phase stability at room temperature for months and at 100°C for >150 hours but also the α-CsPbI3 perovskite solar cells (PSCs) display highly reproducible efficiency of 11.8%, a record for all-inorganic lead halide PSCs. Therefore, using the bication EDA presents a novel and promising strategy to design all-inorganic lead halide PSCs with high performance and reliability. PMID:28975149

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

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

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.

APPLICATION OF VACUUM SALT DISTILLATION TECHNOLOGY FOR THE REMOVAL OF FLUORIDE AND CHLORIDE FROM LEGACY FISSILE MATERIALS

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

Pierce, R.; Peters, T.

2011-11-01

Between September 2009 and January 2011, the Savannah River National Laboratory (SRNL) and the Savannah River Site (SRS) HB-Line Facility designed, developed, tested, and successfully deployed a production-scale system for the distillation of sodium chloride (NaCl) and potassium chloride (KCl) from plutonium oxide (PuO{sub 2}). Subsequent efforts adapted the vacuum salt distillation (VSD) technology for the removal of chloride and fluoride from less-volatile halide salts at the same process temperature and vacuum. Calcium chloride (CaCl{sub 2}), calcium fluoride (CaF{sub 2}), and plutonium fluoride (PuF{sub 3}) were of particular concern. To enable the use of the same operating conditions for themore » distillation process, SRNL employed in situ exchange reactions to convert the less-volatile halide salts to compounds that facilitated the distillation of halide without removal of plutonium. SRNL demonstrated the removal of halide from CaCl{sub 2}, CaF{sub 2} and PuF{sub 3} below 1000 C using VSD technology.« less

Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics.

PubMed

Hoke, Eric T; Slotcavage, Daniel J; Dohner, Emma R; Bowring, Andrea R; Karunadasa, Hemamala I; McGehee, Michael D

2015-01-01

We report on reversible, light-induced transformations in (CH 3 NH 3 )Pb(Br x I 1- x ) 3 . Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics.

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.

Halide salts and their structural properties in presence of secondary amine based molecule: A combined experimental and theoretical analysis

NASA Astrophysics Data System (ADS)

Ghosh, Pritam; Hazra, Abhijit; Ghosh, Meenakshi; Chandra Murmu, Naresh; Banerjee, Priyabrata

2018-04-01

Biologically relevant halide salts and its solution state structural properties are always been significant. In general, exposure of halide salts into polar solution medium results in solvation which in turn separates the cationic and anionic part of the salt. However, the conventional behaviour of salts might alter in presence of any secondary amine based compound, i.e.; moderately strong Lewis acid. In its consequence, to investigate the effect of secondary amine based compound in the salt solution, novel (E)-2-(4-bromobenzylidene)-1-(perfluorophenyl) hydrazine has been synthesized and used as secondary amine source. The secondary amine compound interestingly shows a drastic color change upon exposure to fluoride salts owing to hydrogen bonding interaction. Several experimental methods, e.g.; SCXRD, UV-Vis, FT-IR, ESI-MS and DLS together with modern DFT (i.e.; DFT-D3) have been performed to explore the structural properties of the halide salts upon exposure to secondary amine based compound. The effect of counter cation of the fluoride salt in binding with secondary amine source has also been investigated.

Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence

PubMed Central

Xing, Guichuan; Wu, Bo; Wu, Xiangyang; Li, Mingjie; Du, Bin; Wei, Qi; Guo, Jia; Yeow, Edwin K. L.; Sum, Tze Chien; Huang, Wei

2017-01-01

The slow bimolecular recombination that drives three-dimensional lead-halide perovskites' outstanding photovoltaic performance is conversely a fundamental limitation for electroluminescence. Under electroluminescence working conditions with typical charge densities lower than 1015 cm−3, defect-states trapping in three-dimensional perovskites competes effectively with the bimolecular radiative recombination. Herein, we overcome this limitation using van-der-Waals-coupled Ruddlesden-Popper perovskite multi-quantum-wells. Injected charge carriers are rapidly localized from adjacent thin few layer (n≤4) multi-quantum-wells to the thick (n≥5) multi-quantum-wells with extremely high efficiency (over 85%) through quantum coupling. Light emission originates from excitonic recombination in the thick multi-quantum-wells at much higher decay rate and efficiency than bimolecular recombination in three-dimensional perovskites. These multi-quantum-wells retain the simple solution processability and high charge carrier mobility of two-dimensional lead-halide perovskites. Importantly, these Ruddlesden-Popper perovskites offer new functionalities unavailable in single phase constituents, permitting the transcendence of the slow bimolecular recombination bottleneck in lead-halide perovskites for efficient electroluminescence. PMID:28239146

Transcending the slow bimolecular recombination in lead-halide perovskites for electroluminescence.

PubMed

Xing, Guichuan; Wu, Bo; Wu, Xiangyang; Li, Mingjie; Du, Bin; Wei, Qi; Guo, Jia; Yeow, Edwin K L; Sum, Tze Chien; Huang, Wei

2017-02-27

The slow bimolecular recombination that drives three-dimensional lead-halide perovskites' outstanding photovoltaic performance is conversely a fundamental limitation for electroluminescence. Under electroluminescence working conditions with typical charge densities lower than 10 15  cm -3 , defect-states trapping in three-dimensional perovskites competes effectively with the bimolecular radiative recombination. Herein, we overcome this limitation using van-der-Waals-coupled Ruddlesden-Popper perovskite multi-quantum-wells. Injected charge carriers are rapidly localized from adjacent thin few layer (n≤4) multi-quantum-wells to the thick (n≥5) multi-quantum-wells with extremely high efficiency (over 85%) through quantum coupling. Light emission originates from excitonic recombination in the thick multi-quantum-wells at much higher decay rate and efficiency than bimolecular recombination in three-dimensional perovskites. These multi-quantum-wells retain the simple solution processability and high charge carrier mobility of two-dimensional lead-halide perovskites. Importantly, these Ruddlesden-Popper perovskites offer new functionalities unavailable in single phase constituents, permitting the transcendence of the slow bimolecular recombination bottleneck in lead-halide perovskites for efficient electroluminescence.

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

Slavney, Adam H.; Leppert, Linn; Bartesaghi, Davide

In this study, halide double perovskites have recently been developed as less toxic analogs of the lead perovskite solar-cell absorbers APbX 3 (A = monovalent cation; X = Br or I). However, all known halide double perovskites have large bandgaps that afford weak visible-light absorption. The first halide double perovskite evaluated as an absorber, Cs 2AgBiBr 6 (1), has a bandgap of 1.95 eV. Here, we show that dilute alloying decreases 1’s bandgap by ca. 0.5 eV. Importantly, time-resolved photoconductivity measurements reveal long-lived carriers with microsecond lifetimes in the alloyed material, which is very promising for photovoltaic applications. The alloyedmore » perovskite described herein is the first double perovskite to show comparable bandgap energy and carrier lifetime to those of (CH 3NH 3)PbI 3. By describing how energy- and symmetry-matched impurity orbitals, at low concentrations, dramatically alter 1’s band edges, we open a potential pathway for the large and diverse family of halide double perovskites to compete with APbX 3 absorbers.« less

Calcium looping process for high purity hydrogen production integrated with capture of carbon dioxide, sulfur and halides

DOEpatents

Ramkumar, Shwetha; Fan, Liang-Shih

2013-07-30

A process for producing hydrogen comprising the steps of: (i) gasifying a fuel into a raw synthesis gas comprising CO, hydrogen, steam, sulfur and halide contaminants in the form of H.sub.2S, COS, and HX, wherein X is a halide; (ii) passing the raw synthesis gas through a water gas shift reactor (WGSR) into which CaO and steam are injected, the CaO reacting with the shifted gas to remove CO.sub.2, sulfur and halides in a solid-phase calcium-containing product comprising CaCO.sub.3, CaS and CaX.sub.2; (iii) separating the solid-phase calcium-containing product from an enriched gaseous hydrogen product; and (iv) regenerating the CaO by calcining the solid-phase calcium-containing product at a condition selected from the group consisting of: in the presence of steam, in the presence of CO.sub.2, in the presence of synthesis gas, in the presence of H.sub.2 and O.sub.2, under partial vacuum, and combinations thereof.

Colloidal thallium halide nanocrystals with reasonable luminescence, carrier mobility and diffusion length.

PubMed

Mir, Wasim J; Warankar, Avinash; Acharya, Ashutosh; Das, Shyamashis; Mandal, Pankaj; Nag, Angshuman

2017-06-01

Colloidal lead halide based perovskite nanocrystals (NCs) have been recently established as an interesting class of defect-tolerant NCs with potential for superior optoelectronic applications. The electronic band structure of thallium halides (TlX, where X = Br and I) show a strong resemblance to lead halide perovskites, where both Pb 2+ and Tl + exhibit a 6s 2 inert pair of electrons and strong spin-orbit coupling. Although the crystal structure of TlX is not perovskite, the similarities of its electronic structure with lead halide perovskites motivated us to prepare colloidal TlX NCs. These TlX NCs exhibit a wide bandgap (>2.5 eV or <500 nm) and the potential to exhibit a reduced density of deep defect states. Optical pump terahertz (THz) probe spectroscopy with excitation fluence in the range of 0.85-5.86 × 10 13 photons per cm 2 on NC films shows that the TlBr NCs possess high effective carrier mobility (∼220 to 329 cm 2 V -1 s -1 ), long diffusion length (∼0.77 to 0.98 μm), and reasonably high photoluminescence efficiency (∼10%). This combination of properties is remarkable compared to other wide-bandgap (>2.5 eV) semiconductor NCs, which suggests a reduction in the deep-defect states in the TlX NCs. Furthermore, the ultrafast carrier dynamics and temperature-dependent reversible structural phase transition together with its influence on the optical properties of the TlX NCs are studied.

Transformation of sintered CsPbBr 3 nanocrystals to cubic CsPbI 3 and gradient CsPbBr xI 3–x through halide exchange

DOE PAGES

Hoffman, Jacob B.; Schleper, A. Lennart; Kamat, Prashant V.

2016-06-20

All-inorganic cesium lead halide (CsPbX 3, X = Br –, I –) perovskites could potentially provide comparable photovoltaic performance with enhanced stability compared to organic–inorganic lead halide species. However, small-bandgap cubic CsPbI3 has been difficult to study due to challenges forming CsPbI 3 in the cubic phase. Here, a low-temperature procedure to form cubic CsPbI 3 has been developed through a halide exchange reaction using films of sintered CsPbBr 3 nanocrystals. The reaction was found to be strongly dependent upon temperature, featuring an Arrhenius relationship. Additionally, film thickness played a significant role in determining internal film structure at intermediate reactionmore » times. Thin films (50 nm) showed only a small distribution of CsPbBr xI 3–x species, while thicker films (350 nm) exhibited much broader distributions. Furthermore, internal film structure was ordered, featuring a compositional gradient within film. Transient absorption spectroscopy showed the influence of halide exchange on the excited state of the material. In thicker films, charge carriers were rapidly transferred to iodide-rich regions near the film surface within the first several picoseconds after excitation. Furthermore, this ultrafast vectorial charge-transfer process illustrates the potential of utilizing compositional gradients to direct charge flow in perovskite-based photovoltaics.« less

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.

Effect of halide-mixing on the switching behaviors of organic-inorganic hybrid perovskite memory

NASA Astrophysics Data System (ADS)

Hwang, Bohee; Gu, Chungwan; Lee, Donghwa; Lee, Jang-Sik

2017-03-01

Mixed halide perovskite materials are actively researched for solar cells with high efficiency. Their hysteresis which originates from the movement of defects make perovskite a candidate for resistive switching memory devices. We demonstrate the resistive switching device based on mixed-halide organic-inorganic hybrid perovskite CH3NH3PbI3-xBrx (x = 0, 1, 2, 3). Solvent engineering is used to deposit the homogeneous CH3NH3PbI3-xBrx layer on the indium-tin oxide-coated glass substrates. The memory device based on CH3NH3PbI3-xBrx exhibits write endurance and long retention, which indicate reproducible and reliable memory properties. According to the increase in Br contents in CH3NH3PbI3-xBrx the set electric field required to make the device from low resistance state to high resistance state decreases. This result is in accord with the theoretical calculation of migration barriers, that is the barrier to ionic migration in perovskites is found to be lower for Br- (0.23 eV) than for I- (0.29-0.30 eV). The resistive switching may be the result of halide vacancy defects and formation of conductive filaments under electric field in the mixed perovskite layer. It is observed that enhancement in operating voltage can be achieved by controlling the halide contents in the film.

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.

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

King, W.A.; Kubas, G.J.

The present invention provides: a composition of the formula M{sup +x}(Ga(Y){sub 4}{sup {minus}}){sub x} where M is a metal selected from the group consisting of lithium, sodium, potassium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; a composition of the formula (R){sub x}Q{sup +}Ga(Y){sub 4}{sup {minus}} where Q is selected from themore » group consisting of carbon, nitrogen, sulfur, phosphorus and oxygen, each R is a ligand selected from the group consisting of alkyl, aryl, and hydrogen, x is an integer selected from the group consisting of 3 and 4 depending upon Q, and each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; an ionic polymerization catalyst composition including an active cationic portion and a gallium based weakly coordinating anion; and bridged anion species of the formula M{sup +x}{sub y}[X(GaY{sub 3}){sub z}]{sup {minus}y}{sub x} where M is a metal selected from the group consisting of lithium, sodium, potassium, magnesium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, X is a bridging group between two gallium atoms, y is an integer selected from the group consisting 1 and 2, z is an integer of at least 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide.« less

Predicting the thermodynamic stability of double-perovskite halides from density functional theory

DOE PAGES

Han, Dan; Zhang, Tao; Huang, Menglin; ...

2018-05-24

Recently, a series of double-perovskite halide compounds such as Cs 2AgBiCl 6 and Cs 2AgBiBr 6 have attracted intensive interest as promising alternatives to the solar absorber material CH 3NH 3PbI 3 because they are Pb-free and may exhibit enhanced stability. The thermodynamic stability of a number of double-perovskite halides has been predicted based on density functional theory (DFT) calculations of compound formation energies. In this paper, we found that the stability prediction can be dependent on the approximations used for the exchange-correlation functionals, e.g., the DFT calculations using the widely used Perdew, Burke, Ernzerhof (PBE) functional predict that Csmore » 2AgBiBr 6 is thermodynamically unstable against phase-separation into the competing phases such as AgBr, Cs 2AgBr 3, Cs 3Bi 2Br 9, etc., obviously inconsistent with the good stability observed experimentally. The incorrect prediction by the PBE calculation results from its failure to predict the correct ground-state structures of AgBr, AgCl, and CsCl. By contrast, the DFT calculations based on local density approximation, optB86b-vdW, and optB88-vdW functionals predict the ground-state structures of these binary halides correctly. Furthermore, the optB88-vdW functional is found to give the most accurate description of the lattice constants of the double-perovskite halides and their competing phases. Given these two aspects, we suggest that the optB88-vdW functional should be used for predicting thermodynamic stability in the future high-throughput computational material design or the construction of the Materials Genome database for new double-perovskite halides. As a result, using different exchange-correlation functionals has little influence on the dispersion of the conduction and the valence bands near the electronic bandgap; however, the calculated bandgap can be affected indirectly by the optimized lattice constant, which varies for different functionals.« less

Predicting the thermodynamic stability of double-perovskite halides from density functional theory

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

Han, Dan; Zhang, Tao; Huang, Menglin

Recently, a series of double-perovskite halide compounds such as Cs 2AgBiCl 6 and Cs 2AgBiBr 6 have attracted intensive interest as promising alternatives to the solar absorber material CH 3NH 3PbI 3 because they are Pb-free and may exhibit enhanced stability. The thermodynamic stability of a number of double-perovskite halides has been predicted based on density functional theory (DFT) calculations of compound formation energies. In this paper, we found that the stability prediction can be dependent on the approximations used for the exchange-correlation functionals, e.g., the DFT calculations using the widely used Perdew, Burke, Ernzerhof (PBE) functional predict that Csmore » 2AgBiBr 6 is thermodynamically unstable against phase-separation into the competing phases such as AgBr, Cs 2AgBr 3, Cs 3Bi 2Br 9, etc., obviously inconsistent with the good stability observed experimentally. The incorrect prediction by the PBE calculation results from its failure to predict the correct ground-state structures of AgBr, AgCl, and CsCl. By contrast, the DFT calculations based on local density approximation, optB86b-vdW, and optB88-vdW functionals predict the ground-state structures of these binary halides correctly. Furthermore, the optB88-vdW functional is found to give the most accurate description of the lattice constants of the double-perovskite halides and their competing phases. Given these two aspects, we suggest that the optB88-vdW functional should be used for predicting thermodynamic stability in the future high-throughput computational material design or the construction of the Materials Genome database for new double-perovskite halides. As a result, using different exchange-correlation functionals has little influence on the dispersion of the conduction and the valence bands near the electronic bandgap; however, the calculated bandgap can be affected indirectly by the optimized lattice constant, which varies for different functionals.« less

Gallium based low-interaction anions

DOEpatents

King, Wayne A.; Kubas, Gregory J.

2000-01-01

The present invention provides: a composition of the formula M.sup.+x (Ga(Y).sub.4.sup.-).sub.x where M is a metal selected from the group consisting of lithium, sodium, potassium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; a composition of the formula (R).sub.x Q.sup.+ Ga(Y).sub.4.sup.- where Q is selected from the group consisting of carbon, nitrogen, sulfur, phosphorus and oxygen, each R is a ligand selected from the group consisting of alkyl, aryl, and hydrogen, x is an integer selected from the group consisting of 3 and 4 depending upon Q, and each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide; an ionic polymerization catalyst composition including an active cationic portion and a gallium based weakly coordinating anion; and bridged anion species of the formula M.sup.+x.sub.y [X(Ga(Y.sub.3).sub.z ].sup.-y.sub.x where M is a metal selected from the group consisting of lithium, sodium, potassium, magnesium, cesium, calcium, strontium, thallium, and silver, x is an integer selected from the group consisting of 1 or 2, X is a bridging group between two gallium atoms, y is an integer selected from the group consisting 1 and 2, z is an integer of at least 2, each Y is a ligand selected from the group consisting of aryl, alkyl, hydride and halide with the proviso that at least one Y is a ligand selected from the group consisting of aryl, alkyl and halide.

Spectral Features and Charge Dynamics of Lead Halide Perovskites: Origins and Interpretations.

PubMed

Sum, Tze Chien; Mathews, Nripan; Xing, Guichuan; Lim, Swee Sien; Chong, Wee Kiang; Giovanni, David; Dewi, Herlina Arianita

2016-02-16

Lead halide perovskite solar cells are presently the forerunner among the third generation solution-processed photovoltaic technologies. With efficiencies exceeding 20% and low production costs, they are prime candidates for commercialization. Critical insights into their light harvesting, charge transport, and loss mechanisms have been gained through time-resolved optical probes such as femtosecond transient absorption spectroscopy (fs-TAS), transient photoluminescence spectroscopy, and time-resolved terahertz spectroscopy. Specifically, the discoveries of long balanced electron-hole diffusion lengths and gain properties in halide perovskites underpin their significant roles in uncovering structure-function relations and providing essential feedback for materials development and device optimization. In particular, fs-TAS is becoming increasingly popular in perovskite characterization studies, with commercial one-box pump-probe systems readily available as part of a researcher's toolkit. Although TAS is a powerful probe in the study of charge dynamics and recombination mechanisms, its instrumentation and data interpretation can be daunting even for experienced researchers. This issue is exacerbated by the sensitive nature of halide perovskites where the kinetics are especially susceptible to pump fluence, sample preparation and handling and even degradation effects that could lead to disparate conclusions. Nonetheless, with end-users having a clear understanding of TAS's capabilities, subtleties, and limitations, cutting-edge work with deep insights can still be performed using commercial setups as has been the trend for ubiquitous spectroscopy instruments like absorption, fluorescence, and transient photoluminescence spectrometers. Herein, we will first briefly examine the photophysical processes in lead halide perovskites, highlighting their novel properties. Next, we proceed to give a succinct overview of the fundamentals of pump-probe spectroscopy in relation to the spectral features of halide perovskites and their origins. In the process, we emphasize some key findings of seminal photophysical studies and draw attention to the interpretations that remain divergent and the open questions. This is followed by a general description into how we prepare and conduct the TAS characterization of CH3NH3PbI3 thin films in our laboratory with specific discussions into the potential pitfalls and the influence of thin film processing on the kinetics. Lastly, we conclude with our views on the challenges and opportunities from the photophysical perspective for the field and our expectations for systems beyond lead halide perovskites.

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 kinetics can be tailored to yield improved thin film homogeneity. Because degradation of the as-formed perovskite film is in many ways analogous to its initial formation, the same suite of monitoring techniques reveals the moisture-induced transformation of low band gap methylammonium lead iodide (CH3NH3PbI3) to wide band gap hydrate compounds. The rate of degradation is increased upon exposure to light. Interestingly, the hydration process is reversible under certain conditions. This facile formation and subsequent chemical lability raises the question of whether CH3NH3PbI3 and its analogues are thermodynamically stable phases, thus posing a significant challenge to the development of transformative perovskite photovoltaics. Adequately addressing issues of structural and chemical stability under real-world operating conditions is paramount if perovskite solar cells are to make an impact beyond the benchtop. Expanding our fundamental knowledge of lead halide perovskite formation and degradation pathways can facilitate fabrication of stable, high-quality perovskite thin films for the next generation of photovoltaic and light emitting devices.

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, crystallization kinetics can be tailored to yield improved thin film homogeneity. Because degradation of the as-formed perovskite film is in many ways analogous to its initial formation, the same suite of monitoring techniques reveals the moisture-induced transformation of low band gap methylammonium lead iodide (CH 3NH 3PbI 3) to wide band gap hydrate compounds. The rate of degradation is increased upon exposure to light. Interestingly, the hydration process is reversible under certain conditions. This facile formation and subsequent chemical lability raises the question of whether CH 3NH 3PbI 3 and its analogues are thermodynamically stable phases, thus posing a significant challenge to the development of transformative perovskite photovoltaics. Adequately addressing issues of structural and chemical stability under real-world operating conditions is paramount if perovskite solar cells are to make an impact beyond the benchtop. Expanding our fundamental knowledge of lead halide perovskite formation and degradation pathways can facilitate fabrication of stable, high-quality perovskite thin films for the next generation of photovoltaic and light emitting devices.« less

Silicon nanocrystal inks, films, and methods

DOEpatents

Wheeler, Lance Michael; Kortshagen, Uwe Richard

2015-09-01

Silicon nanocrystal inks and films, and methods of making and using silicon nanocrystal inks and films, are disclosed herein. In certain embodiments the nanocrystal inks and films include halide-terminated (e.g., chloride-terminated) and/or halide and hydrogen-terminated nanocrystals of silicon or alloys thereof. Silicon nanocrystal inks and films can be used, for example, to prepare semiconductor devices.

40 CFR Appendix A to Part 430 - Methods 1650 and 1653

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Methods 1650 and 1653 A Appendix A to...—Methods 1650 and 1653 Method 1650—Adsorbable Organic Halides by Adsorption and Coulometric Titration 1.0Scope and Application 1.1This method is for determination of adsorbable organic halides (AOX) associated...

40 CFR Appendix A to Part 430 - Methods 1650 and 1653

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 30 2011-07-01 2011-07-01 false Methods 1650 and 1653 A Appendix A to...—Methods 1650 and 1653 Method 1650—Adsorbable Organic Halides by Adsorption and Coulometric Titration 1.0Scope and Application 1.1This method is for determination of adsorbable organic halides (AOX) associated...

40 CFR Appendix A to Part 430 - Methods 1650 and 1653

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 31 2012-07-01 2012-07-01 false Methods 1650 and 1653 A Appendix A to... Part 430—Methods 1650 and 1653 Method 1650—Adsorbable Organic Halides by Adsorption and Coulometric Titration 1.0Scope and Application 1.1This method is for determination of adsorbable organic halides (AOX...

Fabrication of Low-Loss Halide Glass Fibers.

DTIC Science & Technology

1985-09-01

chalcogenides, have some merit. Well known, also are the polycrystalline halide materials such as KRS-5, TlBr , *TlI and AgCl and their single...tension of the melt zone is high enough to *" eliminate sagging in the fibers. Using this technique, ( TlBr )I (KRS-5), TlBr , CuCl, AgCl, and AgBr have

Ligand-free, palladium-catalyzed dihydrogen generation from TMDS: dehalogenation of aryl halides on water.

PubMed

Bhattacharjya, Anish; Klumphu, Piyatida; Lipshutz, Bruce H

2015-03-06

A mild and environmentally attractive dehalogenation of functionalized aryl halides has been developed using nanoparticles formed from PdCl2 in the presence of tetramethyldisiloxane (TMDS) on water. The active catalyst and reaction medium can be recycled. This method can also be applied to cascade reactions in a one-pot sequence.

Halide and Oxy-Halide Eutectic Systems for High-Performance, High-Temperature Heat Transfer Fluids (Fact Sheet)

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

Not Available

2012-12-01

The University of Arizona, Arizona Statue University (ASU), and Georgia Institute of Technology is one of the 2012 SunShot CSP R&D awardees for their Multidisciplinary University Research Initiative (MURI): High Operating Temperature (HOT) Fluids. This fact sheet explains the motivation, description, and impact of the project.

Method for calcining nuclear waste solutions containing zirconium and halides

DOEpatents

Newby, Billie J.

1979-01-01

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

Using Group-Inquiry to Study Differing Reaction Conditions in the E2 Elimination of Cyclohexyl Halides

ERIC Educational Resources Information Center

Long, Robert D.

2012-01-01

In this experiment, students individually conduct one of several variations of an E2 dehydrohalogenation reaction on a cyclohexyl halide substrate for 30 min, which is sufficient only for a partial reaction to occur. The variations examine reaction conditions including different leaving groups, decreased reaction temperature, or reduced base…

One-dimensional, two-dimensional, and three-dimensional photonic crystals fabricated with interferometric techniques on ultrafine-grain silver halide emulsions

NASA Astrophysics Data System (ADS)

Ulibarrena, Manuel; Carretero, Luis; Acebal, Pablo; Madrigal, Roque; Blaya, Salvador; Fimia, Antonio

2004-09-01

Holographic techniques have been used for manufacturing multiple band one-dimensional, two-dimensional, and three-dimensional photonic crystals with different configurations, by multiplexing reflection and transmission setups on a single layer of holographic material. The recording material used for storage is an ultra fine grain silver halide emulsion, with an average grain size around 20 nm. The results are a set of photonic crystals with the one-dimensional, two-dimensional, and three-dimensional index modulation structure consisting of silver halide particles embedded in the gelatin layer of the emulsion. The characterisation of the fabricated photonic crystals by measuring their transmission band structures has been done and compared with theoretical calculations.

Relationships between Lead Halide Perovskite Thin-Film Fabrication, Morphology, and Performance in Solar Cells.

PubMed

Sharenko, Alexander; Toney, Michael F

2016-01-20

Solution-processed lead halide perovskite thin-film solar cells have achieved power conversion efficiencies comparable to those obtained with several commercial photovoltaic technologies in a remarkably short period of time. This rapid rise in device efficiency is largely the result of the development of fabrication protocols capable of producing continuous, smooth perovskite films with micrometer-sized grains. Further developments in film fabrication and morphological control are necessary, however, in order for perovskite solar cells to reliably and reproducibly approach their thermodynamic efficiency limit. This Perspective discusses the fabrication of lead halide perovskite thin films, while highlighting the processing-property-performance relationships that have emerged from the literature, and from this knowledge, suggests future research directions.

Alkali halide microstructured optical fiber for X-ray detection

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

DeHaven, S. L., E-mail: stanton.l.dehaven@nasa.gov, E-mail: russel.a.wincheski@nasa.gov; Wincheski, R. A., E-mail: stanton.l.dehaven@nasa.gov, E-mail: russel.a.wincheski@nasa.gov; Albin, S., E-mail: salbin@nsu.edu

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. Themore » results and associated materials difference are discussed.« less

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

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

Selig, W.

1980-01-01

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

Nanowire Lasers of Formamidinium Lead Halide Perovskites and Their Stabilized Alloys with Improved Stability

DOE PAGES

Fu, Yongping; Zhu, Haiming; Schrader, Alex W.; ...

2016-01-04

The excellent intrinsic optoelectronic properties of methylammonium lead halide perovskites (MAPbX 3, X = Br, I), such as high photoluminescence quantum efficiency, long carrier lifetime, and high gain coupled with the facile solution growth of nanowires make them promising new materials for ultralow-threshold nanowire lasers. However, their photo and thermal stabilities need to be improved for practical applications. Herein, we report a low-temperature solution growth of single crystal nanowires of formamidinium lead halide perovskites (FAPbX 3) that feature red-shifted emission and better thermal stability compared to MAPbX 3. We demonstrate optically pumped room-temperature near-infrared (~820 nm) and green lasing (~560more » nm) from FAPbI 3 (and MABr-stabilized FAPbI 3) and FAPbBr 3 nanowires with low lasing thresholds of several microjoules per square centimeter and high quality factors of about 1500–2300. More remarkably, the FAPbI 3 and MABr-stabilized FAPbI 3 nanowires display durable room-temperature lasing under ~10 8 shots of sustained illumination of 402 nm pulsed laser excitation (150 fs, 250 kHz), substantially exceeding the stability of MAPbI 3 (~10 7 laser shots). We further demonstrate tunable nanowire lasers in wider wavelength region from FA-based lead halide perovskite alloys (FA,MA)PbI 3 and (FA,MA)Pb(I,Br) 3 through cation and anion substitutions. The results suggest that formamidinium lead halide perovskite nanostructures could be more promising and stable materials for the development of light-emitting diodes and continuous-wave lasers.« less

Observation of Enhanced Hole Extraction in Br Concentration Gradient Perovskite Materials.

PubMed

Kim, Min-Cheol; Kim, Byeong Jo; Son, Dae-Yong; Park, Nam-Gyu; Jung, Hyun Suk; Choi, Mansoo

2016-09-14

Enhancing hole extraction inside the perovskite layer is the key factor for boosting photovoltaic performance. Realization of halide concentration gradient perovskite materials has been expected to exhibit rapid hole extraction due to the precise bandgap tuning. Moreover, a formation of Br-rich region on the tri-iodide perovskite layer is expected to enhance moisture stability without a loss of current density. However, conventional synthetic techniques of perovskite materials such as the solution process have not achieved the realization of halide concentration gradient perovskite materials. In this report, we demonstrate the fabrication of Br concentration gradient mixed halide perovskite materials using a novel and facile halide conversion method based on vaporized hydrobromic acid. Accelerated hole extraction and enhanced lifetime due to Br gradient was verified by observing photoluminescence properties. Through the combination of secondary ion mass spectroscopy and transmission electron microscopy with energy-dispersive X-ray spectroscopy analysis, the diffusion behavior of Br ions in perovskite materials was investigated. The Br-gradient was found to be eventually converted into a homogeneous mixed halide layer after undergoing an intermixing process. Br-substituted perovskite solar cells exhibited a power conversion efficiency of 18.94% due to an increase in open circuit voltage from 1.08 to 1.11 V and an advance in fill-factor from 0.71 to 0.74. Long-term stability was also dramatically enhanced after the conversion process, i.e., the power conversion efficiency of the post-treated device has remained over 97% of the initial value under high humid conditions (40-90%) without any encapsulation for 4 weeks.

Well-defined N-heterocyclic carbene silver halides of 1-cyclohexyl-3-arylmethylimidazolylidenes: synthesis, structure and catalysis in A3-reaction of aldehydes, amines and alkynes.

PubMed

Li, Yanbo; Chen, Xiaofeng; Song, Yin; Fang, Ling; Zou, Gang

2011-03-07

Structurally well-defined N-heterocyclic carbene silver chlorides and bromides supported by 1-cyclohexyl-3-benzylimidazolylidene (CyBn-NHC) or 1-cyclohexyl-3-naphthalen-2-ylmethylimidazolylidene (CyNaph-NHC) were synthesized by reaction of the corresponding imidazolium halides with silver(I) oxide while cationic bis(CyBn-NHC) silver nitrate was isolated under similar conditions using imidazolium iodide in the presence of sodium nitrate. Single-crystal X-ray diffraction revealed a dimeric structure through a nonpolar weak-hydrogen-bond supported Ag-Ag bond for 1-cyclohexyl-3-benzylimidazolylidene silver halides [(CyBn-NHC)AgX](2) (X = Cl, 1; Br, 2) but a monomeric structure for N-heterocyclic carbene silver halides with the more sterically demanding 1-cyclohexyl-3-naphthalen-2-ylmethylimidazolylidene ligand (CyNaph-NHC)AgX (X = Cl, 4; Br, 5). Cationic biscarbene silver nitrate [(CyBn-NHC)(2)Ag](+)NO(3)(-)3 assumed a cis orientation with respect to the two carbene ligands. The monomeric complexes (CyNaph-NHC)AgX 4 and 5 showed higher catalytic activity than the dimeric [(CyBn-NHC)AgX](2)1 and 2 as well as the cationic biscarbene silver nitrate 3 in the model three component reaction of 3-phenylpropionaldehyde, phenylacetylene and piperidine with chloride 4 performing best and giving product in almost quantitative yield within 2 h at 100 °C. An explanation for the structure-activity relationship in N-heterocyclic carbene silver halide catalyzed three component reaction is given based on a slightly modified mechanism from the one in literature.

Applications of tapered flat silver halide fiber elements for infrared biospectroscopy with aspects of optical stability and biocompatibility

NASA Astrophysics Data System (ADS)

Delbeck, Sven; Küpper, Lukas; Heise, Herbert M.

2018-02-01

Spectroscopic analysis of different biofluids and bodyfluid-like media has been realized by using tapered flat silver halide fiber elements as infrared biosensors. Optical stability and biocompatibility testing of the sensor elements have been performed with in-vitro samples under representative physiological conditions. After improving the reproducibility of manufacturing the sensor elements, the incoupling of radiation and the general handling including their chemical composition characterization, the fiber sensors were further optimized for the experiments. Stability tests in physiological solutions as well as porcine blood have shown that best results for biospectroscopic applications are available for the mid-IR fingerprint region, with the most stable behaviour as analyzed by the single-beam spectra. Despite several contrary reports, the silver halide material tested is toxic to cell lines chosen from the DIN standard specification for biocompatibility testing. Spectral changes as well as the results based on the DIN standard showed that pretreatment of the fibers is unavoidable to prevent direct contact of cells or human tissue and the silver halide material. Further applications of tapered flat silver halide fibers for the quantification of analytes in bodyfluids have also been tested by ensheathing the fiber-optic sensor element with a dialysis membrane. With the successfully produced prototype, results of diffusion rates and performance of a membrane-ensheathed fiber probe have been obtained. An invitro monitoring fiber sensor was developed aiming at the implantation of a microdialysis system for the analytical quantification of biomolecules such as glucose, lactate and others.

Nanowire Lasers of Formamidinium Lead Halide Perovskites and Their Stabilized Alloys with Improved Stability.

PubMed

Fu, Yongping; Zhu, Haiming; Schrader, Alex W; Liang, Dong; Ding, Qi; Joshi, Prakriti; Hwang, Leekyoung; Zhu, X-Y; Jin, Song

2016-02-10

The excellent intrinsic optoelectronic properties of methylammonium lead halide perovskites (MAPbX3, X = Br, I), such as high photoluminescence quantum efficiency, long carrier lifetime, and high gain coupled with the facile solution growth of nanowires make them promising new materials for ultralow-threshold nanowire lasers. However, their photo and thermal stabilities need to be improved for practical applications. Herein, we report a low-temperature solution growth of single crystal nanowires of formamidinium lead halide perovskites (FAPbX3) that feature red-shifted emission and better thermal stability compared to MAPbX3. We demonstrate optically pumped room-temperature near-infrared (∼820 nm) and green lasing (∼560 nm) from FAPbI3 (and MABr-stabilized FAPbI3) and FAPbBr3 nanowires with low lasing thresholds of several microjoules per square centimeter and high quality factors of about 1500-2300. More remarkably, the FAPbI3 and MABr-stabilized FAPbI3 nanowires display durable room-temperature lasing under ∼10(8) shots of sustained illumination of 402 nm pulsed laser excitation (150 fs, 250 kHz), substantially exceeding the stability of MAPbI3 (∼10(7) laser shots). We further demonstrate tunable nanowire lasers in wider wavelength region from FA-based lead halide perovskite alloys (FA,MA)PbI3 and (FA,MA)Pb(I,Br)3 through cation and anion substitutions. The results suggest that formamidinium lead halide perovskite nanostructures could be more promising and stable materials for the development of light-emitting diodes and continuous-wave lasers.

Identical Origin for Halide and Sulfate Efflorescences on Meteorite Finds and Sulfate Veins in Orgueil

NASA Technical Reports Server (NTRS)

Zolensky, M. E.

2000-01-01

Halide and sulfate efflorescences are common on meteorite finds, especially those from cold deserts. Meanwhile, the late-stage sulfate veins in Orgueil are universally accepted as having originated by the action of late-stage high fO2 aqueous alteration on an asteroid. I suggest here that these phenomena have essentially the same origin.

Identical Origin for Halide and Sulfate Efflorescences On Meteorite Finds and Sulfate Veins In Orgueil

NASA Technical Reports Server (NTRS)

Zolensky, Michael E.

1999-01-01

Halide and sulfate efflorescences are common on meteorite finds, especially those from cold deserts. Meanwhile, the late-stage sulfate veins in Orgueil are universally accepted as having originated by the action of late-stage high fO2 aqueous alteration on an asteroid. I suggest here that these phenomena have essentially the same origin.

Pentavalent uranium trans-dihalides and -pseudohalides.

PubMed

Lewis, Andrew J; Nakamaru-Ogiso, Eiko; Kikkawa, James M; Carroll, Patrick J; Schelter, Eric J

2012-05-21

Pentavalent uranium complexes of the formula U(V)X(2)[N(SiMe(3))(2)](3) (X = F(-), Cl(-), Br(-), N(3)(-), NCS(-)) are accessible from the oxidation of U(III)[N(SiMe(3))(2)](3) through two sequential, one-electron oxidation reactions (halides) and substitution through salt metathesis (pseudohalides). Uranium(v) mixed-halides are also synthesized by successive one-electron oxidation reactions.

Method for removing chlorine compounds from hydrocarbon mixtures

DOEpatents

Janoski, Edward J.; Hollstein, Elmer J.

1985-12-31

A process for removing halide ions from a hydrocarbon feedstream containing halogenated hydrocarbons wherein the contaminated feedstock is contacted with a solution of a suitable oxidizing acid containing a lanthanide oxide, the acid being present in a concentration of at least about 50 weight percent for a time sufficient to remove substantially all of the halide ion from the hydrocarbon feedstock.

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.

Method for removing chlorine compounds from hydrocarbon mixtures

DOEpatents

Janoski, E.J.; Hollstein, E.J.

1984-09-29

A process for removing halide ions from a hydrocarbon feedstream containing halogenated hydrocarbons wherein the contaminated feedstock is contacted with a solution of a suitable oxidizing acid containing a lanthanide oxide, the acid being present in a concentration of at least about 50 weight percent for a time sufficient to remove substantially all of the halide ion from the hydrocarbon feedstock.

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

ERIC Educational Resources Information Center

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

2015-01-01

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

Fire extinguishant materials

NASA Technical Reports Server (NTRS)

Altman, R. L.; Mayer, L. A.; Ling, A. C. (Inventor)

1983-01-01

Fire extinguishant composition comprising a mixture of a finely divided aluminum compound and alkali metal, stannous or plumbous halide is provided. Aluminum compound may be aluminum hydroxide, alumina or boehmite but preferably it is an alkali metal dawsonite. The metal halide may be an alkali metal, e.g. potassium iodide, bromide or chloride or stannous or plumbous iodide, bromide or chloride. Potassium iodide is preferred.

Nickel-Catalyzed Coupling Reactions of Alkyl Electrophiles, Including Unactivated Tertiary Halides, to Generate Carbon–Boron Bonds

PubMed Central

Dudnik, Alexander S.

2012-01-01

Through the use of a catalyst formed in situ from NiBr2•diglyme and a pybox ligand (both of which are commercially available), we have achieved our first examples of coupling reactions of unactivated tertiary alkyl electrophiles, as well as our first success with nickel-catalyzed couplings that generate bonds other than C–C bonds. Specifically, we have determined that this catalyst accomplishes Miyaura-type borylations of unactivated tertiary, secondary, and primary alkyl halides with diboron reagents to furnish alkylboronates, a family of compounds with substantial (and expanding) utility, under mild conditions; indeed, the umpolung borylation of a tertiary alkyl bromide can be achieved at a temperature as low as −10 °C. The method exhibits good functional-group compatibility and is regiospecific, both of which can be issues with traditional approaches to the synthesis of alkylboronates. In contrast to seemingly related nickel-catalyzed C–C bond-forming processes, tertiary halides are more reactive than secondary or primary halides in this nickel-catalyzed C–B bond-forming reaction; this divergence is particularly noteworthy in view of the likelihood that both transformations follow an inner-sphere electron-transfer pathway for oxidative addition. PMID:22668072

Treatment of halogen-containing waste and other waste materials

DOEpatents

Forsberg, Charles W.; Beahm, Edward C.; Parker, George W.

1997-01-01

A process for treating a halogen-containing waste material. The process provides a bath of molten glass containing a sacrificial metal oxide capable of reacting with a halogen in the waste material. The sacrificial metal oxide is present in the molten glass in at least a stoichiometric amount with respect to the halogen in the waste material. The waste material is introduced into the bath of molten glass to cause a reaction between the halogen in the waste material and the sacrificial metal oxide to yield a metal halide. The metal halide is a gas at the temperature of the molten glass. The gaseous metal halide is separated from the molten glass and contacted with an aqueous scrubber solution of an alkali metal hydroxide to yield a metal hydroxide or metal oxide-containing precipitate and a soluble alkali metal halide. The precipitate is then separated from the aqueous scrubber solution. The molten glass containing the treated waste material is removed from the bath as a waste glass. The process of the invention can be used to treat all types of waste material including radioactive wastes. The process is particularly suited for separating halogens from halogen-containing wastes.

Treatment of halogen-containing waste and other waste materials

DOEpatents

Forsberg, C.W.; Beahm, E.C.; Parker, G.W.

1997-03-18

A process is described for treating a halogen-containing waste material. The process provides a bath of molten glass containing a sacrificial metal oxide capable of reacting with a halogen in the waste material. The sacrificial metal oxide is present in the molten glass in at least a stoichiometric amount with respect to the halogen in the waste material. The waste material is introduced into the bath of molten glass to cause a reaction between the halogen in the waste material and the sacrificial metal oxide to yield a metal halide. The metal halide is a gas at the temperature of the molten glass. The gaseous metal halide is separated from the molten glass and contacted with an aqueous scrubber solution of an alkali metal hydroxide to yield a metal hydroxide or metal oxide-containing precipitate and a soluble alkali metal halide. The precipitate is then separated from the aqueous scrubber solution. The molten glass containing the treated waste material is removed from the bath as a waste glass. The process of the invention can be used to treat all types of waste material including radioactive wastes. The process is particularly suited for separating halogens from halogen-containing wastes. 3 figs.

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

Surface properties of lead-free halide double perovskites: Possible visible-light photo-catalysts for water splitting

NASA Astrophysics Data System (ADS)

Volonakis, George; Giustino, Feliciano

2018-06-01

Halide double perovskites based on combinations of monovalent and trivalent cations have been proposed as promising lead-free alternatives to lead halide perovskites. Among the newly synthesized compounds Cs2BiAgCl6, Cs2BiAgBr6, Cs2SbAgCl6, and Cs2InAgCl6, some exhibit bandgaps in the visible range and all have low carrier effective masses; therefore, these materials constitute potential candidates for various opto-electronic applications. Here, we use first-principles calculations to investigate the electronic properties of the surfaces of these four compounds and determine, for the first time, their ionization potential and electron affinity. We find that the double perovskites Cs2BiAgCl6 and Cs2BiAgBr6 are potentially promising materials for photo-catalytic water splitting, while Cs2InAgCl6 and Cs2SbAgCl6 would require controlling their surface termination to obtain energy levels appropriate for water splitting. The energy of the halogen p orbitals is found to control the conduction band level; therefore, we propose that mixed halides could be used to fine-tune the electronic affinity.

High level theoretical study of benzene-halide adducts: the importance of C-H-anion hydrogen bonding.

PubMed

Coletti, Cecilia; Re, Nazzareno

2009-02-26

High level ab initio calculations were performed on the interaction of halide anions (F(-), Cl(-), Br(-), and I(-)) to benzene. For these systems recent experimental and theoretical data are rather scarce, in spite of their growingly acknowledged importance for binding in complex biological systems. We have thus explored the complete basis set limit and the effect of counterpoise basis set superposition error corrections on the minimum geometries and energies of benzene-halide adducts in their possible interaction modes. The binding energy and enthalpy values (ranging from -15.3 kcal/mol for fluoride to -6.1 kcal/mol for iodide) show that the hydrogen bonding occurring in these complexes cannot be described as a weak interaction. We have furthermore investigated the topology of the minima and of other selected sections of the potential energy surface, so to gain further insight on the nature of the halide-benzene interaction. In particular, the geometry corresponding to the C(6v) symmetry, although being overall repulsive, has displayed the unprecedented presence of a small flex (a minimum in C(6v) symmetry) with interaction energy close to zero or slightly attractive.

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

dos Reis, Roberto; Yang, Hao; Ophus, Colin

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

SYNERGISTIC EFFECT OF HALIDE IONS ON THE CORROSION INHIBITION OF MILD STEEL IN SULPHURIC ACID USING METHYL, N-METHYL ETHYL AND ETHYL SUBSTITUTED γ-2,c-6-DIPHENYL PIPERIDIN-4-ONE SEMICARBAZONES

NASA Astrophysics Data System (ADS)

Priya, V. Shanmuga; Rani, C. Uma; Velrani, S.

The synergistic effect of halide ions such as KCl, KBr and KI on the corrosion inhibition of mild steel in 1 N sulphuric acid by γ-2,c-6-diphenyl-t-3-methyl piperdin-4-ones with semicarbazone (01SC), γ-2,c-6-diphenyl-N-methyl-t-3-ethyl piperdin-4-ones with semicarbazone (02SC) and 2,6-diphenyl-t-3-ethyl piperdin-4-one with semicarbazone (03SC) has been examined by weight loss method, potentiodynamic polarization measurements and electrochemical AC impedance spectroscopy. Results show that substituted γ-2,c-6-diphenyl piperidin-4-ones with semicarbazone act as the perfect corrosion inhibitors and their inhibition efficiency increases with the addition of halide ions. The inhibitor (01SC) shows the inhibition efficiency of 78.28% (0.2mM) by using a weight loss method. The influence of I-, Br- and Cl- anions raises the inhibition efficiency of the substituted 2,6-diphenyl piperidin-4-ones with semicarbazone due to the synergistic effect. The synergistic effect of halide ions was formed in the following order: KI > KBr > KCl.

Holographic Optical Elements Recorded in Silver Halide Sensitized Gelatin Emulsions. Part 2. Reflection Holographic Optical Elements

NASA Astrophysics Data System (ADS)

Kim, Jong Man; Choi, Byung So; Choi, Yoon Sun; Kim, Jong Min; Bjelkhagen, Hans I.; Phillips, Nicholas J.

2002-03-01

Silver halide sensitized gelatin (SHSG) holograms are similar to holograms recorded in dichromated gelatin (DCG), the main recording material for holographic optical elements (HOEs). The drawback of DCG is its low energetic sensitivity and limited spectral response. Silver halide materials can be processed in such a way that the final hologram will have properties like a DCG hologram. Recently this technique has become more interesting since the introduction of new ultra-fine-grain silver halide (AgHal) emulsions. In particular, high spatial-frequency fringes associated with HOEs of the reflection type are difficult to construct when SHSG processing methods are employed. Therefore an optimized processing technique for reflection HOEs recorded in the new AgHal materials is introduced. Diffraction efficiencies over 90% can be obtained repeatably for reflection diffraction gratings. Understanding the importance of a selective hardening process has made it possible to obtain results similar to conventional DCG processing. The main advantage of the SHSG process is that high-sensitivity recording can be performed with laser wavelengths anywhere within the visible spectrum. This simplifies the manufacturing of high-quality, large-format HOEs, also including high-quality display holograms of the reflection type in both monochrome and full color.

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

Alternative Electrochemical Salt Waste Forms, Summary of FY11-FY12 Results

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

Riley, Brian J.; Mccloy, John S.; Crum, Jarrod V.

2014-01-17

The Fuel Cycle Research and Development Program, sponsored by the U.S. Department of Energy Office of Nuclear Energy, is currently investigating alternative waste forms for wastes generated from nuclear fuel processing. One such waste results from an electrochemical separations process, called the “Echem” process. The Echem process utilizes a molten KCl-LiCl salt to dissolve the fuel. This process results in a spent salt containing alkali, alkaline earth, lanthanide halides and small quantities of actinide halides, where the primary halide is chloride with a minor iodide fraction. Pacific Northwest National Laboratory (PNNL) is concurrently investigating two candidate waste forms for themore » Echem spent-salt: high-halide minerals (i.e., sodalite and cancrinite) and tellurite (TeO2)-based glasses. Both of these candidates showed promise in fiscal year (FY) 2009 and FY2010 with a simplified nonradioactive simulant of the Echem waste. Further testing was performed on these waste forms in FY2011 and FY2012 to assess the possibility of their use in a sustainable fuel cycle. This report summarizes the combined results from FY2011 and FY2012 efforts.« less

Lanthanum halide scintillators for time-of-flight 3-D pet

DOEpatents

Karp, Joel S [Glenside, PA; Surti, Suleman [Philadelphia, PA

2008-06-03

A Lanthanum Halide scintillator (for example LaCl.sub.3 and LaBr.sub.3) with fast decay time and good timing resolution, as well as high light output and good energy resolution, is used in the design of a PET scanner. The PET scanner includes a cavity for accepting a patient and a plurality of PET detector modules arranged in an approximately cylindrical configuration about the cavity. Each PET detector includes a Lanthanum Halide scintillator having a plurality of Lanthanum Halide crystals, a light guide, and a plurality of photomultiplier tubes arranged respectively peripherally around the cavity. The good timing resolution enables a time-of-flight (TOF) PET scanner to be developed that exhibits a reduction in noise propagation during image reconstruction and a gain in the signal-to-noise ratio. Such a PET scanner includes a time stamp circuit that records the time of receipt of gamma rays by respective PET detectors and provides timing data outputs that are provided to a processor that, in turn, calculates time-of-flight (TOF) of gamma rays through a patient in the cavity and uses the TOF of gamma rays in the reconstruction of images of the patient.

Depth profile of halide anions under highly charged biological membrane

NASA Astrophysics Data System (ADS)

Sung, Woongmo; Wang, Wenjie; Lee, Jonggwan; Vaknin, David; Kim, Doseok

2015-03-01

Halide ion (Cl- and I-) distribution under a cationic Langmuir monolayer consisting of 1,2-dipalmitoyl-3 trimethylammonium-propane (DPTAP) molecules was investigated by vibrational sum-frequency generation (VSFG) and X-ray spectroscopy. From VSFG spectra, it was observed that large halide anions (I-) screen surface charge more efficiently so that interfacial water alignment becomes more randomized. On the other hand, number density of ions directly measured by X-ray fluorescence spectroscopy at grazing incidence angle reveals that the ion densities within 6 ~ 8 nm are the same for both I- and Cl-. Since the observed ion densities in both cases are almost equal to the charge density of the DPTAP monolayer, we propose that larger halide anions are attracted closer to the surface making direct binding with the charged headgroups of the molecules in the monolayer, accomplishing charge neutrality in short distance. This direct adsorption of anions also disturbs the monolayer structure both in terms of the conformation of alkyl chains and the vertical configuration of the monolayer, with iodine having the stronger effect. Our study shows that the length scale that ions neutralize a charged interface varies significantly and specifically even between monovalent ions.

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.

Effects of Annealing Conditions on Mixed Lead Halide Perovskite Solar Cells and Their Thermal Stability Investigation.

PubMed

Yang, Haifeng; Zhang, Jincheng; Zhang, Chunfu; Chang, Jingjing; Lin, Zhenhua; Chen, Dazheng; Xi, He; Hao, Yue

2017-07-21

In this work, efficient mixed organic cation and mixed halide (MA 0.7 FA 0.3 Pb(I 0.9 Br 0.1 )₃) perovskite solar cells are demonstrated by optimizing annealing conditions. AFM, XRD and PL measurements show that there is a better perovskite film quality for the annealing condition at 100 °C for 30 min. The corresponding device exhibits an optimized PCE of 16.76% with V OC of 1.02 V, J SC of 21.55 mA/cm² and FF of 76.27%. More importantly, the mixed lead halide perovskite MA 0.7 FA 0.3 Pb(I 0.9 Br 0.1 )₃ can significantly increase the thermal stability of perovskite film. After being heated at 80 °C for 24 h, the PCE of the MA 0.7 FA 0.3 Pb(I 0.9 Br 0.1 )₃ device still remains at 70.00% of its initial value, which is much better than the control MAPbI₃ device, where only 46.50% of its initial value could be preserved. We also successfully fabricated high-performance flexible mixed lead halide perovskite solar cells based on PEN substrates.

Induced amphotropic and thermotropic ionic liquid crystallinity in phosphonium halides: "lubrication" by hydroxyl groups.

PubMed

Ma, Kefeng; Somashekhar, B S; Gowda, G A Nagana; Khetrapal, C L; Weiss, Richard G

2008-03-18

The influence of covalently attaching hydroxymethylene to the methyl groups of methyl-tri-n-alkylphosphonium halides (where the alkyl chains are decyl, tetradecyl, or octadecyl and the halide is chloride or bromide) or adding methanol as a solute to the salts on their solid, liquid-crystalline (smectic A2), and isotropic phases has been investigated using a variety of experimental techniques. These structural and compositional changes are found to induce liquid crystallinity in some cases and to enhance the temperature range and lower the onset temperature of the liquid-crystalline phases in some others. The results are interpreted in terms of the lengths of the three n-alkyl chains attached to the phosphorus cation, the nature of the halide anion, the influence of H-bonding interactions at the head group regions of the layered phases, and other solvent-solute interactions. The fact that at least 1 molar equiv of methanol must be added to effect complete (isothermal) conversion of a solid methyl-tri-n-alkylphosphonium salt to a liquid crystal demonstrates a direct and strong association between individual methanol molecules and the phosphonium salts. Possible applications of such systems are suggested.

New Approach To Produce Water Free of Bacteria, Viruses, and Halogens in a Recyclable System▿

PubMed Central

Ahmed, Abd El-Shafey I.; Cavalli, Gabriel; Bushell, Michael E.; Wardell, John N.; Pedley, Steve; Charles, Katarina; Hay, John N.

2011-01-01

The antimicrobial activity of a new cross-linked N-halamine polymer against bacteria and viruses was evaluated. The polymer achieved a 9-log10 reduction of bacteria (both Escherichia coli and Staphylococcus aureus) in 1.5 h and a 5-log10 reduction of bacteriophage PRD1 in 3 h. At the same time, the ability of the nonhalogenated polymer to trap halide ions was examined. The polymer was incorporated into a multifiltration system to study the ability to produce water free of bacteria, viruses, and halide ions. The antimicrobial activity, useful lifetime, halide ion level, and recycling possibilities of the system were quantified on a laboratory scale. A design for a large-scale multifiltration system based on this polymer is proposed. PMID:21115711

Lead Halide Perovskites: Challenges and Opportunities in Advanced Synthesis and Spectroscopy

DOE PAGES

Rosales, Bryan A.; Hanrahan, Michael P.; Boote, Brett W.; ...

2017-03-28

Hybrid lead perovskites containing a mixture of organic and inorganic cations and anions have lead to solar cell devices with better performance and stability than their single halide analogs. Here, 207Pb solid-state nuclear magnetic resonance and single particle photoluminescence spectroscopies show that the structure and composition of mixed-halide and—likely—other hybrid lead perovskites is much more complex than previously thought and is highly dependent on their synthesis. While a majority of reports in the area focus on the construction of photovoltaic devices, this perspective focuses instead on achieving a better understanding of the fundamental chemistry and photophysics of these materials, asmore » this will aid not only in constructing improved devices, but also in generating new uses for these unique materials.« less

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

Reaction between aminoalkyl radicals and akyl halides: Dehalogenation by electron transfer?

NASA Astrophysics Data System (ADS)

Lalevée, J.; Fouassier, J. P.; Blanchard, N.; Ingold, K. U.

2011-07-01

Aminoalkyl radicals, such as Et2NCrad HCH3, have low oxidation potentials and are therefore powerful reducing agents. We have found that Et2NCrad HCH3 reacts with CCl4 and CBr4 in di-tert-butyl peroxide with bimolecular rate constants (measured by LFP) close, or equal, to the diffusion-controlled limit. For the less reactive halide, CH2Br2, the reaction rate is increased substantially by the addition of acetonitrile as a co-solvent. It is tentatively concluded that these reactions occur by electron-transfer from the aminoalkyl to the organohalide with formation of the iminium ion, Et2N+dbnd CHCH3 (NMR detection), halide ion and a halomethyl radical, e.g., rad CCl3 and rad CHCl2 (ESR, spin-trapping detection).

Alloying effects on superionic conductivity in lithium indium halides for all-solid-state batteries

NASA Astrophysics Data System (ADS)

Zevgolis, Alysia; Wood, Brandon C.; Mehmedović, Zerina; Hall, Alex T.; Alves, Thomaz C.; Adelstein, Nicole

2018-04-01

Alloying of anions is a promising engineering strategy for tuning ionic conductivity in halide-based inorganic solid electrolytes. We explain the alloying effects in Li3InBr6-xClx, in terms of strain, chemistry, and microstructure, using first-principles molecular dynamics simulations and electronic structure analysis. We find that strain and bond chemistry can be tuned through alloying and affect the activation energy and maximum diffusivity coefficient. The similar conductivities of the x = 3 and x = 6 compositions can be understood by assuming that the alloy separates into Br-rich and Cl-rich regions. Phase-separation increases diffusivity at the interface and in the expanded Cl-region, suggesting microstructure effects are critical. Similarities with other halide superionic conductors are highlighted.

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

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.

Solution-Phase Synthesis of Cesium Lead Halide Perovskite Nanowires.

PubMed

Zhang, Dandan; Eaton, Samuel W; Yu, Yi; Dou, Letian; Yang, Peidong

2015-07-29

Halide perovskites have attracted much attention over the past 5 years as a promising class of materials for optoelectronic applications. However, compared to hybrid organic-inorganic perovskites, the study of their pure inorganic counterparts, like cesium lead halides (CsPbX3), lags far behind. Here, a catalyst-free, solution-phase synthesis of CsPbX3 nanowires (NWs) is reported. These NWs are single-crystalline, with uniform growth direction, and crystallize in the orthorhombic phase. Both CsPbBr3 and CsPbI3 are photoluminescence active, with composition-dependent temperature and self-trapping behavior. These NWs with a well-defined morphology could serve as an ideal platform for the investigation of fundamental properties and the development of future applications in nanoscale optoelectronic devices based on all-inorganic perovskites.

Highly luminescent colloidal nanoplates of perovskite cesium lead halide and their oriented assemblies

DOE PAGES

Bekenstein, Yehonadav; Koscher, Brent A.; Eaton, Samuel W.; ...

2015-12-15

Anisotropic colloidal quasi-two-dimensional nanoplates (NPLs) hold great promise as functional materials due to their combination of low dimensional optoelectronic properties and versatility through colloidal synthesis. Recently, lead-halide perovskites have emerged as important optoelectronic materials with excellent efficiencies in photovoltaic and light-emitting applications. Here we report the synthesis of quantum confined all inorganic cesium lead halide nanoplates in the perovskite crystal structure that are also highly luminescent (PLQY 84%). The controllable self-assembly of nanoplates either into stacked columnar phases or crystallographic-oriented thin-sheet structures is demonstrated. Furthermore, the broad accessible emission range, high native quantum yields, and ease of self-assembly make perovskitemore » NPLs an ideal platform for fundamental optoelectronic studies and the investigation of future devices.« less

Lead halide perovskites: Crystal-liquid duality, phonon glass electron crystals, and large polaron formation

PubMed Central

Miyata, Kiyoshi; Atallah, Timothy L.; Zhu, X.-Y.

2017-01-01

Lead halide perovskites have been demonstrated as high performance materials in solar cells and light-emitting devices. These materials are characterized by coherent band transport expected from crystalline semiconductors, but dielectric responses and phonon dynamics typical of liquids. This “crystal-liquid” duality implies that lead halide perovskites belong to phonon glass electron crystals, a class of materials believed to make the most efficient thermoelectrics. We show that the crystal-liquid duality and the resulting dielectric response are responsible for large polaron formation and screening of charge carriers, leading to defect tolerance, moderate charge carrier mobility, and radiative recombination properties. Large polaron formation, along with the phonon glass character, may also explain the marked reduction in hot carrier cooling rates in these materials. PMID:29043296

[BMIM][PF(6)] promotes the synthesis of halohydrin esters from diols using potassium halides.

PubMed

Oromí-Farrús, Mireia; Eras, Jordi; Villorbina, Gemma; Torres, Mercè; Llopis-Mestre, Veronica; Welton, Tom; Canela, Ramon

2008-10-01

Haloesterification of diverse diols with various carboxylic acids was achieved using potassium halides (KX) as the only halide source in ionic liquids. The best yield was obtained in [BMIM][PF(6)] when 1,2-octanediol, palmitic acid and KBr were used. This yield was 85% and the regioisomer with the bromine in primary position was present in a 75:25 ratio. The regioisomeric ratio could be improved using either KCl or some phenylcarboxylic acids. [BMIM][PF(6)] acts as both reaction media and catalyst of the reaction. To the best of our knowledge, this type of combined reaction using an ionic liquid is unprecedented. The other solvents tested did not lead either to the same yield or to the same regioisomeric ratio.

Determination of the refractive index and thickness of holographic silver halide materials by use of polarized reflectances.

PubMed

Beléndez, Augusto; Beléndez, Tarsicio; Neipp, Cristian; Pascual, Inmaculada

2002-11-10

A method to determine the refractive index and thickness of silver halide emulsions used in holography is presented. The emulsions are in the form of a layer of film deposited on a thick glass plate. The experimental reflectances of p-polarized light are measured as a function of the incident angles, and the values of refractive index, thickness, and extinction coefficient of the emulsion are obtained by using the theoretical equation for reflectance. As examples, five commercial holographic silver halide emulsions are analyzed. The procedure to obtain the measurements and the numerical analysis of the experimental data are simple, and agreement of the calculated reflectances, by use of the thickness and refractive index obtained, with the measured reflectances is satisfactory.

Magnetodielectric Response from Spin-Orbital Interaction Occurring at Interface of Ferromagnetic Co and Organometal Halide Perovskite Layers via Rashba Effect

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

Li, Mingxing; Li, Ling; Mukherjee, Rupam

The spin on a ferromagnetic Co surface can interact with the asymmetric orbital on an organometal halide perovskite surface, leading to an anisotropic magnetodielectric effect. Here, this study presents an opportunity to integrate ferromagnetic and semiconducting properties through the Rasbha effect for achieving spin–dependent electronic functionalities based on thin–film design.

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

PREPARATION OF ANHYDROUS CERIUM CHLORIDE, URANIUM BROMIDE OR PLUTONIUM FLUORIDE

DOEpatents

Marmon, K.M.; Wichers, E.

1961-05-01

A process is given for preparing anhydrous metal halides and converting metal oxalates to anhydrous metal halides which are free from oxyhalides. In accordance with one embodiment of the invention, cerous chloride is prepared by passing hydrogen chloride gas over hydrated cerous oxalate below lOO deg C until no more gas is absorbed and then continuing the treatmert at higher temperatures.

Magnetodielectric Response from Spin-Orbital Interaction Occurring at Interface of Ferromagnetic Co and Organometal Halide Perovskite Layers via Rashba Effect

DOE PAGES

Li, Mingxing; Li, Ling; Mukherjee, Rupam; ...

2016-12-05

The spin on a ferromagnetic Co surface can interact with the asymmetric orbital on an organometal halide perovskite surface, leading to an anisotropic magnetodielectric effect. Here, this study presents an opportunity to integrate ferromagnetic and semiconducting properties through the Rasbha effect for achieving spin–dependent electronic functionalities based on thin–film design.

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

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

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.

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 absorbers.

Relaxed Eddy Accumulation Measurements of Ozone Depleting Compounds from a Mesohaline Saltmarsh Invaded by Lepidium latifolium.

NASA Astrophysics Data System (ADS)

Deventer, M. J.; Jiao, Y.; Rhew, R. C.

2017-12-01

Natural emissions of methyl bromide (CH3Br) and methyl chloride (CH3Cl) from terrestrial ecosystems might explain the missing source of these compounds to the atmosphere. Methyl halides are a major source for stratospheric halogens, which catalyzing ozone depletion. Real-world measurements of their exchange fluxes are limited, typically occurring at coarse time scales using intrusive measurement techniques (e.g., laboratory incubations of soil and vegetation samples). To improve the current understanding of the net budget and to provide a more solid foundation for up-scaling purposes, the surface-atmosphere exchange for both methyl halides has been studied during 2016/2017 in a year-long field campaign at Rush Ranch (38.2004 °N, 122.0265 °W), a 4.6 km2 large (natural) brackish saltmarsh in the San Francisco Bay National Estuarine in Suisun Bay (CA, United States), using the non-intrusive micrometeorological Relaxed Eddy Accumulation (REA) technique. With REA flux measurements, a large area of the salt marsh (on the order of multiple acres) can be studied without disturbance. Concurrently, static flux chamber incubations were conducted over different vegetation species, to identify their relevance in terms of methyl halide emissions. Our results confirm substantial emissions of methyl halides from the studied saltmarsh. A rough global extrapolation of these results yields yearly emissions of 52 Gg yr-1 (CH3Cl) and 8 Gg yr-1 for CH3Br, respectively, which is close to estimates based on chamber based observations from southern California saltmarshes. Chamber incubations at Rush Ranch revealed that the invasive species Lepidium latifolium (perennial pepperweed) emits a significant amount of methyl halides, less than the native alkali heath (Frankenia salina) but much more than the native pickleweed (Salicornia spp.) Due to aggressive invasiveness and it's capability to form dense monospecific patches, L. latifolium is the main driver of halide emissions at Rush Ranch. If L. latifolium. invasion of Salicornia-dominated marsh ecosystems continuous, natural emissions of ozone depleting substances may increase in the future.

Electrochemical Exfoliation of Graphite in Aqueous Sodium Halide Electrolytes toward Low Oxygen Content Graphene for Energy and Environmental Applications.

PubMed

Munuera, J M; Paredes, J I; Enterría, M; Pagán, A; Villar-Rodil, S; Pereira, M F R; Martins, J I; Figueiredo, J L; Cenis, J L; Martínez-Alonso, A; Tascón, J M D

2017-07-19

Graphene and graphene-based materials have shown great promise in many technological applications, but their large-scale production and processing by simple and cost-effective means still constitute significant issues in the path of their widespread implementation. Here, we investigate a straightforward method for the preparation of a ready-to-use and low oxygen content graphene material that is based on electrochemical (anodic) delamination of graphite in aqueous medium with sodium halides as the electrolyte. Contrary to previous conflicting reports on the ability of halide anions to act as efficient exfoliating electrolytes in electrochemical graphene exfoliation, we show that proper choice of both graphite electrode (e.g., graphite foil) and sodium halide concentration readily leads to the generation of large quantities of single-/few-layer graphene nanosheets possessing a degree of oxidation (O/C ratio down to ∼0.06) lower than that typical of anodically exfoliated graphenes obtained with commonly used electrolytes. The halide anions are thought to play a role in mitigating the oxidation of the graphene lattice during exfoliation, which is also discussed and rationalized. The as-exfoliated graphene materials exhibited a three-dimensional morphology that was suitable for their practical use without the need to resort to any kind of postproduction processing. When tested as dye adsorbents, they outperformed many previously reported graphene-based materials (e.g., they adsorbed ∼920 mg g -1 for methyl orange) and were useful sorbents for oils and nonpolar organic solvents. Supercapacitor cells assembled directly from the as-exfoliated products delivered energy and power density values (up to 15.3 Wh kg -1 and 3220 W kg -1 , respectively) competitive with those of many other graphene-based devices but with the additional advantage of extreme simplicity of preparation.

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

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

Hu, Q; Moran, J E

2004-01-22

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

Ca-Fe and Alkali-Halide Alteration of an Allende Type B CAI: Aqueous Alteration in Nebular or Asteroidal Settings

NASA Technical Reports Server (NTRS)

Ross, D. K.; Simon, J. I.; Simon, S. B.; Grossman, L.

2012-01-01

Ca-Fe and alkali-halide alteration of CAIs is often attributed to aqueous alteration by fluids circulating on asteroidal parent bodies after the various chondritic components have been assembled, although debate continues about the roles of asteroidal vs. nebular modification processes [1-7]. Here we report de-tailed observations of alteration products in a large Type B2 CAI, TS4 from Allende, one of the oxidized subgroup of CV3s, and propose a speculative model for aqueous alteration of CAIs in a nebular setting. Ca-Fe alteration in this CAI consists predominantly of end-member hedenbergite, end-member andradite, and compositionally variable, magnesian high-Ca pyroxene. These phases are strongly concentrated in an unusual "nodule" enclosed within the interior of the CAI (Fig. 1). The Ca, Fe-rich nodule superficially resembles a clast that pre-dated and was engulfed by the CAI, but closer inspection shows that relic spinel grains are enclosed in the nodule, and corroded CAI primary phases interfinger with the Fe-rich phases at the nodule s margins. This CAI also contains abundant sodalite and nepheline (alkali-halide) alteration that occurs around the rims of the CAI, but also penetrates more deeply into the CAI. The two types of alteration (Ca-Fe and alkali-halide) are adjacent, and very fine-grained Fe-rich phases are associated with sodalite-rich regions. Both types of alteration appear to be replacive; if that is true, it would require substantial introduction of Fe, and transport of elements (Ti, Al and Mg) out of the nodule, and introduction of Na and Cl into alkali-halide rich zones. Parts of the CAI have been extensively metasomatized.

A STUDY OF THE STABILITY OF ZIRCONIUM AND HAFNIUM TETRAHALIDES ON HITTING A HOT SURFACE IN VACUUM (in Russian)

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

Tsirel'nikov, V.I.; Komissarova, L.N.; Spitsyn, V.I.

1962-09-01

The decomposition coefficients of the chlorides, bromides, and iodides of Zr and Hf were determined as a function of the temperature of a hot surface. The tetrahalides were carefully purified in an inert atmosphere of argon. The halide compound in a quartz ampoule was heated by a removable heater. The vapors passed through a capillary opening and struck a tungsten foil 0.5 mm thick and 12 to 15 mm wide. The Mo foil was heated electrically to control the surface temperature which was measured by an optical pyrometer. The tetrahalide decomposed according to the following reaction: Me(Hal)/sub 4/ yields Memore » + 2(Hal)/sub 2/. The lower halides dissociated completely to metal and free halides, since the temperature was >600 deg C. The Mo backing was dissolved in nitric acid, and the unsupported metal deposit of Zr or Hf was weighed, The decomposition coefficient was calcuweight of metal evaporated. Zrl/sub 4/ decomposed completely (100%) at 1500 deg C, while only 96% of the HfI/sub 4/ was decomposed at this temperature. The ZrBr/sub 4/ and HfBr/sub 4/ were decomposed by 68 and 61% respectively. The ZrCl/sub 4/ and HfCl/sub 4/ were stable at l500 deg C (5% of the ZrCl/sub 4/ was decomposed at l500 deg C). In all cases, the hafnium halide was more stable than the zirconium halide, especially in the case of the iodides. The decomposition was directly proportional to the temperature of the molybdenum target. (TTT)« less

Local Polar Fluctuations in Lead Halide Perovskite Crystals

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

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

2017-03-01

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 (CH3NH3PbBr3) and all-inorganic (CsPbBr3) leadhalide perovskites show that anharmonic, local polar fluctuations are intrinsic to the general lead-halide perovskite structure, and not unique to the dipolar organic cation. MD simulations indicate that head-tohead Cs motion coupledmore » to Br face expansion, occurring on a few hundred femtosecond time scale, drives the local polar fluctuations in CsPbBr3.« less

Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites

NASA Astrophysics Data System (ADS)

Bischak, Connor G.; Hetherington, Craig L.; Wu, Hao; Aloni, Shaul; Ogletree, D. Frank; Limmer, David T.; Ginsberg, Naomi S.

2017-02-01

Nonequilibrium processes occurring in functional materials can significantly impact device efficiencies and are often difficult to characterize due to the broad range of length and time scales involved. In particular, mixed halide hybrid perovskites are promising for optoelectronics, yet the halides reversibly phase separate when photo-excited, significantly altering device performance. By combining nanoscale imaging and multiscale modeling, we elucidate the mechanism underlying this phenomenon, demonstrating that local strain induced by photo-generated polarons promotes halide phase separation and leads to nucleation of light-stabilized iodide-rich clusters. This effect relies on the unique electromechanical properties of hybrid materials, characteristic of neither their organic nor inorganic constituents alone. Exploiting photo-induced phase separation and other nonequilibrium phenomena in hybrid materials, generally, could enable new opportunities for expanding the functional applications in sensing, photoswitching, optical memory, and energy storage.

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

Dou, Letian; Lai, Minliang; Kley, Christopher S.

Halide perovskites are promising semiconductor materials for solution-processed optoelectronic devices. Their strong ionic bonding nature results in highly dynamic crystal lattices, inherently allowing rapid ion exchange at the solid–vapor and solid–liquid interface. In this paper, we show that the anion-exchange chemistry can be precisely controlled in single-crystalline halide perovskite nanomaterials when combined with nanofabrication techniques. We demonstrate spatially resolved multicolor CsPbX 3 (X = Cl, Br, I, or alloy of two halides) nanowire heterojunctions with a pixel size down to 500 nm with the photoluminescence tunable over the entire visible spectrum. In addition, the heterojunctions show distinct electronic states acrossmore » the interface, as revealed by Kelvin probe force microscopy. Finally, these perovskite heterojunctions represent key building blocks for high-resolution multicolor displays beyond current state-of-the-art technology as well as high-density diode/transistor arrays.« less

Structural Search for High Pressure CS2 and Xe-Cl Compounds

NASA Astrophysics Data System (ADS)

Zarifi, Niloofar; Tse, John S.

2018-04-01

The recent successful implementation of several methodologies for the prediction of crystal structures based on the first-principles electronic structure have ushered in a new area of computational chemistry. In this study, the two most popular methods, namely genetic evolution and particle swarm optimization, were applied to the investigation of stable crystalline polymorphs of solid carbon disulfide and xenon halides at high pressure. It was found that both methods have their own merits. However, there are subtleties that need to be considered for the proper execution of the methods. We found a two-dimensional (2D) layered structure that may be responsible for the superconductivity in CS2. Except for XeCl2, no thermodynamically stable crystalline Xe halides were found under 60 GPa in the halide-rich region of the phase diagram.

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

Jiang, Qinglong; Chen, Mingming; Li, Junqiang

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%more » 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.« less

Bluish-white-light-emitting diodes based on two-dimensional lead halide perovskite (C6H5C2H4NH3)2PbCl2Br2

NASA Astrophysics Data System (ADS)

Cai, Peiqing; Wang, Xiangfu; Seo, Hyo Jin; Yan, Xiaohong

2018-04-01

Bluish-white-light-emitting diodes (BWLEDs) are designed based on the two-dimensional mixed halide perovskite (C6H5C2H4NH3)2PbCl2Br2 at room temperature. Bluish-white electroluminescence devices were fabricated by a spin-coating method. The BWLEDs can be turned on at 4.9 V and depict a maximum luminance of ˜70 cd/m2 at 7 V. Low and room temperature photoluminescence spectra show the coexistence of free exciton and self-trapped exciton luminescence in a deformable lattice. The strategy of achieving white electroluminescence (EL) from mixed halide perovskite reported here can be applied to other two-dimensional perovskites to increase the optoelectronic efficiency of the device in the future.

Phase recording for formation of holographic optical elements on silver-halide photographic emulsions

NASA Astrophysics Data System (ADS)

Ganzherli, Nina M.; Gulyaev, Sergey N.; Maurer, Irina A.; Chernykh, Dmitrii F.

2009-05-01

Holographic fabrication methods of regular and nonregular relief-phase structures on silver-halide photographic emulsions are considered. Methods of gelatin photodestruction under short-wave ultra-violet radiation and chemical hardening with the help of dichromated solutions were used as a technique for surface relief formation. The developed techniques permitted us to study specimens of holographic diffusers and microlens rasters with small absorption and high light efficiency.

Merging photoredox and nickel catalysis: decarboxylative cross-coupling of carboxylic acids with vinyl halides.

PubMed

Noble, Adam; McCarver, Stefan J; MacMillan, David W C

2015-01-21

Decarboxylative cross-coupling of alkyl carboxylic acids with vinyl halides has been accomplished through the synergistic merger of photoredox and nickel catalysis. This new methodology has been successfully applied to a variety of α-oxy and α-amino acids, as well as simple hydrocarbon-substituted acids. Diverse vinyl iodides and bromides give rise to vinylation products in high efficiency under mild, operationally simple reaction conditions.

Engaging Alkenyl Halides with Alkylsilicates via Photoredox Dual Catalysis.

PubMed

Patel, Niki R; Kelly, Christopher B; Jouffroy, Matthieu; Molander, Gary A

2016-02-19

Single-electron transmetalation via photoredox/nickel dual catalysis provides the opportunity for the construction of Csp(3)-Csp(2) bonds through the transfer of alkyl radicals under very mild reaction conditions. A general procedure for the cross-coupling of primary and secondary (bis-catecholato)alkylsilicates with alkenyl halides is presented. The developed method allows not only alkenyl bromides and iodides but also previously underexplored alkenyl chlorides to be employed.

Organic Cations Might Not Be Essential to the Remarkable Properties of Band Edge Carriers in Lead Halide Perovskites.

PubMed

Zhu, Haiming; Trinh, M Tuan; Wang, Jue; Fu, Yongping; Joshi, Prakriti P; Miyata, Kiyoshi; Jin, Song; Zhu, X-Y

2017-01-01

A charge carrier in a lead halide perovskite lattice is protected as a large polaron responsible for the remarkable photophysical properties, irrespective of the cation type. All-inorganic-based APbX 3 perovskites may mitigate the stability problem for their applications in solar cells and other optoelectronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Role of Excitons on Light Amplification in Lead Halide Perovskites.

PubMed

Lü, Quan; Wei, Haohan; Sun, Wenzhao; Wang, Kaiyang; Gu, Zhiyuan; Li, Jiankai; Liu, Shuai; Xiao, Shumin; Song, Qinghai

2016-12-01

The role of excitons on the amplifications of lead halide perovskites has been explored. Unlike the photoluminescence, the intensity of amplified spontaneous emission is partially suppressed at low temperature. The detailed analysis and experiments show that the inhibition is attributed to the existence of exciton and a quantitative model has been built to explain the experimental observations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-photon absorption and upconversion luminescence of colloidal CsPbX3 quantum dots

NASA Astrophysics Data System (ADS)

Han, Qiuju; Wu, Wenzhi; Liu, Weilong; Yang, Qingxin; Yang, Yanqiang

2018-01-01

The nonlinear optical and the upconversion luminescence (UCL) properties of CsPbX3 (X = Br or its binary mixtures with Cl, I) quantum dots (QDs) are investigated by femtosecond open-aperture (OA) Z-scan and time-resolved luminescence techniques in nonresonant spectral region. The OA Z-scan results show that CsPbX3 QDs have strong reverse saturable absorption (RSA), which is ascribed to two-photon absorption. Partially changing halide composition from Cl to Br, to I, two-photon absorption cross sections become larger at the same laser excitation intensity. The composition-tunable nonlinear absorption should be attributed to the gradual decrease of the lowest direct band gaps with the halide substitute. Moreover, the strong UCL can be observed under near infrared femtosecond laser excitation. Halide composition-tunable UCL dynamics of CsPbX3 QDs is analyzed by use of two-exponential fitting with deconvolution. When CsPbX3 QDs have similar sizes (10-13 nm), with partially changing halide composition from Cl to Br, to I, the average UCL lifetime becomes longer due to the variation of Kane energy. Our findings suggest all-inorganic perovskite QDs can be used as excellent gain medium for high-performance frequency-upconversion lasers and provide reference to engineer such QDs toward practical optoelectronic applications.

All-Solid-State Mechanochemical Synthesis and Post-Synthetic Transformation of Inorganic Perovskite-type Halides.

PubMed

Pal, Provas; Saha, Sujoy; Banik, Ananya; Sarkar, Arka; Biswas, Kanishka

2018-02-06

All-inorganic and hybrid perovskite type halides are generally synthesized by solution-based methods, with the help of long chain organic capping ligands, complex organometallic precursors, and high boiling organic solvents. Herein, a room temperature, solvent-free, general, and scalable all-solid-state mechanochemical synthesis is demonstrated for different inorganic perovskite type halides, with versatile structural connectivity in three (3D), two (2D), and zero (0D) dimensions. 3D CsPbBr 3 , 2D CsPb 2 Br 5 , 0D Cs 4 PbBr 6 , 3D CsPbCl 3 , 2D CsPb 2 Cl 5 , 0D Cs 4 PbCl 6 , 3D CsPbI 3 , and 3D RbPbI 3 have all been synthesized by this method. The all-solid-state synthesis is materialized through an inorganic retrosynthetic approach, which directs the decision on the solid-state precursors (e.g., CsX and PbX 2 (X=Cl/Br/I) with desired stoichiometric ratios. Moreover, post-synthetic structural transformations from 3D to 2D and 0D perovskite halides were performed by the same mechanochemical synthetic approach at room temperature. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics† †Electronic supplementary information (ESI) available: Experimental details, PL, PDS spectra and XRD patterns. See DOI: 10.1039/c4sc03141e Click here for additional data file.

PubMed Central

Hoke, Eric T.; Slotcavage, Daniel J.; Dohner, Emma R.; Bowring, Andrea R.

2015-01-01

We report on reversible, light-induced transformations in (CH3NH3)Pb(BrxI1–x)3. Photoluminescence (PL) spectra of these perovskites develop a new, red-shifted peak at 1.68 eV that grows in intensity under constant, 1-sun illumination in less than a minute. This is accompanied by an increase in sub-bandgap absorption at ∼1.7 eV, indicating the formation of luminescent trap states. Light soaking causes a splitting of X-ray diffraction (XRD) peaks, suggesting segregation into two crystalline phases. Surprisingly, these photo-induced changes are fully reversible; the XRD patterns and the PL and absorption spectra revert to their initial states after the materials are left for a few minutes in the dark. We speculate that photoexcitation may cause halide segregation into iodide-rich minority and bromide-enriched majority domains, the former acting as a recombination center trap. This instability may limit achievable voltages from some mixed-halide perovskite solar cells and could have implications for the photostability of halide perovskites used in optoelectronics. PMID:28706629

Enormous excitonic effects in bulk, mono- and bi- layers of cuprous halides using many-body perturbation technique

NASA Astrophysics Data System (ADS)

Azhikodan, Dilna; Nautiyal, Tashi

2017-10-01

Cuprous halides (CuX with X = Cl, Br, I), intensely studied about four decades ago by experimentalists for excitons, are again drawing attention of researchers recently. Potential of cuprous halide systems for device applications has not yet been fully explored. We go beyond the one-particle picture to capture the two-particle physics (electron-hole interaction to form excitons). We have deployed the full tool kit of many-body perturbation technique, GW approximation + Bethe Salpeter equation, to unfurl the rich excitonic physics of the bulk as well as layers of CuX. The negative spin-orbit contribution at the valence band top in CuCl, compared to CuBr and CuI, is in good agreement with experiments. We note that CuX have exceptionally strong excitons, defying the linear fit (between the excitonic binding energy and band gap) encompassing many semiconductors. The mono- and bi- layers of cuprous halides are predicted to be rich in excitons, with exceptionally large binding energies and the resonance energies in UV/visible region. Hence this work projects CuX layers as good candidates for optoelectronic applications. With advancement of technology, we look forward to experimental realization of CuX layers and harnessing of their rich excitonic potential.

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.

Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms.

PubMed

Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J; Vegge, Tejs

2014-09-28

Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat to be supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) - almost 27,000 combinations, and have identified novel mixtures, with significantly improved storage capacities. The size of the search space and the chosen fitness function make it possible to verify that the found candidates are the best possible candidates in the search space, proving that the GA implementation is ideal for this kind of computational materials design, requiring calculations on less than two percent of the candidates to identify the global optimum.

Gas-Phase Interaction of Anions with Polyisobutylenes: Collision-Induced Dissociation Study and Quantum Chemical Modeling.

PubMed

Nagy, Lajos; Kuki, Ákos; Deák, György; Purgel, Mihály; Vékony, Ádám; Zsuga, Miklós; Kéki, Sándor

2016-09-01

The gas-phase interaction of anions including fluoride, chloride, bromide, iodide, ethyl sulfate, chlorate, and nitrate with polyisobutylene (PIB) derivatives was studied using collision-induced dissociation (CID). The gas-phase adducts of anions with PIBs ([PIB + anion](-)) were generated from the electrosprayed solution of PIBs in the presence of the corresponding anions. The so-formed adducts subjected to CID showed a loss of anion at different characteristic collision energies, thus allowing the study of the strength of interaction between the anions and nonpolar PIBs having different end-groups. The values of characteristic collision energies (the energy needed to obtain 50% fragmentation) obtained by CID experiments correlated linearly with the binding enthalpies between the anion and PIB, as determined by density functional theory calculations. In the case of halide ions, the critical energies for dissociation, that is, the binding enthalpies for [PIB + anion](-) adducts, increased in the order of I(-) < Br(-) < Cl(-) < F(-). Furthermore, it was found that the binding enthalpies for the adducts formed with halide ions decreased approximately with the square radius of the halide ion, suggesting that the strength of interaction is mainly determined by the "surface" charge density of the halide ion. In addition, the characteristic collision energy versus the number of isobutylene units revealed a linear dependence.

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.

Unveiling the Shape Evolution and Halide-Ion-Segregation in Blue-Emitting Formamidinium Lead Halide Perovskite Nanocrystals Using an Automated Microfluidic Platform.

PubMed

Lignos, Ioannis; Protesescu, Loredana; Emiroglu, Dilara Börte; Maceiczyk, Richard; Schneider, Simon; Kovalenko, Maksym V; deMello, Andrew J

2018-02-14

Hybrid organic-inorganic perovskites and in particular formamidinium lead halide (FAPbX 3 , X = Cl, Br, I) perovskite nanocrystals (NCs) have shown great promise for their implementation in optoelectronic devices. Specifically, the Br and I counterparts have shown unprecedented photoluminescence properties, including precise wavelength tuning (530-790 nm), narrow emission linewidths (<100 meV) and high photoluminescence quantum yields (70-90%). However, the controlled formation of blue emitting FAPb(Cl 1-x Br x ) 3 NCs lags behind their green and red counterparts and the mechanism of their formation remains unclear. Herein, we report the formation of FAPb(Cl 1-x Br x ) 3 NCs with stable emission between 440 and 520 nm in a fully automated droplet-based microfluidic reactor and subsequent reaction upscaling in conventional laboratory glassware. The thorough parametric screening allows for the elucidation of parametric zones (FA-to-Pb and Br-to-Cl molar ratios, temperature, and excess oleic acid) for the formation of nanoplatelets and/or NCs. In contrast to CsPb(Cl 1-x Br x ) 3 NCs, based on online parametric screening and offline structural characterization, we demonstrate that the controlled synthesis of Cl-rich perovskites (above 60 at% Cl) with stable emission remains a challenge due to fast segregation of halide ions.

Hybrid Lead Halide Perovskites for Ultrasensitive Photoactive Switching in Terahertz Metamaterial Devices.

PubMed

Manjappa, Manukumara; Srivastava, Yogesh Kumar; Solanki, Ankur; Kumar, Abhishek; Sum, Tze Chien; Singh, Ranjan

2017-08-01

The recent meteoric rise in the field of photovoltaics with the discovery of highly efficient solar-cell devices is inspired by solution-processed organic-inorganic lead halide perovskites that exhibit unprecedented light-to-electricity conversion efficiencies. The stunning performance of perovskites is attributed to their strong photoresponsive properties that are thoroughly utilized in designing excellent perovskite solar cells, light-emitting diodes, infrared lasers, and ultrafast photodetectors. However, optoelectronic application of halide perovskites in realizing highly efficient subwavelength photonic devices has remained a challenge. Here, the remarkable photoconductivity of organic-inorganic lead halide perovskites is exploited to demonstrate a hybrid perovskite-metamaterial device that shows extremely low power photoswitching of the metamaterial resonances in the terahertz part of the electromagnetic spectrum. Furthermore, a signature of a coupled phonon-metamaterial resonance is observed at higher pump powers, where the Fano resonance amplitude is extremely weak. In addition, a low threshold, dynamic control of the highly confined electric field intensity is also observed in the system, which could tremendously benefit the new generation of subwavelength photonic devices as active sensors, low threshold optically controlled lasers, and active nonlinear devices with enhanced functionalities in the infrared, optical, and the terahertz parts of the electromagnetic spectrum. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

First-principles thermodynamics study of phase stability in inorganic halide perovskite solid solutions

NASA Astrophysics Data System (ADS)

Bechtel, Jonathon S.; Van der Ven, Anton

2018-04-01

Halide substitution gives rise to a tunable band gap as a function of composition in halide perovskite materials. However, photoinduced phase segregation, observed at room temperature in mixed halide A Pb (IxBr1-x) 3 systems, limits open circuit voltages and decreases photovoltaic device efficiencies. We investigate equilibrium phase stability of orthorhombic P n m a γ -phase CsM (XxY1-x) 3 perovskites where M is Pb or Sn, and X and Y are Br, Cl, or I. Finite-temperature phase diagrams are constructed using a cluster expansion effective Hamiltonian parameterized from first-principles density-functional-theory calculations. Solid solution phases for CsM (IxBr1-x) 3 and CsM (BrxCl1-x) 3 are predicted to be stable well below room temperature while CsM (IxCl1-x) 3 systems have miscibility gaps that extend above 400 K. The height of the miscibility gap correlates with the difference in volume between end members. Also layered ground states are found on the convex hull at x =2 /3 for CsSnBr2Cl ,CsPbI2Br , and CsPbBrCl2. The impact of these ground states on the finite temperature phase diagram is discussed in the context of the experimentally observed photoinduced phase segregation.

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

Method of doping interconnections for electrochemical cells

DOEpatents

Pal, Uday B.; Singhal, Subhash C.; Moon, David M.; Folser, George R.

1990-01-01

A dense, electronically conductive interconnection layer 26 is bonded on a porous, tubular, electronically conductive air electrode structure 16, optionally supported by a ceramic support 22, by (A) forming a layer of oxide particles of at least one of the metals Ca, Sr, Co, Ba or Mg on a part 24 of a first surface of the air electrode 16, (B) heating the electrode structure, (C) applying a halide vapor containing at least lanthanum halide and chromium halide to the first surface and applying a source of oxygen to a second opposite surface of the air electrode so that they contact at said first surface, to cause a reaction of the oxygen and halide and cause a dense lanthanum-chromium oxide structure to grow, from the first electrode surface, between and around the oxide particles, where the metal oxide particles get incoporated into the lanthanum-chromium oxide structure as it grows thicker with time, and the metal ions in the oxide particles diffuse into the bulk of the lanthamum-chromium oxide structure, to provide a dense, top, interconnection layer 26 on top of the air electrode 16. A solid electrolyte layer 18 can be applied to the uncovered portion of the air electrode, and a fuel electrode 20 can be applied to the solid electrolyte, to provide an electrochemical cell 10.

Synthesis of Secondary Aromatic Amides via Pd-Catalyzed Aminocarbonylation of Aryl Halides Using Carbamoylsilane as an Amide Source.

PubMed

Tong, Wenting; Cao, Pei; Liu, Yanhong; Chen, Jianxin

2017-11-03

Using N-methoxymethyl-N-organylcarbamoyl(trimethyl)silanes as secondary amides source, the direct transformation of aryl halides into the corresponding secondary aromatic amides via palladium-catalyzed aminocarbonylation is described. The reactions tolerated a broad range of functional groups on the aryl ring except big steric hindrance of substituent. The types and the relative position of substituents on the aryl ring impact the coupling efficiency.

Long wavelength optical mode frequencies and the Anderson-Gruneisen parameter for alkali halide crystals

NASA Astrophysics Data System (ADS)

Gupta, A. P.; Shanker, Jai

1980-02-01

The relation between long wavelength optical mode frequencies and the Anderson-Gruneisen parameter δ for alkali halides studied by Madan suffers from a mathematical error which is rectified in the present communication. A theoretical analysis of δ is presented adopting six potential functions for the short range repulsion energy. Values of δ and γTO calculated from the Varshni-Shukla potential are found in closest agreement with experimental data.

Potentiometric titration of thiols, cationic surfactants and halides using a solid-state silver-silver sulphide electrode.

PubMed

Pinzauti, S; Papeschi, G; La Porta, E

1983-01-01

A rugged, low resistance silver-silver sulphide solid-state electrode for determining pharmaceuticals as authentic samples or in dosage forms by potentiometric titration is described. Sodium tetraphenylborate, mercury(II) acetate and silver nitrate (0.01) M were employed as titrants in the analysis of cationic surfactants (cetylpyridinium chloride, benzethonium chloride, benzalkonium chloride and chlorhexidine salts), antithyroid drugs (methimazole and propylthiouracil) or sodium halides respectively.

Merging Photoredox and Nickel Catalysis: Decarboxylative Cross-Coupling of Carboxylic Acids with Vinyl Halides

PubMed Central

2015-01-01

Decarboxylative cross-coupling of alkyl carboxylic acids with vinyl halides has been accomplished through the synergistic merger of photoredox and nickel catalysis. This new methodology has been successfully applied to a variety of α-oxy and α-amino acids, as well as simple hydrocarbon-substituted acids. Diverse vinyl iodides and bromides give rise to vinylation products in high efficiency under mild, operationally simple reaction conditions. PMID:25521443

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.

Quasicharacteristic radiation of relativistic electrons at orientation motion in lithium halides crystals along charged planes and axes

NASA Astrophysics Data System (ADS)

Maksyuta, N. V.; Vysotskii, V. I.; Efimenko, S. V.

2016-07-01

The paper deals with the investigation of the orientation motion of relativistic electrons in charged (111) planes and charged [110] axes of lithium halides ionic crystals of LiF, LiCl, LiBr and LiI. On the basis of these investigations the spectra of quasicharacteristic radiation for the electron beams with various Lorentz-factors both in planar and axial cases have been calculated numerically.

Highly Efficient Perovskite-Quantum-Dot Light-Emitting Diodes by Surface Engineering.

PubMed

Pan, Jun; Quan, Li Na; Zhao, Yongbiao; Peng, Wei; Murali, Banavoth; Sarmah, Smritakshi P; Yuan, Mingjian; Sinatra, Lutfan; Alyami, Noktan M; Liu, Jiakai; Yassitepe, Emre; Yang, Zhenyu; Voznyy, Oleksandr; Comin, Riccardo; Hedhili, Mohamed N; Mohammed, Omar F; Lu, Zheng Hong; Kim, Dong Ha; Sargent, Edward H; Bakr, Osman M

2016-10-01

A two-step ligand-exchange strategy is developed, in which the long-carbon- chain ligands on all-inorganic perovskite (CsPbX 3 , X = Br, Cl) quantum dots (QDs) are replaced with halide-ion-pair ligands. Green and blue light-emitting diodes made from the halide-ion-pair-capped quantum dots exhibit high external quantum efficiencies compared with the untreated QDs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Radiation creation of cation defects in alkali halide crystals: Review and today's concept (Review Article)

NASA Astrophysics Data System (ADS)

Lushchik, A.; Lushchik, Ch.; Vasil'chenko, E.; Popov, A. I.

2018-04-01

Irradiation of alkali halide crystals creates pairs of Frenkel defects both in anion and cation sublattices. However, the particular nonimpact creation mechanisms (related to the decay of different electronic excitations) of cation Frenkel pairs are still unclear. At helium temperatures, there is yet no direct evidences of the creation of stable (long-lived) elemental cation defects. On the other hand, a number of complex structural defects containing cation vacancies and/or interstitials, were detected after irradiation of alkali halides at higher temperatures. Besides already proved mechanism related to the association of H and VK centers into trihalide molecules, the following possibilities of cation interstitial-vacancy pair creation are analyzed as well: (i) a direct decay of cation or anion excitons, (ii) the transformation of anion Frenkel pairs, formed at the decay of anion excitons or e-h recombination, into cation ones.

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

Lasing from lead halide perovskite semiconductor microcavity system.

PubMed

Wang, Jun; Da, Peimei; Zhang, Zhe; Luo, Song; Liao, Liming; Sun, Zeyuan; Shen, Xuechu; Wu, Shiwei; Zheng, Gengfeng; Chen, Zhanghai

2018-06-07

Organic-inorganic halide perovskite semiconductors are ideal gain media for fabricating laser and photonic devices due to high absorption, photoluminescence (PL) efficiency and low nonradiative recombination losses. Herein, organic-inorganic halide perovskite CH3NH3PbI3 is embedded in the Fabry-Perot (FP) microcavity, and a wavelength-tunable excitonic lasing with a threshold of 12.9 μJ cm-2 and the spectral coherence of 0.76 nm are realized. The lasing threshold decreases and the spectral coherence enhances as the temperature decreases; these results are ascribed to the suppression of exciton irradiative recombination caused by thermal fluctuation. Moreover, both lasing and light emission below threshold from the perovskite microcavity (PM) system demonstrate a redshift with the decreasing temperature. These results provide a feasible platform based on the PM system for the study of light-matter interaction for quantum optics and the development of optoelectronic devices such as polariton lasers.

Chloride, bromide and iodide scintillators with europium

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

Zhuravleva, Mariya; Yang, Kan

A halide scintillator material is disclosed where the halide may comprise chloride, bromide or iodide. The material is single-crystalline and has a composition of the general formula ABX.sub.3 where A is an alkali, B is an alkali earth and X is a halide which general composition was investigated. In particular, crystals of the formula ACa.sub.1-yEu.sub.yI.sub.3 where A=K, Rb and Cs were formed as well as crystals of the formula CsA.sub.1-yEu.sub.yX.sub.3 (where A=Ca, Sr, Ba, or a combination thereof and X=Cl, Br or I or a combination thereof) with divalent Europium doping where 0.ltoreq.y.ltoreq.1, and more particularly Eu doping has beenmore » studied at one to ten mol %. The disclosed scintillator materials are suitable for making scintillation detectors used in applications such as medical imaging and homeland security.« less

Reactions of salts of hexakis(pyridine N-oxide)M(II) complexes (M = Co, Ni, Zn) and alkali halides used in infrared spectroscopy

NASA Astrophysics Data System (ADS)

Padmos, J.; van Veen, A.

A number of salts of hexakis(pyridine N-oxide)zinc(II) complexes decompose in alkali halide pellets. Initially ion exchange occurs, often followed by the formation of Zn(pyno) 3X 2 (pyno = pyridine N-oxide; X = Br, Cl). The analogous cobalt and nickel compounds are nearly always stable. A mull between alkali halide plates gives greater amounts of the same product Washing this product with toluene gives Zn(pyno) 2X 2. Examples of i.r. and far i.r. spectra are given. Energetical and structural effects are discussed. Far i.r. spectra of M(pyno) 3X 2(M = Co, Zn) confirm the structure [M(pyno) 6][MX 4] for these compounds. New compounds are [Zn(pyno) 2(NO 3) 2], [Zn(pyno- d5) 2[NO 3) 2], [Zn(pyno- d5) 6](NO 3) 2 and [Zn(pyno) 6]I 2.

Enhanced Born Charge and Proximity to Ferroelectricity in Thallium Halides

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

Du, Mao-Hua; Singh, David J

2010-01-01

Electronic structure and lattice dynamics calculations on thallium halides show that the Born effective charges in these compounds are more than twice larger than the nominal ionic charges. This is a result of cross-band-gap hybridization between Tl-p and halogen-p states. The large Born charges cause giant splitting between longitudinal and transverse optic phonon modes, bringing the lattice close to ferroelectric instability. Our calculations indeed show spontaneous lattice polarization upon lattice expansion starting at 2%. It is remarkable that the apparently ionic thallium halides with a simple cubic CsCl structure and large differences in electronegativity between cations and anions can bemore » very close to ferroelectricity. This can lead to effective screening of defects and impurities that would otherwise be strong carrier traps and may therefore contribute to the relatively good carrier transport properties in TlBr radiation detectors.« less

Enhanced Born charge and proximity to ferroelectricity in thallium halides

NASA Astrophysics Data System (ADS)

Du, Mao-Hua; Singh, David J.

2010-04-01

Electronic-structure and lattice-dynamics calculations on thallium halides show that the Born effective charges in these compounds are more than twice larger than the nominal ionic charges. This is a result of cross-band-gap hybridization between Tlp and halogen- p states. The large Born charges cause giant splitting between longitudinal and transverse-optic phonon modes, bringing the lattice close to ferroelectric instability. Our calculations indeed show that cubic TlBr develops ferroelectric instabilities upon lattice expansion starting at 2%. It is remarkable that the apparently ionic thallium halides with a simple cubic CsCl structure and large differences in electronegativity between cations and anions can be very close to ferroelectricity. This can lead to effective screening of defects and impurities that would otherwise be strong carrier traps and may therefore contribute to the relatively good carrier transport properties in TlBr radiation detectors.

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.

Memory preservation made prestigious but easy

NASA Astrophysics Data System (ADS)

Fageth, Reiner; Debus, Christina; Sandhaus, Philipp

2011-01-01

Preserving memories combined with story-telling using either photo books for multiple images or high quality products such as one or a few images printed on canvas or images mounted on acryl to create high-quality wall decorations are gradually becoming more popular than classical 4*6 prints and classical silver halide posters. Digital printing via electro photography and ink jet is increasingly replacing classical silver halide technology as the dominant production technology for these kinds of products. Maintaining a consistent and comparable quality of output is becoming more challenging than using silver halide paper for both, prints and posters. This paper describes a unique approach of combining both desktop based software to initiate a compelling project and the use of online capabilities in order to finalize and optimize that project in an online environment in a community process. A comparison of the consumer behavior between online and desktop based solutions for generating photo books will be presented.

Ultrasmooth organic-inorganic perovskite thin-film formation and crystallization for efficient planar heterojunction solar cells.

PubMed

Zhang, Wei; Saliba, Michael; Moore, David T; Pathak, Sandeep K; Hörantner, Maximilian T; Stergiopoulos, Thomas; Stranks, Samuel D; Eperon, Giles E; Alexander-Webber, Jack A; Abate, Antonio; Sadhanala, Aditya; Yao, Shuhua; Chen, Yulin; Friend, Richard H; Estroff, Lara A; Wiesner, Ulrich; Snaith, Henry J

2015-01-30

To date, there have been a plethora of reports on different means to fabricate organic-inorganic metal halide perovskite thin films; however, the inorganic starting materials have been limited to halide-based anions. Here we study the role of the anions in the perovskite solution and their influence upon perovskite crystal growth, film formation and device performance. We find that by using a non-halide lead source (lead acetate) instead of lead chloride or iodide, the perovskite crystal growth is much faster, which allows us to obtain ultrasmooth and almost pinhole-free perovskite films by a simple one-step solution coating with only a few minutes annealing. This synthesis leads to improved device performance in planar heterojunction architectures and answers a critical question as to the role of the anion and excess organic component during crystallization. Our work paves the way to tune the crystal growth kinetics by simple chemistry.

Cobalt co-catalysis for cross-electrophile coupling: diarylmethanes from benzyl mesylates and aryl halides† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc03106g Click here for additional data file.

PubMed Central

Ackerman, Laura K. G.; Anka-Lufford, Lukiana L.; Naodovic, Marina

2015-01-01

The nickel-catalyzed cross-coupling of aryl halides with alkyl radicals derived from alkyl halides has recently been extended to couplings with carbon radicals generated by a co-catalyst. In this study, a new co-catalyst, cobalt phthalocyanine (Co(Pc)), is introduced and demonstrated to be effective for coupling substrates not prone to homolysis. This is because Co(Pc) reacts with electrophiles by an SN2 mechanism instead of by the electron-transfer or halogen abstraction mechanisms previously explored. Studies demonstrating the orthogonal reactivity of (bpy)Ni and Co(Pc), applying this selectivity to the coupling of benzyl mesylates with aryl halides, and the adaptation of these conditions to the less reactive benzyl phosphate ester and an enantioconvergent reaction are presented. PMID:25685312

CVD aluminiding process for producing a modified platinum aluminide bond coat for improved high temperature performance

NASA Technical Reports Server (NTRS)

Nagaraj, Bangalore A. (Inventor); Williams, Jeffrey L. (Inventor)

2003-01-01

A method of depositing by chemical vapor deposition a modified platinum aluminide diffusion coating onto a superalloy substrate comprising the steps of applying a layer of a platinum group metal to the superalloy substrate; passing an externally generated aluminum halide gas through an internal gas generator which is integral with a retort, the internal gas generator generating a modified halide gas; and co-depositing aluminum and modifier onto the superalloy substrate. In one form, the modified halide gas is hafnium chloride and the modifier is hafnium with the modified platinum aluminum bond coat comprising a single phase additive layer of platinum aluminide with at least about 0.5 percent hafnium by weight percent and about 1 to about 15 weight percent of hafnium in the boundary between a diffusion layer and the additive layer. The bond coat produced by this method is also claimed.

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.

Solvation structures and dynamics of alkaline earth metal halides in supercritical water: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Keshri, Sonanki; Mandal, Ratnamala; Tembe, B. L.

2016-09-01

Constrained molecular dynamics simulations of alkaline earth metal halides have been carried out to investigate their structural and dynamical properties in supercritical water. Potentials of mean force (PMFs) for all the alkaline earth metal halides in supercritical water have been computed. Contact ion pairs (CIPs) are found to be more stable than all other configurations of the ion pairs except for MgI2 where solvent shared ion pair (SShIP) is more stable than the CIP. There is hardly any difference in the PMFs between the M2+ (M = Mg, Ca, Sr, Ba) and the X- (X = F, Cl, Br, I) ions whether the second X- ion is present in the first coordination shell of the M2+ ion or not. The solvent molecules in the solvation shells diffuse at a much slower rate compared to the bulk. Orientational distribution functions of solvent molecules are sharper for smaller ions.

Band Gap Tuning and Defect Tolerance of Atomically Thin Two-Dimensional Organic-Inorganic Halide Perovskites.

PubMed

Pandey, Mohnish; Jacobsen, Karsten W; Thygesen, Kristian S

2016-11-03

Organic-inorganic halide perovskites have proven highly successful for photovoltaics but suffer from low stability, which deteriorates their performance over time. Recent experiments have demonstrated that low dimensional phases of the hybrid perovskites may exhibit improved stability. Here we report first-principles calculations for isolated monolayers of the organometallic halide perovskites (C 4 H 9 NH 3 ) 2 MX 2 Y 2 , where M = Pb, Ge, Sn and X,Y = Cl, Br, I. The band gaps computed using the GLLB-SC functional are found to be in excellent agreement with experimental photoluminescence data for the already synthesized perovskites. Finally, we study the effect of different defects on the band structure. We find that the most common defects only introduce shallow or no states in the band gap, indicating that these atomically thin 2D perovskites are likely to be defect tolerant.

Spatially resolved multicolor CsPbX 3 nanowire heterojunctions via anion exchange

DOE PAGES

Dou, Letian; Lai, Minliang; Kley, Christopher S.; ...

2017-06-26

Halide perovskites are promising semiconductor materials for solution-processed optoelectronic devices. Their strong ionic bonding nature results in highly dynamic crystal lattices, inherently allowing rapid ion exchange at the solid–vapor and solid–liquid interface. In this paper, we show that the anion-exchange chemistry can be precisely controlled in single-crystalline halide perovskite nanomaterials when combined with nanofabrication techniques. We demonstrate spatially resolved multicolor CsPbX 3 (X = Cl, Br, I, or alloy of two halides) nanowire heterojunctions with a pixel size down to 500 nm with the photoluminescence tunable over the entire visible spectrum. In addition, the heterojunctions show distinct electronic states acrossmore » the interface, as revealed by Kelvin probe force microscopy. Finally, these perovskite heterojunctions represent key building blocks for high-resolution multicolor displays beyond current state-of-the-art technology as well as high-density diode/transistor arrays.« less

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.

Aqueous photochemical reactions of chloride, bromide, and iodide ions in a diode-array spectrophotometer. Autoinhibition in the photolysis of iodide ions.

PubMed

Kalmár, József; Dóka, Éva; Lente, Gábor; Fábián, István

2014-03-28

The aqueous photoreactions of three halide ions (chloride, bromide and iodide) were studied using a diode array spectrophotometer to drive and detect the process at the same time. The concentration and pH dependences of the halogen formation rates were studied in detail. The experimental data were interpreted by improving earlier models where the cage complex of a halogen atom and an electron has a central role. The triiodide ion was shown to exert a strong inhibiting effect on the reaction sequence leading to its own formation. An assumed chemical reaction between the triiodide ion and the cage complex interpreted the strong autoinhibition effect. It is shown that there is a real danger of unwanted interference from the photoreactions of halide ions when halide salts are used as supporting electrolytes in spectrophotometric experiments using a relatively high intensity UV light source.

Lattice model calculation of elastic and thermodynamic properties at high pressure and temperature. [for alkali halides in NaCl lattice

NASA Technical Reports Server (NTRS)

Demarest, H. H., Jr.

1972-01-01

The elastic constants and the entire frequency spectrum were calculated up to high pressure for the alkali halides in the NaCl lattice, based on an assumed functional form of the inter-atomic potential. The quasiharmonic approximation is used to calculate the vibrational contribution to the pressure and the elastic constants at arbitrary temperature. By explicitly accounting for the effect of thermal and zero point motion, the adjustable parameters in the potential are determined to a high degree of accuracy from the elastic constants and their pressure derivatives measured at zero pressure. The calculated Gruneisen parameter, the elastic constants and their pressure derivatives are in good agreement with experimental results up to about 600 K. The model predicts that for some alkali halides the Grunesen parameter may decrease monotonically with pressure, while for others it may increase with pressure, after an initial decrease.

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.

Composition-Dependent Energy Splitting between Bright and Dark Excitons in Lead Halide Perovskite Nanocrystals.

PubMed

Chen, Lan; Li, Bin; Zhang, Chunfeng; Huang, Xinyu; Wang, Xiaoyong; Xiao, Min

2018-03-14

Perovskite semiconductor nanocrystals with different compositions have shown promise for applications in light-emitting devices. Dark excitonic states may suppress light emission from such nanocrystals by providing an additional nonradiative recombination channel. Here, we study the composition dependence of dark exciton dynamics in nanocrystals of lead halides by time-resolved photoluminescence spectroscopy at cryogenic temperatures. The presence of a spin-related dark state is revealed by magneto-optical spectroscopy. The energy splitting between bright and dark states is found to be highly sensitive to both halide elements and organic cations, which is explained by considering the effects of size confinement and charge screening, respectively, on the exchange interaction. These findings suggest the possibility of manipulating dark exciton dynamics in perovskite semiconductor nanocrystals by composition engineering, which will be instrumental in the design of highly efficient light-emitting devices.

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

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

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, crystallization kinetics can be tailored to yield improved thin film homogeneity. Because degradation of the as-formed perovskite film is in many ways analogous to its initial formation, the same suite of monitoring techniques reveals the moisture-induced transformation of low band gap methylammonium lead iodide (CH 3NH 3PbI 3) to wide band gap hydrate compounds. The rate of degradation is increased upon exposure to light. Interestingly, the hydration process is reversible under certain conditions. This facile formation and subsequent chemical lability raises the question of whether CH 3NH 3PbI 3 and its analogues are thermodynamically stable phases, thus posing a significant challenge to the development of transformative perovskite photovoltaics. Adequately addressing issues of structural and chemical stability under real-world operating conditions is paramount if perovskite solar cells are to make an impact beyond the benchtop. Expanding our fundamental knowledge of lead halide perovskite formation and degradation pathways can facilitate fabrication of stable, high-quality perovskite thin films for the next generation of photovoltaic and light emitting devices.« less

Efficient click chemistry towards fatty acids containing 1,2,3-triazole: Design and synthesis as potential antifungal drugs for Candida albicans.

PubMed

Fu, Nina; Wang, Suiliang; Zhang, Yuqian; Zhang, Caixia; Yang, Dongliang; Weng, Lixing; Zhao, Baomin; Wang, Lianhui

2017-08-18

Candida is an important opportunistic human fungal pathogen. The cis-2-dodecenoic acid (BDSF) showing in vitro activity of against C. albicans growth, germ-tube germination and biofilm formation has been a potential inhibitor for Candida and other fungi. In this study, facile synthetic strategies toward a novel family of BDSF analogue, 1-alkyl-1H-1,2,3-triazole-4-carboxylic acids (ATCs) was developed. The straightforward synthetic method including converting the commercial available alkyl bromide to alkyl azide, consequently with a typical click chemistry method, copper(II) sulfate and sodium ascorbate as catalyst in water to furnish ATCs with mild to good yields. According to antifungal assay, 1-decyl-4,5-dihydro-1H-1,2,3-triazole-4-carboxylic acid (5d) showed antifungal capability slightly better than BDSF. The 1,2,3-triazole unit played a crucial role for the bioactivity of ATCs was also confirmed when compared with two alkyl-aromatic carboxylic acids. Given its simplicity, high antifungal activity, and wide availability of compounds with halide atoms on the end part of the alkyl chains, the method can be extended to develop more excellent ATC drugs for accomplishing the challenges in future antifungal applications. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

A Direct Bandgap Copper-Antimony Halide Perovskite.

PubMed

Vargas, Brenda; Ramos, Estrella; Pérez-Gutiérrez, Enrique; Alonso, Juan Carlos; Solis-Ibarra, Diego

2017-07-12

Since the establishment of perovskite solar cells (PSCs), there has been an intense search for alternative materials to replace lead and improve their stability toward moisture and light. As single-metal perovskite structures have yielded unsatisfactory performances, an alternative is the use of double perovskites that incorporate a combination of metals. To this day, only a handful of these compounds have been synthesized, but most of them have indirect bandgaps and/or do not have bandgaps energies well-suited for photovoltaic applications. Here we report the synthesis and characterization of a unique mixed metal ⟨111⟩-oriented layered perovskite, Cs 4 CuSb 2 Cl 12 (1), that incorporates Cu 2+ and Sb 3+ into layers that are three octahedra thick (n = 3). In addition to being made of abundant and nontoxic elements, we show that this material behaves as a semiconductor with a direct bandgap of 1.0 eV and its conductivity is 1 order of magnitude greater than that of MAPbI 3 (MA = methylammonium). Furthermore, 1 has high photo- and thermal-stability and is tolerant to humidity. We conclude that 1 is a promising material for photovoltaic applications and represents a new type of layered perovskite structure that incorporates metals in 2+ and 3+ oxidation states, thus significantly widening the possible combinations of metals to replace lead in PSCs.

Influence of PbCl{sub 2} content in PbI{sub 2} solution of DMF on the absorption, crystal phase, morphology of lead halide thin films and photovoltaic performance in planar perovskite solar cells

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

Wang, Mao; Shi, Chengwu, E-mail: shicw506@foxmail.com; Zhang, Jincheng

2015-11-15

In this paper, the influence of PbCl{sub 2} content in PbI{sub 2} solution of DMF on the absorption, crystal phase and morphology of lead halide thin films was systematically investigated and the photovoltaic performance of the corresponding planar perovskite solar cells was evaluated. The result revealed that the various thickness lead halide thin film with the small sheet-like, porous morphology and low crystallinity can be produced by adding PbCl{sub 2} powder into PbI{sub 2} solution of DMF as a precursor solution. The planar perovskite solar cell based on the 300-nm-thick CH{sub 3}NH{sub 3}PbI{sub 3−x}Cl{sub x} thin film by the precursormore » solution with the mixture of 0.80 M PbI{sub 2} and 0.20 M PbCl{sub 2} exhibited the optimum photoelectric conversion efficiency of 10.12% along with an open-circuit voltage of 0.93 V, a short-circuit photocurrent density of 15.70 mA cm{sup −2} and a fill factor of 0.69. - Graphical abstract: The figure showed the surface and cross-sectional SEM images of lead halide thin films using the precursor solutions: (a) 0.80 M PbI{sub 2}, (b) 0.80 M PbI{sub 2}+0.20 M PbCl{sub 2}, (c) 0.80 M PbI{sub 2}+0.40 M PbCl{sub 2}, and (d) 0.80 M PbI{sub 2}+0.60 M PbCl{sub 2}. With the increase of the PbCl{sub 2} content in precursor solution, the size of the lead halide nanosheet decreased and the corresponding thin films gradually turned to be porous with low crystallinity. - Highlights: • Influence of PbCl{sub 2} content on absorption, crystal phase and morphology of thin film. • Influence of perovskite film thickness on photovoltaic performance of solar cell. • Lead halide thin film with small sheet-like, porous morphology and low crystallinity. • Planar solar cell with 300 nm-thick perovskite thin film achieved PCE of 10.12%.« less

Protective interlayer for high temperature solid electrolyte electrochemical cells

DOEpatents

Isenberg, Arnold O.; Ruka, Roswell J.

1986-01-01

A high temperature, solid electrolyte electrochemical cell is made, having a first and second electrode with solid electrolyte between them, where the electrolyte is formed by hot chemical vapor deposition, where a solid, interlayer material, which is electrically conductive, oxygen permeable, and protective of electrode material from hot metal halide vapor attack, is placed between the first electrode and the electrolyte, to protect the first electrode from the hot metal halide vapors during vapor deposition.

Protective interlayer for high temperature solid electrolyte electrochemical cells

DOEpatents

Isenberg, Arnold O.; Ruka, Roswell J.; Zymboly, Gregory E.

1985-01-01

A high temperature, solid electrolyte electrochemical cell is made, having a first and second electrode with solid electrolyte between them, where the electrolyte is formed by hot chemical vapor deposition, where a solid, interlayer material, which is electrically conductive, oxygen permeable, and protective of electrode material from hot metal halide vapor attack, is placed between the first electrode and the electrolyte, to protect the first electrode from the hot metal halide vapors during vapor deposition.

Protective interlayer for high temperature solid electrolyte electrochemical cells

DOEpatents

Isenberg, Arnold O.; Ruka, Roswell J.

1987-01-01

A high temperature, solid electrolyte electrochemical cell is made, having a first and second electrode with solid electrolyte between them, where the electrolyte is formed by hot chemical vapor deposition, where a solid, interlayer material, which is electrically conductive, oxygen permeable, and protective of electrode material from hot metal halide vapor attack, is placed between the first electrode and the electrolyte, to protect the first electrode from the hot metal halide vapors during vapor deposition.

Visible Laser Research One Meter Device

DTIC Science & Technology

1980-01-01

OF THIS PAGE (" ol ~n Date Entered) ~z, TABLE OF CONTENTS Section Page List of Illustrations 3 I. INTRODUCTION 5 II. BACKGROUND 15 III. RESULTS 17 A...proven lasers are the excip!ex lasers which include the rare gas halides, halogens and mercury halides (see Table I). Of these exciplex systems, there...Stokes line routinpiy e- ported. (1) 5 Z::I~AVCO EVERETT TABLE I A SUMMARY OF EXCIPLEX LASERS AND THEIR LASING WAVELENGTHS EXCIPLEX , (B -+ X) nm ArF

Ordered Polymers for Space Applications.

DTIC Science & Technology

1987-10-12

nitrogens. Reaction with alkyl halides would form pyridinium halides. Compound 3 was prepared by reaction of DABDT with nicotinic acid in PPA. We have also...HCI. To the clear solution *was added 10.793 g (87.67 mmol) of nicotinic acid and 24.49 g of P205 (the final calculated P20 5 content of the solution...expected to be sensitive enough to detect low levels of this impurity. We used Raman and FTIR spectroscopy, but could not detect assignable differences

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

Palladium-Catalyzed Nitromethylation of Aryl Halides: An Orthogonal Formylation Equivalent

PubMed Central

Walvoord, Ryan R.; Berritt, Simon; Kozlowski, Marisa C.

2012-01-01

An efficient cross-coupling reaction of aryl halides and nitromethane was developed with the use of parallel microscale experimentation. The arylnitromethane products are precursors for numerous useful synthetic products. An efficient method for their direct conversion to the corresponding oximes and aldehydes in a one-pot operation has been discovered. The process exploits inexpensive nitromethane as a carbonyl equivalent, providing a mild and convenient formylation method that is compatible with many functional groups. PMID:22839593

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.

Regioselective and stereospecific cleavage of a terminal oxirane system: a novel synthetic approach to lipid mediator congeners--1,2(2,3)-diacyl-3(1)-halo-sn-glycerols.

PubMed

Stamatov, Stephan D; Stawinski, Jacek

2006-07-01

Glycidyl esters upon treatment with a mixture of carboxylic acid anhydride (CAA) and trimethylsilyl halide (TMSX) in the presence of tetra-n-butylammonium halide (Bu(4)NX, X=Cl, Br or I) undergo stereospecific and regioselective opening of the oxirane ring to afford mixed-(or mono)-acid 1,2(2,3)-diacyl-3(1)-halo-sn-glycerols in high yields.

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.

SLR digital camera for forensic photography

NASA Astrophysics Data System (ADS)

Har, Donghwan; Son, Youngho; Lee, Sungwon

2004-06-01

Forensic photography, which was systematically established in the late 19th century by Alphonse Bertillon of France, has developed a lot for about 100 years. The development will be more accelerated with the development of high technologies, in particular the digital technology. This paper reviews three studies to answer the question: Can the SLR digital camera replace the traditional silver halide type ultraviolet photography and infrared photography? 1. Comparison of relative ultraviolet and infrared sensitivity of SLR digital camera to silver halide photography. 2. How much ultraviolet or infrared sensitivity is improved when removing the UV/IR cutoff filter built in the SLR digital camera? 3. Comparison of relative sensitivity of CCD and CMOS for ultraviolet and infrared. The test result showed that the SLR digital camera has a very low sensitivity for ultraviolet and infrared. The cause was found to be the UV/IR cutoff filter mounted in front of the image sensor. Removing the UV/IR cutoff filter significantly improved the sensitivity for ultraviolet and infrared. Particularly for infrared, the sensitivity of the SLR digital camera was better than that of the silver halide film. This shows the possibility of replacing the silver halide type ultraviolet photography and infrared photography with the SLR digital camera. Thus, the SLR digital camera seems to be useful for forensic photography, which deals with a lot of ultraviolet and infrared photographs.

Remarkably Enhancing Green-Excitation Efficiency for Solar Energy Utilization: Red Phosphors Ba2ZnS3:Eu2+, X- Co-Doped Halide Ions (X = Cl, Br, I).

PubMed

Luo, Tingting; Du, Yun; Qiu, Zhongxian; Li, Yanmei; Wang, Xiaofang; Zhou, Wenli; Zhang, Jilin; Yu, Liping; Lian, Shixun

2017-05-15

Eu 2+ -activated Ba 2 ZnS 3 has been reported as a red phosphor with a broad emission band peaking at 650 nm under blue excitation for white-LED. In this study, Ba 2 ZnS 3 :Eu 2+ , X - (X = F, Cl, Br, I) phosphors doped with halide ions were prepared by traditional high-temperature solid-state reaction. Phase identification of powders was performed by X-ray powder diffraction analysis, confirming the existence of single-phase Ba 2 ZnS 3 crystals without dopant. The corresponding excitation spectra showed an additional broad band in the green region peaking at 550 nm when the phosphor was halogenated except by the smallest F - . It was proved that the green-excitation efficiency successively strengthened from Cl - , to Br - , to I - , which suggested larger halide ions made a greater contribution to the further splitting of the t 2g energy level of the doped Eu 2+ ions in the host Ba 2 ZnS 3 , and the optimized formula Ba 1.995 ZnS 2.82 :Eu 2+ 0.005 , I - 0.18 showed a potential application in solar spectral conversion for agricultural greenhouse and solar cell. Defect chemistry theory and crystal field theory provided insights into the key role of halide ions in enhancing green-excitation efficiency.

Calix[4]pyrrole: A New Ion-Pair Receptor As Demonstrated by Liquid-Liquid Extraction

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

Wintergerst, Mr. Matthieu; Levitskaia, Tatiana G.; Moyer, Bruce A

Solvent-extraction studies provide confirming evidence that meso-octamethylcalix[4]pyrrole acts as an ion-pair receptor for cesium chloride and cesium bromide in nitrobenzene solution. The stoichiometry of the interaction under extraction conditions from water to nitrobenzene was determined from plots of the cesium distribution ratios vs cesium salt and receptor concentration, indicating the formation of an ionpaired 1:1:1 cesium:calix[4]pyrrole:halide complex. The extraction results were modeled to evaluate the equilibria inherent to the solvent-extraction system, with either chloride or bromide. The binding energy between the halide anion and the calix[4]pyrrole was found to be about 7 kJ/mol larger for cesium chloride than for themore » cesium bromide. The ion-pairing free energies between the calix[4]pyrrole-halide complex and the cesium cation are nearly the same within experimental uncertainty for either halide, consistent with a structural model in which the Cs+ cation resides in the calix bowl. These results are unexpected since nitrobenzene is a polar solvent that generally leads to dissociated complexes in the organic phase when used as a diluent in extraction studies of univalent ions. Control studies involving nitrate revealed no evidence of ion pairing for CsNO3 under conditions identical to those where it is observed for CsCl and CsBr.« less

Calix[4]pyrrole: A New Ion-Pair Receptor As Demonstrated by Liquid-Liquid Extraction

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

Wintergerst, Mr. Matthieu; Levitskaia, Tatiana G.; Moyer, Bruce A

Solvent extraction studies provide confirming evidence that meso-octamethylcalix[4]pyrrole acts as an ion-pair receptor for cesium chloride and cesium bromide in nitrobenzene solution. The stoichiometry of the interaction under extraction conditions from water to nitrobenzene was determined from plots of the cesium distribution ratios vs. cesium salt and receptor concentration, indicating the formation of an ion-paired 1:1:1 cesium:calix[4]pyrrole:halide complex. The extraction results were modeled to evaluate the equilibria inherent to the solvent extraction system, either with chloride or bromide. The binding energy between the halide anion and the calix[4]pyrrole was found to be about 7 kJ/mol larger for cesium chloride thanmore » for the cesium bromide. The ion-pairing free energies between the calix[4]pyrrole-halide complex and the cesium cation are nearly the same within experimental uncertainty for either halide, consistent with a structural model in which the Cs+ cation resides in the calix bowl. These results are unexpected since nitrobenzene is a very polar solvent that generally leads to dissociated complexes in the organic phase when used as a diluent in extraction studies of univalent ions. Control studies involving nitrate revealed no evidence of ion-pairing for CsNO3 under conditions identical to those where it is observed for CsCl and CsBr.« less

Hydridomethyl iridium complex

DOEpatents

Bergman, Robert G.; Buchanan, J. Michael; Stryker, Jeffrey M.; Wax, Michael J.

1989-01-01

A process for functionalizing methane comprising: (a) reacting methane with a hydridoalkyl metal complex of the formula: CpIr[P(R.sub.1).sub.3 ]H(R.sub.2) wherein Cp represents a cyclopentadienyl or alkylcyclopentadienyl radical having from 1 to 5 carbon atoms; Ir represents an iridium atom; P represents a phosphorus atom; R.sub.1 represents an alkyl group; R.sub.2 represents an alkyl group having at least two carbon atoms; and H represents a hydrogen atom, in the presence of a liquid alkane R.sub.3 H having at least three carbon atoms to form a hydridomethyl complex of the formula: CpIr[P(R.sub.1).sub.3 ]HMe where Me represents a methyl radical. (b) reacting said hydridomethyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas: CX'X"X'"X"" or CHX'X"X'"; wherein X', X", X"', and X"" represent halogens selected from bromine, iodine and chlorine, to halomethyl complex of step (a) having the formula: CpIr[P(R.sub.1).sub.3 ]MeX: (c) reacting said halomethyl complex with a mercuric halide of the formula HgX.sub.2 to form a methyl mercuric halide of the formula HgMeX; and (d) reacting said methyl mercuric halide with a molecular halogen of the formula X.sub.2 to form methyl halide.

Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation.

PubMed

Zhao, Xin-Gang; Yang, Ji-Hui; Fu, Yuhao; Yang, Dongwen; Xu, Qiaoling; Yu, Liping; Wei, Su-Huai; Zhang, Lijun

2017-02-22

Hybrid organic-inorganic halide perovskites with the prototype material of CH 3 NH 3 PbI 3 have recently attracted intense interest as low-cost and high-performance photovoltaic absorbers. Despite the high power conversion efficiency exceeding 20% achieved by their solar cells, two key issues-the poor device stabilities associated with their intrinsic material instability and the toxicity due to water-soluble Pb 2+ -need to be resolved before large-scale commercialization. Here, we address these issues by exploiting the strategy of cation-transmutation to design stable inorganic Pb-free halide perovskites for solar cells. The idea is to convert two divalent Pb 2+ ions into one monovalent M + and one trivalent M 3+ ions, forming a rich class of quaternary halides in double-perovskite structure. We find through first-principles calculations this class of materials have good phase stability against decomposition and wide-range tunable optoelectronic properties. With photovoltaic-functionality-directed materials screening, we identify 11 optimal materials with intrinsic thermodynamic stability, suitable band gaps, small carrier effective masses, and low excitons binding energies as promising candidates to replace Pb-based photovoltaic absorbers in perovskite solar cells. The chemical trends of phase stabilities and electronic properties are also established for this class of materials, offering useful guidance for the development of perovskite solar cells fabricated with them.

Effect of halide salts on development of surface browning on fresh-cut 'Granny Smith' (Malus × domestica Borkh) apple slices during storage at low temperature.

PubMed

Li, Yongxin; Wills, Ron B H; Golding, John B; Huque, Roksana

2015-03-30

The postharvest life of fresh-cut apple slices is limited by browning on cut surfaces. Dipping in halide salt solutions was examined for their inhibition of surface browning on 'Granny Smith' apple slices and the effects on biochemical factors associated with browning. Delay in browning by salts was greatest with chloride = phosphate > sulfate > nitrate with no difference between sodium, potassium and calcium ions. The effectiveness of sodium halides on browning was fluoride > chloride = bromide > iodide = control. Polyphenol oxidase (PPO) activity of tissue extracted from chloride- and fluoride-treated slices was not different to control but when added into the assay solution, NaF > NaCl both showed lower PPO activity at pH 3-5 compared to control buffer. The level of polyphenols in treated slices was NaF > NaCl > control. Addition of chlorogenic acid to slices enhanced browning but NaCl and NaF counteracted this effect. There was no effect of either halide salt on respiration, ethylene production, ion leakage, and antioxidant activity. Dipping apple slices in NaCl is a low cost treatment with few impediments to commercial use and could be a replacement for other anti-browning additives. The mode of action of NaCl and NaF is through decreasing PPO activity resulting in reduced oxidation of polyphenols. © 2014 Society of Chemical Industry.

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.

Phase Segregation in Potassium-Doped Lead Halide Perovskites from 39K Solid-State NMR at 21.1 T.

PubMed

Kubicki, Dominik J; Prochowicz, Daniel; Hofstetter, Albert; Zakeeruddin, Shaik M; Grätzel, Michael; Emsley, Lyndon

2018-06-13

Organic-inorganic lead halide perovskites are a promising family of light absorbers for a new generation of solar cells, with reported efficiencies currently exceeding 22%. A common problem of solar cells fabricated using these materials is that their efficiency depends on their cycling history, an effect known as current-voltage ( J- V) hysteresis. Potassium doping has recently emerged as a universal way to overcome this adverse phenomenon. While the atomistic origins of J- V hysteresis are still not fully understood, it is essential to rationalize the atomic-level effect of protocols that lead to its suppression. Here, using 39 K MAS NMR at 21.1 T we provide for the first time atomic-level characterization of the potassium-containing phases that are formed upon KI doping of multication and multianion lead halide perovskites. We find no evidence of potassium incorporation into 3D perovskite lattices of the recently reported materials. Instead, we observe formation of a mixture of potassium-rich phases and unreacted KI. In the case of Br-containing lead halide perovskites doped with KI, a mixture of KI and KBr ensues, leading to a change in the Br/I ratio in the perovskite phase with respect to the undoped perovskite. Simultaneous Cs and K doping leads to the formation of nonperovskite Cs/K lead iodide phases.

High Color Rendering Index White-Light Emission from UV-Driven LEDs Based on Single Luminescent Materials: Two-Dimensional Perovskites (C6H5C2H4NH3)2PbBr xCl4- x.

PubMed

Yang, Shuming; Lin, Zhenghuan; Wang, Jingwei; Chen, Yunxiang; Liu, Zhengde; Yang, E; Zhang, Jian; Ling, Qidan

2018-05-09

Two-dimensional (2D) white-light-emitting hybrid perovskites (WHPs) are promising active materials for single-component white-light-emitting diodes (WLEDs) driven by UV. However, the reported WHPs exhibit low quantum yields (≤9%) and low color rendering index (CRI) values less than 85, which does not satisfy the demand of solid-state lighting applications. In this work, we report a series of mixed-halide 2D layered WHPs (C 6 H 5 C 2 H 4 NH 3 ) 2 PbBr x Cl 4- x (0 < x < 4) obtained from the phenethylammonium cation. Unlike the reported WHPs including (C 6 H 5 C 2 H 4 NH 3 ) 2 PbCl 4 , the mixed-halide perovskites display morphology-dependent white emission for the different extents of self-absorption. Additionally, the amount of Br has a huge influence on the photophysical properties of mixed-halide WHPs. With the increasing content of Br, the quantum yields of WHPs increase gradually from 0.2 to 16.9%, accompanied by tunable color temperatures ranging from 4000 K ("warm" white light) to 7000 K ("cold" white light). When applied to the WLEDs, the mixed-halide perovskite powders exhibit tunable white electroluminescent emission with very high CRI of 87-91.

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.

Coordination trends in alkali metal crown ether uranyl halide complexes: the series [A(crown)]2[UO(2)X(4)] where A=Li, Na, K and X=Cl, Br.

PubMed

Danis, J A; Lin, M R; Scott, B L; Eichhorn, B W; Runde, W H

2001-07-02

UO(2)(C(2)H(3)O(2))(2).2H(2)O reacts with AX or A(C(2)H(3)O(2) or ClO(4)) (where A = Li, Na, K; X = Cl, Br) and crown ethers in HCl or HBr aqueous solutions to give the sandwich-type compounds [K(18-crown-6)](2)[UO(2)Cl(4)] (1), [K(18-crown-6)](2)[UO(2)Br(4)] (2), [Na(15-crown-5)](2)[UO(2)Cl(4)] (3), [Na(15-crown-5)](2)[UO(2)Br(4)] (4), [Li(12-crown-4)](2)[UO(2)Cl(4)] (5), and [Li(12-crown-4)](2)[UO(2)Br(4)] (6). The compounds have been characterized by single-crystal X-ray diffraction, powder diffraction, elemental analysis, IR, and Raman spectroscopy. The [UO(2)X(4)](2-) ions coordinate to two [A(crown)](+) cations through the four halides only (2), through two halides only (3), through the two uranyl oxygens and two halides (3, 4), or through the two uranyl oxygen atoms only (5, 6). Raman spectra reveal nu(U-O) values that correlate with expected trends. The structural trends are discussed within the context of classical principles of hard-soft acid-base theory.

High-Performance CH3NH3PbI3-Inverted Planar Perovskite Solar Cells with Fill Factor Over 83% via Excess Organic/Inorganic Halide.

PubMed

Jahandar, Muhammad; Khan, Nasir; Lee, Hang Ken; Lee, Sang Kyu; Shin, Won Suk; Lee, Jong-Cheol; Song, Chang Eun; Moon, Sang-Jin

2017-10-18

The reduction of charge carrier recombination and intrinsic defect density in organic-inorganic halide perovskite absorber materials is a prerequisite to achieving high-performance perovskite solar cells with good efficiency and stability. Here, we fabricated inverted planar perovskite solar cells by incorporation of a small amount of excess organic/inorganic halide (methylammonium iodide (CH 3 NH 3 I; MAI), formamidinium iodide (CH(NH 2 ) 2 I; FAI), and cesium iodide (CsI)) in CH 3 NH 3 PbI 3 perovskite film. Larger crystalline grains and enhanced crystallinity in CH 3 NH 3 PbI 3 perovskite films with excess organic/inorganic halide reduce the charge carrier recombination and defect density, leading to enhanced device efficiency (MAI+: 14.49 ± 0.30%, FAI+: 16.22 ± 0.38% and CsI+: 17.52 ± 0.56%) compared to the efficiency of a control MAPbI 3 device (MAI: 12.63 ± 0.64%) and device stability. Especially, the incorporation of a small amount of excess CsI in MAPbI 3 perovskite film leads to a highly reproducible fill factor of over 83%, increased open-circuit voltage (from 0.946 to 1.042 V), and short-circuit current density (from 18.43 to 20.89 mA/cm 2 ).

Carbon Isotope Fractionation Effects During Degradation of Methyl Halides in Agricultural Soils

NASA Astrophysics Data System (ADS)

Miller, L. G.; Baesman, S. M.; Oremland, R. S.; Bill, M.; Goldstein, A. H.

2001-12-01

Fumigation of agricultural soils prior to planting row crops constitutes the largest anthropogenic source of methyl bromide (MeBr) to the atmosphere. Typically, more than 60% of the MeBr added is lost to the atmosphere during the 5-6 day fumigation period. The remainder is oxidized by bacteria or otherwise degraded in the soil. In experiments using washed cells of methylotrophic bacteria isolated from agricultural soil (strain IMB-1), oxidation of MeBr, methyl chloride (MeCl) and methyl iodide to CO2 resulted in large (up to 70‰ ) fractionation of stable carbon isotopes (Miller, et al. 2001). By contrast, fractionation measured in field soils using both in situ techniques and bottle incubations with MeBr was less than 35‰ . This discrepancy was initially attributed to the large transportation losses that occur without isotopic fractionation during field fumigation. However, this rationale cannot explain why bottle incubations with soil resulted in lower fractionation factors than incubations with bacterial cultures. We conducted additional laboratory bottle experiments to examine the biological and chemical controls of carbon isotope fractionation during degradation of MeBr and MeCl by soils and bacteria. Soils were collected from a strawberry field in Santa Cruz County, California within two weeks of the start of each experiment. The rate of removal of methyl halides from the headspace was greatest during incubations at soil moisture contents around 8%. Increasing the amount of soil and hence native bacteria in each bottle minimized the lag in uptake by up to several days. No lag was observed during incubations of soils with added IMB-1. Stable isotope fractionation factors were similar for degradation by live soil and live soil with added IMB-1. Heat-killed controls of cell cultures showed little uptake (<10% over 5 days) and no isotope fractionation. Heat-killed soil controls, by contrast, demonstrated significant loss of MeBr (20-30%) with isotope fractionation factors comparable to live soil. Loss of MeCl during the same time was lower (<10%) however isotope fractionation was comparable to live soil. Our results indicate that bacterial oxidation in soil rapidly consumes methyl halides but only partly controls the fractionation of carbon isotopes. Two chemical processes also act to remove MeBr in soil, hydrolysis and nucleophilic exchange with Cl-, both of which result in fractionation of carbon isotopes. Hydrolysis does not remove MeCl. It seems likely that fractionation in soil could result from a combination of biological and chemical processes, but since they all have sizeable fractionation factors associated with the removal of methyl halides, the relative rate of each process may not be as important as the total amount of methyl halide degraded. Attempts to constrain our understanding of atmospheric methyl halide budgets using stable isotope signatures of sources and sinks will have to rely on this type of information regarding the net isotopic impact of methyl halide uptake by soils. Miller, L.G., Kalin, R.M., McCauley, S.E., Hamilton, J.T.G., Harper, D.B., Millet, D.B., Oremland, R.S., and Goldstein, A.H. (2001) Large carbon isotope fractionation associated with oxidation of methyl halides by methylotrophic bacteria, PNAS, vol. 98, 5833-5837.

Colloidal thallium halide nanocrystals with reasonable luminescence, carrier mobility and diffusion length† †Electronic supplementary information (ESI) available: Synthesis and additional characterization of nanocrystals, characterization of nanocrystal films, temperature-dependent phase transition, coefficient of volume expansion, PL decay dynamics, tabulated best fit parameters, and methodology analysis of ultrafast optical pump THz probe (OPTP) spectroscopy. See DOI: 10.1039/c7sc01219e Click here for additional data file.

PubMed Central

Mir, Wasim J.; Warankar, Avinash; Acharya, Ashutosh; Das, Shyamashis

2017-01-01

Colloidal lead halide based perovskite nanocrystals (NCs) have been recently established as an interesting class of defect-tolerant NCs with potential for superior optoelectronic applications. The electronic band structure of thallium halides (TlX, where X = Br and I) show a strong resemblance to lead halide perovskites, where both Pb2+ and Tl+ exhibit a 6s2 inert pair of electrons and strong spin–orbit coupling. Although the crystal structure of TlX is not perovskite, the similarities of its electronic structure with lead halide perovskites motivated us to prepare colloidal TlX NCs. These TlX NCs exhibit a wide bandgap (>2.5 eV or <500 nm) and the potential to exhibit a reduced density of deep defect states. Optical pump terahertz (THz) probe spectroscopy with excitation fluence in the range of 0.85–5.86 × 1013 photons per cm2 on NC films shows that the TlBr NCs possess high effective carrier mobility (∼220 to 329 cm2 V–1 s–1), long diffusion length (∼0.77 to 0.98 μm), and reasonably high photoluminescence efficiency (∼10%). This combination of properties is remarkable compared to other wide-bandgap (>2.5 eV) semiconductor NCs, which suggests a reduction in the deep-defect states in the TlX NCs. Furthermore, the ultrafast carrier dynamics and temperature-dependent reversible structural phase transition together with its influence on the optical properties of the TlX NCs are studied. PMID:28970882

Characterization of silver halide fiber optics and hollow silica waveguides for use in the construction of a mid-infrared attenuated total reflection fourier transform infrared (ATR FT-IR) spectroscopy probe.

PubMed

Damin, Craig A; Sommer, André J

2013-11-01

Advances in fiber optic materials have allowed for the construction of fibers and waveguides capable of transmitting infrared radiation. An investigation of the transmission characteristics associated with two commonly used types of infrared-transmitting fibers/waveguides for prospective use in a fiber/waveguide-coupled attenuated total internal reflection (ATR) probe was performed. Characterization of silver halide polycrystalline fiber optics and hollow silica waveguides was done on the basis of the transmission of infrared light using a conventional fiber optic coupling accessory and an infrared microscope. Using the fiber optic coupling accessory, the average percent transmission for three silver halide fibers was 18.1 ± 6.1% relative to a benchtop reflection accessory. The average transmission for two hollow waveguides (HWGs) using the coupling accessory was 8.0 ± 0.3%. (Uncertainties in the relative percent transmission represent the standard deviations.) Reduced transmission observed for the HWGs was attributed to the high numerical aperture of the coupling accessory. Characterization of the fibers/waveguides using a zinc selenide lens objective on an infrared microscope indicated 24.1 ± 7.2% of the initial light input into the silver halide fibers was transmitted. Percent transmission obtained for the HWGs was 98.7 ± 0.1%. Increased transmission using the HWGs resulted from the absence or minimization of insertion and scattering losses due to the hollow air core and a better-matched numerical aperture. The effect of bending on the transmission characteristics of the fibers/waveguides was also investigated. Significant deviations in the transmission of infrared light by the solid-core silver halide fibers were observed for various bending angles. Percent transmission greater than 98% was consistently observed for the HWGs at the bending angles. The combined benefits of high percent transmission, reproducible instrument responses, and increased bending tolerance indicated HWGs should be preferred in the construction of a fiber/waveguide-coupled ATR probe.

Structural, dynamical, and transport properties of the hydrated halides: How do At{sup −} bulk properties compare with those of the other halides, from F{sup −} to I{sup −}?

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

Réal, Florent, E-mail: florent.real@univ-lille1.fr; Severo Pereira Gomes, André; Guerrero Martínez, Yansel Omar

2016-03-28

The properties of halides from the lightest, fluoride (F{sup −}), to the heaviest, astatide (At{sup −}), have been studied in water using a polarizable force-field approach based on molecular dynamics (MD) simulations at the 10 ns scale. The selected force-field explicitly treats the cooperativity within the halide-water hydrogen bond networks. The force-field parameters have been adjusted to ab initio data on anion/water clusters computed at the relativistic Möller-Plesset second-order perturbation theory level of theory. The anion static polarizabilities of the two heaviest halides, I{sup −} and At{sup −}, were computed in the gas phase using large and diffuse atomic basis sets,more » and taking into account both electron correlation and spin-orbit coupling within a four-component framework. Our MD simulation results show the solvation properties of I{sup −} and At{sup −} in aqueous phase to be very close. For instance, their first hydration shells are structured and encompass 9.2 and 9.1 water molecules at about 3.70 ± 0.05 Å, respectively. These values have to be compared to the F{sup −}, Cl{sup −}, and Br{sup −} ones, i.e., 6.3, 8.4, and 9.0 water molecules at 2.74, 3.38, and 3.55 Å, respectively. Moreover our computations predict the solvation free energy of At{sup −} in liquid water at ambient conditions to be 68 kcal mol{sup −1}, a value also close the I{sup −} one, about 70 kcal mol{sup −1}. In all, our simulation results for I{sup −} are in excellent agreement with the latest neutron- and X-ray diffraction studies. Those for the At{sup −} ion are predictive, as no theoretical or experimental data are available to date.« less

Spectral and dynamical properties of single excitons, biexcitons, and trions in cesium-lead-halide perovskite quantum dots

DOE PAGES

Makarov, Nikolay Sergeevich; Guo, Shaojun; Isaienko, Oleksandr; ...

2016-02-16

Organic–inorganic lead-halide perovskites have been the subject of recent intense interest due to their unusually strong photovoltaic performance. A new addition to the perovskite family is all-inorganic Cs–Pb-halide perovskite nanocrystals, or quantum dots, fabricated via a moderate-temperature colloidal synthesis. While being only recently introduced to the research community, these nanomaterials have already shown promise for a range of applications from color-converting phosphors and light-emitting diodes to lasers, and even room-temperature single-photon sources. Knowledge of the optical properties of perovskite quantum dots still remains vastly incomplete. Here we apply various time-resolved spectroscopic techniques to conduct a comprehensive study of spectral andmore » dynamical characteristics of single- and multiexciton states in CsPbX3 nanocrystals with X being either Br, I, or their mixture. Specifically, we measure exciton radiative lifetimes, absorption cross-sections, and derive the degeneracies of the band-edge electron and hole states. We also characterize the rates of intraband cooling and nonradiative Auger recombination and evaluate the strength of exciton–exciton coupling. The overall conclusion of this work is that spectroscopic properties of Cs–Pb-halide quantum dots are largely similar to those of quantum dots of more traditional semiconductors such as CdSe and PbSe. At the same time, we observe some distinctions including, for example, an appreciable effect of the halide identity on radiative lifetimes, considerably shorter biexciton Auger lifetimes, and apparent deviation of their size dependence from the “universal volume scaling” previously observed for many traditional nanocrystal systems. The high efficiency of Auger decay in perovskite quantum dots is detrimental to their prospective applications in light-emitting devices and lasers. Furthermore, this points toward the need for the development of approaches for effective suppression of Auger recombination in these nanomaterials, using perhaps insights gained from previous studies of II–VI nanocrystals.« less

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.

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

Ding, Shunmin; Tian, Chengcheng; Zhu, Xiang

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.

A Critical Evaluation of Studies Employing Alkenyl Halide ’Mechanistic Probe’ as Indicators of Single Electron Transfer Processes.

DTIC Science & Technology

1987-07-07

College Station, TX 77843 Pittsburgh, PA 15260 Introduction: Chemical reactions come about through the reorganization of valence electrons. The notion...Contmnue on reverie of necessary and odentify 0)’ Wooc ,7umor r) Recently it has been suggested that many reaction traditionally classed in polar terms may...evaluates the utility of these alkenyl halide probes as mechanistic probes for SET. Reactions which interfere with the standard analysis ~ include the

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.

Minimizing the amount of nitromethane in palladium-catalyzed cross-coupling with aryl halides.

PubMed

Walvoord, Ryan R; Kozlowski, Marisa C

2013-09-06

A method for the formation of arylnitromethanes is described that employs readily available aryl halides or triflates and small amounts of nitromethane in a dioxane solvent, thereby reducing the hazards associated with this reagent. Specifically, 2-10 equiv (1-5% v/v) of nitromethane can be employed in comparison to prior work that used nitromethane as solvent (185 equiv). The present transformation provides high yields at relatively low temperatures and tolerates an array of functionality, including heterocycles and substantial steric encumbrance.

Double-chamber electrode for spectrochemical determination of chlorine and other halogens

USGS Publications Warehouse

de Paiva, Azevedo; Specht, A.W.; Harner, R.S.

1954-01-01

A double-chamber, graphite electrode, suitable for d.c. arc determination of halogens by means of the alkaline earth halide bands, is described. An upper chamber holds the alkaline earth compound and an interconnected, lower chamber holds the halogen compound. This arrangement assures that there will be an abundance of alkaline earths in the arc by the time the halogen is volatilized from the lower chamber, and thereby promotes maximum emission of the alkaline earth halide bands. ?? 1954.

Aqueous electrolytes for redox flow battery systems

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

Liu, Tianbiao; Li, Bin; Wei, Xiaoliang

An aqueous redox flow battery system includes an aqueous catholyte and an aqueous anolyte. The aqueous catholyte may comprise (i) an optionally substituted thiourea or a nitroxyl radical compound and (ii) a catholyte aqueous supporting solution. The aqueous anolyte may comprise (i) metal cations or a viologen compound and (ii) an anolyte aqueous supporting solution. The catholyte aqueous supporting solution and the anolyte aqueous supporting solution independently may comprise (i) a proton source, (ii) a halide source, or (iii) a proton source and a halide source.